# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 loop_ _publ_author_name _publ_author_address 'Suresh K Bhargava' ; Research School of Chemistry, Australian National University, Canberra, A. C. T. 0200, Australia ; 'Martin A Bennett' ; Department of Applied Chemistry, RMIT University, GPO Box 2476V, Melbourne, Victoria, 3001, Australia ; 'Nedaossadat Mirzadeh' ; Department of Applied Chemistry, RMIT University, GPO Box 2476V, Melbourne, Victoria, 3001, Australia ; 'Steven Priver' ; Department of Applied Chemistry, RMIT University, GPO Box 2476V, Melbourne, Victoria, 3001, Australia ; 'Jorg Wagler' ; Research School of Chemistry Institute of Advanced Studies Australian National University, Canberra, A. C. T. 0200, Australia and Institut f\"ur Anorganische Chemie Technische Universit\"at Bergakademie Freiberg Leipziger Str. 29 09596 Freiberg Bundesrepublik Deutschland ; ; A.C.Willis ; ; Research School of Chemistry, Australian National University, Canberra, A. C. T. 0200, Australia ; _publ_contact_author_name 'Suresh K Bhargava' _publ_contact_author_email SURESH.BHARGAVA@RMIT.EDU.AU _publ_section_title ; Synthesis and interconversions of digold(I), tetragold(I), digold(II), gold(I)-gold(III) and digold(III) complexes of fluorine-substituted aryl carbanions. ; _journal_coden_ASTM ? _journal_coeditor_code ? _journal_coeditor_name ? _journal_coeditor_notes ; ? ; _journal_date_accepted ? _journal_date_from_coeditor ? _journal_date_printers_final ? _journal_date_printers_first ? _journal_date_proofs_in ? _journal_date_proofs_out ? # #============================================================================= # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? _journal_techeditor_code ? _journal_techeditor_notes ; ? ; _journal_volume ? _journal_year ? # Number 2 (monoclinic) in the manuscript # 1. SUBMISSION DETAILS _publ_contact_author ;Wagler, J\"org Institut f\"ur Anorganische Chemie Technische Universit\"at Bergakademie Freiberg Leipziger Str. 29 09596 Freiberg Bundesrepublik Deutschland and Willis, Anthony C. Research School of Chemistry, Australian National University, Canberra, A. C. T. 0200, Australia ; _publ_contact_author_fax 'JW: +49 3731 39-4058, ACW: 61 2 6125 0750' _publ_contact_author_phone 'JW: +49 3731 39-3556, ACW: 61 2 6125 4109' # Attachment 'ben0508_preraemod.cif.txt' data_ben0508_prerae _database_code_depnum_ccdc_archive 'CCDC 725984' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_date 06-02-08 _audit_creation_method CRYSTALS_ver_12.18 _audit_update_record ; 2006-02-09 - Preliminary Report on C36 H20 Au2 F8 P2 by Anthony C. Willis for Neda Mirzadeh and Martin Bennett 2006-02-09 - passes checkcif tests with minor warnings ; _oxford_structure_analysis_title '2061717 ben0508' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 12.7411(5) _cell_length_b 12.9877(6) _cell_length_c 19.6902(8) _cell_angle_alpha 90 _cell_angle_beta 99.839(2) _cell_angle_gamma 90 _cell_volume 3210.4(2) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1 ' _symmetry_space_group_name_Hall -P2yn loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x+1/2,y+1/2,-z+1/2 x+1/2,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Au -2.0133 8.8022 16.8819 0.4611 18.5913 8.6216 25.5582 1.4826 5.8600 36.3956 12.0658 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0171 0.0103 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' P 0.1023 0.0942 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C36 H20 Au2 F8 P2 # Dc = 2.19 Fooo = 1996.02 Mu = 93.02 M = 1060.42 # Found Formula = C36 H20 Au2.04 F8 P2 # Dc = 2.21 FOOO = 1996.02 Mu = 94.75 M = 1067.91 _chemical_formula_sum 'C36 H20 Au2.04 F8 P2' _chemical_formula_moiety 'C36 H20 Au2 F8 P2, 2(Au0.02) ' _chemical_compound_source ' from RMIT University ' _chemical_formula_weight 1067.91 _cell_measurement_reflns_used 335063 _cell_measurement_theta_min 3 _cell_measurement_theta_max 27 _cell_measurement_temperature 200 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_min 0.22 _exptl_crystal_size_mid 0.31 _exptl_crystal_size_max 0.34 _exptl_crystal_density_diffrn 2.209 _exptl_crystal_density_meas 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 1996.019 _exptl_absorpt_coefficient_mu 9.475 # Sheldrick geometric approximatio 0.02 0.02 # Absorption correction _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.071 # 0.092 _exptl_absorpt_correction_T_max 0.124 # 0.160 _exptl_absorpt_process_details ; from symmetry-related measurements Sortav (Blessing, 1995 & 1997) ; # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method ' \f and \w scans with CCD ' _diffrn_special_details ; CCD data collecting conditions- phi and omega scans of width 0.5deg at rate 30 sec/frame, crystal-detector distance 40mm, multiple scan sets so over 95 percent of data collected with 4-fold redundancy or more. ; # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius BV, 1997)' _computing_data_reduction 'Denzo/Scalepack (Otwinowski & Minor, 1996)' _computing_cell_refinement 'Denzo/Scalepack ' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'CRYSTALS (Watkin et al 2003)' _computing_publication_material 'CRYSTALS ' _computing_molecular_graphics ; ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) ; _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 200 _diffrn_reflns_number 38605 _reflns_number_total 7378 _diffrn_reflns_av_R_equivalents 0.077 # Number of reflections with Friedels Law is 7378 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 7510 _diffrn_reflns_theta_min 2.621 _diffrn_reflns_theta_max 27.5 _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 25.189 _diffrn_measured_fraction_theta_full 0.994 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _reflns_limit_h_min -16 _reflns_limit_h_max 16 _reflns_limit_k_min 0 _reflns_limit_k_max 16 _reflns_limit_l_min 0 _reflns_limit_l_max 25 _oxford_diffrn_Wilson_B_factor 2.39 _oxford_diffrn_Wilson_scale 24.85 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -2.92 _refine_diff_density_max 1.50 _refine_ls_number_reflns 4549 _refine_ls_number_restraints 12 _refine_ls_number_parameters 441 #_refine_ls_R_factor_ref 0.0429 _refine_ls_wR_factor_ref 0.0458 _refine_ls_goodness_of_fit_ref 1.0752 #_reflns_number_all 7358 _refine_ls_R_factor_all 0.0686 _refine_ls_wR_factor_all 0.0529 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.0\s(I) _reflns_number_gt 4549 _refine_ls_R_factor_gt 0.0429 _refine_ls_wR_factor_gt 0.0458 _refine_ls_shift/su_max 0.001198 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 10.6 -6.68 8.83 ; #============================================================================= # 4. TEXT _publ_section_comment ; The crystallographic asymmetric unit consists of one [AuP(C~6~F~4~)(C~6~H~5~)~2~]~2~ molecule. Refinement of this molecule by routine procedures alone yields an R-factor of 0.048 for unit weights. A subsequent difference electon density map shows two outstanding peaks which have no chemical significance but have coordinates related to those of the Au atoms by the relationship (1-x, 1.65-y, 1.5-z) or (x, y+0.3, z), depending on how they are paired up. It would appear that stacking faults or pseudo-symmetry are leading to the creation of a ghost of the molecule, with only the Au atoms being apparent. A more sophisticated refinement might be required. To test how much improvement could be expected to occur, the extra peaks have been included as Au atoms with low occupancies which were refined. The final occupancies were each 0.019(1) and the R-factor 0.044 for unit weights. The largest features in the final difference electron density map are close to the Au atoms. ; _refine_special_details ; The crystallographic asymmetric unit consists of one [AuP(C~6~F~4~)(C~6~H~5~)~2~]~2~ molecule. Refinement of this molecule by routine procedures alone yields an R-factor of 0.048 for unit weights. A subsequent difference electon density map shows two outstanding peaks which have no chemical significance but have coordinates related to those of the Au atoms by the relationship (1-x, 1.65-y, 1.5-z) or (x, y+0.3, z), depending on how they are paired up. It would appear that stacking faults or pseudo-symmetry are leading to the creation of a ghost of the molecule, with only the Au atoms being apparent. A more sophisticated refinement might be required. To test how much improvement could be expected to occur, the extra peaks have been included as Au atoms with low occupancies which were refined. The final occupancies were each 0.019(1) and the R-factor 0.044 for unit weights. The largest features in the final difference electron density map are close to the Au atoms. ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions #Captions to figures ; ? ; _publ_section_exptl_refinement # see also _refine_ls_hydrogen for refinement keywords. ; Hydrogen atoms were included at idealized positions and ride on the atom to which they are attached. ; _publ_section_exptl_prep ; The compound was prepared by NM and recrystallized from dichloromethane/hexane. ; #**************************************************************************** # Insert your own references if required - in alphabetical order _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (2000). maXus Computer Program for the Solution and Refinement of Crystal Structures. Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Blessing, R. H.; Acta Crystallogr., Section A, 51, 33-37 (1995). Blessing, R. H.; J. Appl. Crystallogr., 30, 421-426 (1997). Coppens, P. (1970). The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis. Crystallographic Computing. F. R. Ahmed, S. R. Hall and C. P. Huber, eds., Munksgaard. Copenhagen. pp 255-270. Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius BV, COLLECT Software, 1997-2001) Otwinowski, Z. & Minor, W. (1996), Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods Enzymol. 276, 1997, 307-326. Ed Carter, C.W. & Sweet, R.M., Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994), Acta Cryst, A50, 411-437 Molecular Structure Corporation. (1992-1997). teXsan. Single Crystal Structure Analysis Software. Version 1.8. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Johnson, C.K. (1976) ORTEP-II, A Fortran Thermal-Ellipsoid Plot Program, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Au1 Au 0.523818(18) 0.67449(2) 0.826284(13) 0.0342 1.0000 Uani . . . . . . Au2 Au 0.472159(19) 0.67421(2) 0.681189(13) 0.0351 1.0000 Uani . . . . . . Au91 Au 0.4774(10) 0.9799(13) 0.6758(6) 0.0340 0.0191(8) Uiso . . P . . . Au92 Au 0.5291(11) 0.9777(14) 0.8204(6) 0.0340 0.0189(8) Uiso . . P . . . P1 P 0.67392(14) 0.76198(15) 0.81311(10) 0.0356 1.0000 Uani . . . . . . P2 P 0.32214(14) 0.58521(16) 0.69398(10) 0.0363 1.0000 Uani . . . . . . F113 F 0.5492(4) 0.7542(5) 0.5480(2) 0.0654 1.0000 Uani . . . . . . F114 F 0.7078(5) 0.8778(5) 0.5265(3) 0.0721 1.0000 Uani . . . . . . F115 F 0.8546(4) 0.9460(4) 0.6330(3) 0.0554 1.0000 Uani . . . . . . F116 F 0.8416(4) 0.8903(4) 0.7616(2) 0.0555 1.0000 Uani . . . . . . F213 F 0.4562(4) 0.5853(4) 0.9581(2) 0.0504 1.0000 Uani . . . . . . F214 F 0.3050(4) 0.4511(4) 0.9805(2) 0.0509 1.0000 Uani . . . . . . F215 F 0.1526(4) 0.3903(4) 0.8757(3) 0.0569 1.0000 Uani . . . . . . F216 F 0.1512(4) 0.4613(4) 0.7480(2) 0.0567 1.0000 Uani . . . . . . C111 C 0.6816(6) 0.7955(6) 0.7245(4) 0.0379 1.0000 Uani . . . . . . C112 C 0.6042(6) 0.7593(5) 0.6693(4) 0.0358 1.0000 Uani . . . . . . C113 C 0.6181(6) 0.7871(7) 0.6033(4) 0.0437 1.0000 Uani . . . . . . C114 C 0.7001(7) 0.8502(7) 0.5910(4) 0.0469 1.0000 Uani . . . . . . C115 C 0.7732(6) 0.8847(6) 0.6442(4) 0.0452 1.0000 Uani . . . . . . C116 C 0.7650(6) 0.8569(6) 0.7095(4) 0.0397 1.0000 Uani . . . . . . C121 C 0.6875(6) 0.8822(7) 0.8616(4) 0.0433 1.0000 Uani . U . . . . C122 C 0.5944(7) 0.9384(7) 0.8594(5) 0.0536 1.0000 Uani . U . . . . C123 C 0.5972(9) 1.0328(8) 0.8915(5) 0.0662 1.0000 Uani . U . . . . C124 C 0.6927(10) 1.0729(8) 0.9262(6) 0.0730 1.0000 Uani . . . . . . C125 C 0.7843(9) 1.0165(9) 0.9293(5) 0.0704 1.0000 Uani . . . . . . C126 C 0.7827(7) 0.9225(8) 0.8969(4) 0.0523 1.0000 Uani . . . . . . C131 C 0.7923(6) 0.6836(6) 0.8426(4) 0.0387 1.0000 Uani . . . . . . C132 C 0.8215(6) 0.6668(6) 0.9127(4) 0.0439 1.0000 Uani . . . . . . C133 C 0.9075(7) 0.6014(7) 0.9356(5) 0.0527 1.0000 Uani . . . . . . C134 C 0.9599(7) 0.5533(7) 0.8901(5) 0.0558 1.0000 Uani . . . . . . C135 C 0.9304(7) 0.5680(7) 0.8203(5) 0.0536 1.0000 Uani . . . . . . C136 C 0.8455(6) 0.6347(7) 0.7959(4) 0.0432 1.0000 Uani . . . . . . C211 C 0.3130(5) 0.5540(6) 0.7837(4) 0.0370 1.0000 Uani . . . . . . C212 C 0.3932(5) 0.5877(6) 0.8383(4) 0.0346 1.0000 Uani . . . . . . C213 C 0.3858(6) 0.5526(6) 0.9036(4) 0.0400 1.0000 Uani . . . . . . C214 C 0.3077(6) 0.4872(6) 0.9174(4) 0.0399 1.0000 Uani . . . . . . C215 C 0.2296(6) 0.4548(6) 0.8634(4) 0.0413 1.0000 Uani . . . . . . C216 C 0.2325(6) 0.4916(6) 0.7984(4) 0.0400 1.0000 Uani . . . . . . C221 C 0.3174(6) 0.4602(6) 0.6528(4) 0.0370 1.0000 Uani . . . . . . C222 C 0.4127(7) 0.4102(6) 0.6561(4) 0.0467 1.0000 Uani . . . . . . C223 C 0.4158(8) 0.3094(7) 0.6309(5) 0.0633 1.0000 Uani . . . . . . C224 C 0.3246(8) 0.2599(7) 0.6031(5) 0.0565 1.0000 Uani . . . . . . C225 C 0.2283(8) 0.3106(7) 0.5974(4) 0.0515 1.0000 Uani . . . . . . C226 C 0.2237(6) 0.4107(7) 0.6210(4) 0.0464 1.0000 Uani . . . . . . C231 C 0.2025(6) 0.6564(6) 0.6573(4) 0.0408 1.0000 Uani . . . . . . C232 C 0.1784(7) 0.6661(7) 0.5857(4) 0.0468 1.0000 Uani . . . . . . C233 C 0.0953(7) 0.7281(7) 0.5559(4) 0.0498 1.0000 Uani . . . . . . C234 C 0.0370(6) 0.7824(6) 0.5970(5) 0.0474 1.0000 Uani . . . . . . C235 C 0.0601(7) 0.7731(7) 0.6667(5) 0.0533 1.0000 Uani . . . . . . C236 C 0.1442(7) 0.7100(7) 0.6984(4) 0.0464 1.0000 Uani . . . . . . H1221 H 0.5253 0.9102 0.8347 0.0643 1.0000 Uiso R . . . . . H1231 H 0.5299 1.0731 0.8897 0.0792 1.0000 Uiso R . . . . . H1241 H 0.6945 1.1421 0.9486 0.0894 1.0000 Uiso R . . . . . H1251 H 0.8528 1.0438 0.9554 0.0837 1.0000 Uiso R . . . . . H1261 H 0.8504 0.8828 0.8986 0.0618 1.0000 Uiso R . . . . . H1321 H 0.7818 0.7006 0.9463 0.0520 1.0000 Uiso R . . . . . H1331 H 0.9307 0.5900 0.9862 0.0616 1.0000 Uiso R . . . . . H1341 H 1.0210 0.5066 0.9076 0.0665 1.0000 Uiso R . . . . . H1351 H 0.9689 0.5315 0.7872 0.0645 1.0000 Uiso R . . . . . H1361 H 0.8236 0.6468 0.7453 0.0511 1.0000 Uiso R . . . . . H2221 H 0.4804 0.4458 0.6765 0.0552 1.0000 Uiso R . . . . . H2231 H 0.4859 0.2736 0.6335 0.0774 1.0000 Uiso R . . . . . H2241 H 0.3273 0.1871 0.5868 0.0677 1.0000 Uiso R . . . . . H2251 H 0.1612 0.2747 0.5760 0.0611 1.0000 Uiso R . . . . . H2261 H 0.1539 0.4477 0.6154 0.0541 1.0000 Uiso R . . . . . H2321 H 0.2215 0.6279 0.5559 0.0556 1.0000 Uiso R . . . . . H2331 H 0.0772 0.7337 0.5046 0.0593 1.0000 Uiso R . . . . . H2341 H -0.0222 0.8286 0.5754 0.0551 1.0000 Uiso R . . . . . H2351 H 0.0167 0.8118 0.6959 0.0639 1.0000 Uiso R . . . . . H2361 H 0.1612 0.7041 0.7497 0.0554 1.0000 Uiso R . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02580(16) 0.03334(19) 0.04195(16) -0.00006(11) 0.00121(12) -0.00193(11) Au2 0.02741(17) 0.0335(2) 0.04254(16) -0.00015(12) 0.00069(12) -0.00245(11) P1 0.0258(8) 0.0351(10) 0.0446(9) -0.0016(8) 0.0025(7) -0.0016(8) P2 0.0245(8) 0.0367(10) 0.0458(10) -0.0024(8) 0.0004(7) -0.0009(8) F113 0.073(4) 0.074(4) 0.043(2) -0.001(2) -0.006(2) -0.025(3) F114 0.096(4) 0.075(4) 0.047(3) 0.002(3) 0.017(3) -0.035(3) F115 0.048(3) 0.048(3) 0.073(3) 0.000(2) 0.020(2) -0.015(2) F116 0.037(2) 0.074(4) 0.052(3) 0.001(2) 0.000(2) -0.021(2) F213 0.051(3) 0.056(3) 0.040(2) 0.000(2) -0.002(2) -0.010(2) F214 0.060(3) 0.046(3) 0.050(2) 0.006(2) 0.017(2) -0.003(2) F215 0.051(3) 0.052(3) 0.073(3) -0.006(2) 0.027(2) -0.019(2) F216 0.038(3) 0.068(4) 0.062(3) -0.007(3) 0.002(2) -0.019(2) C111 0.028(3) 0.034(4) 0.049(4) 0.001(3) 0.000(3) 0.000(3) C112 0.035(4) 0.022(3) 0.051(4) 0.003(3) 0.009(3) -0.003(3) C113 0.039(4) 0.044(5) 0.046(4) 0.000(3) 0.003(3) -0.011(4) C114 0.050(5) 0.051(5) 0.040(4) 0.004(3) 0.008(3) -0.007(4) C115 0.039(4) 0.036(5) 0.062(5) 0.003(4) 0.010(4) -0.004(3) C116 0.027(3) 0.036(4) 0.054(4) -0.008(3) 0.002(3) -0.003(3) C121 0.036(4) 0.045(5) 0.049(4) 0.006(3) 0.009(3) -0.005(3) C122 0.051(5) 0.042(5) 0.068(5) -0.006(4) 0.010(4) 0.005(4) C123 0.069(6) 0.052(6) 0.078(6) -0.015(5) 0.011(5) 0.016(5) C124 0.095(9) 0.047(6) 0.081(7) -0.018(5) 0.027(6) -0.004(6) C125 0.067(7) 0.064(7) 0.079(6) -0.015(6) 0.006(5) -0.026(6) C126 0.044(5) 0.058(6) 0.053(4) -0.010(4) 0.002(4) -0.013(4) C131 0.032(4) 0.032(4) 0.050(4) 0.003(3) 0.001(3) 0.000(3) C132 0.038(4) 0.042(5) 0.051(4) 0.008(4) 0.003(3) 0.000(4) C133 0.052(5) 0.043(5) 0.059(5) 0.015(4) -0.002(4) 0.001(4) C134 0.043(5) 0.038(5) 0.085(6) 0.016(4) 0.007(4) 0.005(4) C135 0.041(4) 0.040(5) 0.079(6) 0.000(4) 0.012(4) 0.012(4) C136 0.041(4) 0.036(4) 0.050(4) -0.001(3) 0.002(3) 0.009(4) C211 0.025(3) 0.030(4) 0.054(4) -0.004(3) 0.003(3) 0.001(3) C212 0.029(3) 0.028(4) 0.046(4) 0.000(3) 0.004(3) -0.003(3) C213 0.034(4) 0.034(4) 0.049(4) -0.004(3) 0.001(3) -0.002(3) C214 0.037(4) 0.035(4) 0.048(4) 0.000(3) 0.010(3) 0.004(3) C215 0.036(4) 0.031(4) 0.060(4) -0.007(3) 0.016(3) -0.004(3) C216 0.025(3) 0.045(5) 0.049(4) -0.006(3) 0.004(3) -0.003(3) C221 0.032(4) 0.038(4) 0.041(3) -0.003(3) 0.005(3) -0.002(3) C222 0.044(4) 0.037(4) 0.057(4) 0.000(3) 0.003(4) 0.004(4) C223 0.062(6) 0.047(6) 0.085(6) -0.008(5) 0.023(5) 0.019(5) C224 0.074(6) 0.033(5) 0.063(5) -0.002(4) 0.010(5) -0.003(4) C225 0.063(6) 0.039(5) 0.050(4) -0.004(4) 0.004(4) -0.011(4) C226 0.032(4) 0.044(5) 0.059(5) -0.003(4) -0.003(3) -0.009(4) C231 0.032(4) 0.028(4) 0.060(4) 0.003(3) 0.001(3) -0.005(3) C232 0.043(4) 0.048(5) 0.048(4) -0.001(4) 0.004(3) -0.001(4) C233 0.045(5) 0.049(5) 0.055(4) 0.008(4) 0.006(4) 0.003(4) C234 0.034(4) 0.035(4) 0.069(5) 0.009(4) -0.004(4) 0.001(3) C235 0.048(5) 0.044(5) 0.067(5) 0.001(4) 0.009(4) 0.005(4) C236 0.041(4) 0.041(5) 0.056(5) 0.000(4) 0.006(4) 0.010(4) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.6291(12) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Au1 . Au2 . 2.8201(4) yes Au1 . P1 . 2.2772(19) yes Au1 . C212 . 2.057(7) yes Au2 . P2 . 2.2842(19) yes Au2 . C112 . 2.059(7) yes Au91 . Au92 . 2.811(18) no P1 . C111 . 1.817(8) yes P1 . C121 . 1.823(9) yes P1 . C131 . 1.831(8) yes P2 . C211 . 1.836(8) yes P2 . C221 . 1.811(8) yes P2 . C231 . 1.823(8) yes F113 . C113 . 1.346(9) yes F114 . C114 . 1.340(9) yes F115 . C115 . 1.355(9) yes F116 . C116 . 1.361(8) yes F213 . C213 . 1.343(8) yes F214 . C214 . 1.334(8) yes F215 . C215 . 1.343(8) yes F216 . C216 . 1.365(8) yes C111 . C112 . 1.417(10) yes C111 . C116 . 1.400(10) yes C112 . C113 . 1.388(10) yes C113 . C114 . 1.381(11) yes C114 . C115 . 1.354(12) yes C115 . C116 . 1.356(11) yes C121 . C122 . 1.387(12) yes C121 . C126 . 1.392(11) yes C122 . C123 . 1.377(13) yes C122 . H1221 . 1.000 no C123 . C124 . 1.391(15) yes C123 . H1231 . 1.000 no C124 . C125 . 1.370(16) yes C124 . H1241 . 1.000 no C125 . C126 . 1.376(14) yes C125 . H1251 . 1.000 no C126 . H1261 . 1.000 no C131 . C132 . 1.384(11) yes C131 . C136 . 1.386(11) yes C132 . C133 . 1.399(12) yes C132 . H1321 . 1.000 no C133 . C134 . 1.359(13) yes C133 . H1331 . 1.000 no C134 . C135 . 1.374(13) yes C134 . H1341 . 1.000 no C135 . C136 . 1.405(11) yes C135 . H1351 . 1.000 no C136 . H1361 . 1.000 no C211 . C212 . 1.419(10) yes C211 . C216 . 1.376(10) yes C212 . C213 . 1.383(10) yes C213 . C214 . 1.370(10) yes C214 . C215 . 1.391(11) yes C215 . C216 . 1.374(11) yes C221 . C222 . 1.368(11) yes C221 . C226 . 1.406(10) yes C222 . C223 . 1.404(12) yes C222 . H2221 . 1.000 no C223 . C224 . 1.359(14) yes C223 . H2231 . 1.000 no C224 . C225 . 1.380(13) yes C224 . H2241 . 1.000 no C225 . C226 . 1.386(12) yes C225 . H2251 . 1.000 no C226 . H2261 . 1.000 no C231 . C232 . 1.395(11) yes C231 . C236 . 1.378(11) yes C232 . C233 . 1.379(12) yes C232 . H2321 . 1.000 no C233 . C234 . 1.381(12) yes C233 . H2331 . 1.000 no C234 . C235 . 1.359(12) yes C234 . H2341 . 1.000 no C235 . C236 . 1.407(12) yes C235 . H2351 . 1.000 no C236 . H2361 . 1.000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag Au2 . Au1 . P1 . 86.58(5) yes Au2 . Au1 . C212 . 93.6(2) yes P1 . Au1 . C212 . 176.7(2) yes Au1 . Au2 . P2 . 86.78(5) yes Au1 . Au2 . C112 . 93.5(2) yes P2 . Au2 . C112 . 177.9(2) yes Au1 . P1 . C111 . 114.4(2) yes Au1 . P1 . C121 . 112.0(2) yes C111 . P1 . C121 . 106.4(4) yes Au1 . P1 . C131 . 110.4(3) yes C111 . P1 . C131 . 105.2(3) yes C121 . P1 . C131 . 108.1(4) yes Au2 . P2 . C211 . 114.2(2) yes Au2 . P2 . C221 . 111.6(2) yes C211 . P2 . C221 . 103.3(3) yes Au2 . P2 . C231 . 111.0(2) yes C211 . P2 . C231 . 107.9(3) yes C221 . P2 . C231 . 108.4(3) yes P1 . C111 . C112 . 120.8(5) yes P1 . C111 . C116 . 120.4(6) yes C112 . C111 . C116 . 118.8(7) yes C111 . C112 . Au2 . 124.4(5) yes C111 . C112 . C113 . 116.6(6) yes Au2 . C112 . C113 . 118.9(5) yes C112 . C113 . F113 . 120.3(7) yes C112 . C113 . C114 . 122.6(7) yes F113 . C113 . C114 . 117.1(7) yes C113 . C114 . F114 . 120.3(7) yes C113 . C114 . C115 . 120.1(7) yes F114 . C114 . C115 . 119.5(8) yes F115 . C115 . C114 . 120.8(7) yes F115 . C115 . C116 . 119.8(7) yes C114 . C115 . C116 . 119.4(7) yes F116 . C116 . C111 . 119.7(7) yes F116 . C116 . C115 . 117.9(7) yes C111 . C116 . C115 . 122.4(7) yes P1 . C121 . C122 . 115.5(6) yes P1 . C121 . C126 . 125.4(7) yes C122 . C121 . C126 . 119.0(9) yes C121 . C122 . C123 . 120.0(9) yes C121 . C122 . H1221 . 120.0 no C123 . C122 . H1221 . 120.0 no C122 . C123 . C124 . 120.7(10) yes C122 . C123 . H1231 . 119.7 no C124 . C123 . H1231 . 119.6 no C123 . C124 . C125 . 119.3(10) yes C123 . C124 . H1241 . 120.4 no C125 . C124 . H1241 . 120.3 no C124 . C125 . C126 . 120.6(10) yes C124 . C125 . H1251 . 119.7 no C126 . C125 . H1251 . 119.7 no C121 . C126 . C125 . 120.5(9) yes C121 . C126 . H1261 . 119.8 no C125 . C126 . H1261 . 119.8 no P1 . C131 . C132 . 118.1(6) yes P1 . C131 . C136 . 120.9(6) yes C132 . C131 . C136 . 120.8(7) yes C131 . C132 . C133 . 118.6(8) yes C131 . C132 . H1321 . 120.7 no C133 . C132 . H1321 . 120.7 no C132 . C133 . C134 . 120.9(8) yes C132 . C133 . H1331 . 119.6 no C134 . C133 . H1331 . 119.6 no C133 . C134 . C135 . 121.0(8) yes C133 . C134 . H1341 . 119.5 no C135 . C134 . H1341 . 119.5 no C134 . C135 . C136 . 119.4(8) yes C134 . C135 . H1351 . 120.3 no C136 . C135 . H1351 . 120.3 no C135 . C136 . C131 . 119.3(8) yes C135 . C136 . H1361 . 120.3 no C131 . C136 . H1361 . 120.3 no P2 . C211 . C212 . 120.3(5) yes P2 . C211 . C216 . 120.2(6) yes C212 . C211 . C216 . 119.3(7) yes C211 . C212 . Au1 . 125.0(5) yes C211 . C212 . C213 . 116.6(6) yes Au1 . C212 . C213 . 118.2(5) yes F213 . C213 . C212 . 119.7(6) yes F213 . C213 . C214 . 116.6(7) yes C212 . C213 . C214 . 123.7(7) yes F214 . C214 . C213 . 122.5(7) yes F214 . C214 . C215 . 118.4(7) yes C213 . C214 . C215 . 119.1(7) yes C214 . C215 . F215 . 120.0(7) yes C214 . C215 . C216 . 118.5(7) yes F215 . C215 . C216 . 121.5(7) yes F216 . C216 . C211 . 121.2(7) yes F216 . C216 . C215 . 116.1(6) yes C211 . C216 . C215 . 122.7(7) yes P2 . C221 . C222 . 116.3(6) yes P2 . C221 . C226 . 124.8(6) yes C222 . C221 . C226 . 118.9(7) yes C221 . C222 . C223 . 120.3(8) yes C221 . C222 . H2221 . 119.9 no C223 . C222 . H2221 . 119.9 no C222 . C223 . C224 . 120.7(9) yes C222 . C223 . H2231 . 119.7 no C224 . C223 . H2231 . 119.7 no C223 . C224 . C225 . 119.7(9) yes C223 . C224 . H2241 . 120.2 no C225 . C224 . H2241 . 120.2 no C224 . C225 . C226 . 120.5(9) yes C224 . C225 . H2251 . 119.7 no C226 . C225 . H2251 . 119.8 no C221 . C226 . C225 . 119.9(8) yes C221 . C226 . H2261 . 120.1 no C225 . C226 . H2261 . 120.1 no P2 . C231 . C232 . 118.1(6) yes P2 . C231 . C236 . 121.4(6) yes C232 . C231 . C236 . 120.0(8) yes C231 . C232 . C233 . 120.2(8) yes C231 . C232 . H2321 . 119.9 no C233 . C232 . H2321 . 119.9 no C232 . C233 . C234 . 120.0(8) yes C232 . C233 . H2331 . 120.0 no C234 . C233 . H2331 . 120.0 no C233 . C234 . C235 . 120.0(8) yes C233 . C234 . H2341 . 120.0 no C235 . C234 . H2341 . 120.0 no C234 . C235 . C236 . 121.1(8) yes C234 . C235 . H2351 . 119.4 no C236 . C235 . H2351 . 119.4 no C235 . C236 . C231 . 118.6(8) yes C235 . C236 . H2361 . 120.7 no C231 . C236 . H2361 . 120.7 no #------------------------------------------------------------------------------ loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Au1 F115 3.380(5) . 3_646 no F113 C133 3.21(1) . 4_464 no F114 F214 2.770(8) . 4_564 no F114 C224 3.09(1) . 2_666 no F114 C214 3.20(1) . 4_564 no F115 F214 3.249(7) . 4_564 no F115 C234 3.31(1) . 1_655 no F115 C235 3.43(1) . 1_655 no F213 F213 2.872(9) . 2_667 no F213 F214 3.112(7) . 2_667 no F213 C234 3.24(1) . 4_565 no F213 C233 3.40(1) . 4_565 no F213 C213 3.578(9) . 2_667 no F214 C132 3.24(1) . 2_667 no F214 C233 3.29(1) . 3_546 no F214 C133 3.47(1) . 2_667 no F214 C234 3.50(1) . 3_546 no F215 C134 3.29(1) . 1_455 no F216 C122 3.477(9) . 3_546 no C214 C234 3.36(1) . 3_546 no C214 C233 3.59(1) . 3_546 no #------------------------------------------------------------------------------ loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion _geom_torsion_publ_flag Au1 Au2 P2 C211 . . . . -3.0(3) no Au1 Au2 P2 C221 . . . . -119.7(3) no Au1 Au2 P2 C231 . . . . 119.2(3) no Au1 Au2 C112 C111 . . . . -0.0(6) no Au1 Au2 C112 C113 . . . . -177.6(6) no Au1 P1 C111 C112 . . . . -6.1(7) no Au1 P1 C111 C116 . . . . 174.5(6) no Au1 P1 C121 C122 . . . . -41.7(8) no Au1 P1 C121 C126 . . . . 141.4(7) no Au1 P1 C131 C132 . . . . -71.0(6) no Au1 P1 C131 C136 . . . . 103.2(7) no Au1 C212 C211 P2 . . . . 1.2(9) no Au1 C212 C211 C216 . . . . 176.6(6) no Au1 C212 C213 F213 . . . . 8(1) no Au1 C212 C213 C214 . . . . -174.3(6) no Au2 Au1 P1 C111 . . . . 4.5(3) no Au2 Au1 P1 C121 . . . . 125.6(3) no Au2 Au1 P1 C131 . . . . -113.9(3) no Au2 Au1 C212 C211 . . . . -2.9(6) no Au2 Au1 C212 C213 . . . . 172.1(6) no Au2 P2 C211 C212 . . . . 2.1(7) no Au2 P2 C211 C216 . . . . -173.3(5) no Au2 P2 C221 C222 . . . . 36.5(7) no Au2 P2 C221 C226 . . . . -146.3(6) no Au2 P2 C231 C232 . . . . 70.0(7) no Au2 P2 C231 C236 . . . . -102.1(7) no Au2 C112 C111 P1 . . . . 3.7(9) no Au2 C112 C111 C116 . . . . -176.9(6) no Au2 C112 C113 F113 . . . . -3(1) no Au2 C112 C113 C114 . . . . 175.2(7) no P1 Au1 Au2 P2 . . . . 179.54(7) no P1 Au1 Au2 C112 . . . . -2.5(2) no P1 C111 C112 C113 . . . . -178.6(6) no P1 C111 C116 F116 . . . . 1(1) no P1 C111 C116 C115 . . . . -179.3(6) no P1 C121 C122 C123 . . . . -176.8(8) no P1 C121 C126 C125 . . . . 177.0(7) no P1 C131 C132 C133 . . . . 175.7(6) no P1 C131 C136 C135 . . . . -174.5(6) no P2 Au2 Au1 C212 . . . . 2.9(2) no P2 C211 C212 C213 . . . . -173.9(6) no P2 C211 C216 F216 . . . . -8(1) no P2 C211 C216 C215 . . . . 171.2(6) no P2 C221 C222 C223 . . . . 174.5(7) no P2 C221 C226 C225 . . . . -173.3(6) no P2 C231 C232 C233 . . . . -173.2(7) no P2 C231 C236 C235 . . . . 172.6(7) no F113 C113 C112 C111 . . . . 178.7(7) no F113 C113 C114 F114 . . . . 1(1) no F113 C113 C114 C115 . . . . -178.9(8) no F114 C114 C113 C112 . . . . -177.6(8) no F114 C114 C115 F115 . . . . -1(1) no F114 C114 C115 C116 . . . . 179.8(8) no F115 C115 C114 C113 . . . . 179.5(8) no F115 C115 C116 F116 . . . . -2(1) no F115 C115 C116 C111 . . . . 178.7(7) no F116 C116 C111 C112 . . . . -178.4(7) no F116 C116 C115 C114 . . . . 178.0(7) no F213 C213 C212 C211 . . . . -176.9(7) no F213 C213 C214 F214 . . . . -5(1) no F213 C213 C214 C215 . . . . 176.9(7) no F214 C214 C213 C212 . . . . 177.1(7) no F214 C214 C215 F215 . . . . 1(1) no F214 C214 C215 C216 . . . . -179.8(7) no F215 C215 C214 C213 . . . . 179.7(7) no F215 C215 C216 F216 . . . . 2(1) no F215 C215 C216 C211 . . . . -177.0(7) no F216 C216 C211 C212 . . . . 177.0(7) no F216 C216 C215 C214 . . . . -176.9(7) no C111 P1 C121 C122 . . . . 84.0(7) no C111 P1 C121 C126 . . . . -93.0(8) no C111 P1 C131 C132 . . . . 165.1(6) no C111 P1 C131 C136 . . . . -20.7(8) no C111 C112 C113 C114 . . . . -3(1) no C111 C116 C115 C114 . . . . -2(1) no C112 Au2 Au1 C212 . . . . -179.2(3) no C112 C111 P1 C121 . . . . -130.3(6) no C112 C111 P1 C131 . . . . 115.2(6) no C112 C111 C116 C115 . . . . 1(1) no C112 C113 C114 C115 . . . . 2(1) no C113 C112 C111 C116 . . . . 1(1) no C113 C114 C115 C116 . . . . -0(1) no C116 C111 P1 C121 . . . . 50.4(7) no C116 C111 P1 C131 . . . . -64.2(7) no C121 P1 C131 C132 . . . . 51.8(7) no C121 P1 C131 C136 . . . . -134.0(7) no C121 C122 C123 C124 . . . . 0(2) no C121 C126 C125 C124 . . . . -1(2) no C122 C121 P1 C131 . . . . -163.6(7) no C122 C121 C126 C125 . . . . 0(1) no C122 C123 C124 C125 . . . . -1(2) no C123 C122 C121 C126 . . . . 0(1) no C123 C124 C125 C126 . . . . 2(2) no C126 C121 P1 C131 . . . . 19.5(9) no C131 C132 C133 C134 . . . . -2(1) no C131 C136 C135 C134 . . . . -1(1) no C132 C131 C136 C135 . . . . -0(1) no C132 C133 C134 C135 . . . . 0(1) no C133 C132 C131 C136 . . . . 2(1) no C133 C134 C135 C136 . . . . 1(1) no C211 P2 C221 C222 . . . . -86.7(7) no C211 P2 C221 C226 . . . . 90.6(7) no C211 P2 C231 C232 . . . . -164.2(6) no C211 P2 C231 C236 . . . . 23.7(8) no C211 C212 C213 C214 . . . . 1(1) no C211 C216 C215 C214 . . . . 4(1) no C212 C211 P2 C221 . . . . 123.5(6) no C212 C211 P2 C231 . . . . -121.8(6) no C212 C211 C216 C215 . . . . -4(1) no C212 C213 C214 C215 . . . . -1(1) no C213 C212 C211 C216 . . . . 1(1) no C213 C214 C215 C216 . . . . -1(1) no C216 C211 P2 C221 . . . . -51.9(7) no C216 C211 P2 C231 . . . . 62.8(7) no C221 P2 C231 C232 . . . . -53.0(8) no C221 P2 C231 C236 . . . . 134.9(7) no C221 C222 C223 C224 . . . . -0(1) no C221 C226 C225 C224 . . . . -2(1) no C222 C221 P2 C231 . . . . 159.1(6) no C222 C221 C226 C225 . . . . 4(1) no C222 C223 C224 C225 . . . . 2(2) no C223 C222 C221 C226 . . . . -3(1) no C223 C224 C225 C226 . . . . -1(1) no C226 C221 P2 C231 . . . . -23.7(8) no C231 C232 C233 C234 . . . . 1(1) no C231 C236 C235 C234 . . . . -1(1) no C232 C231 C236 C235 . . . . 1(1) no C232 C233 C234 C235 . . . . -1(1) no C233 C232 C231 C236 . . . . -1(1) no C233 C234 C235 C236 . . . . 1(1) no #------------------------------------------------------------------------------ #===END # Attachment 'ben0601mod.cif.txt' data_ben0601 _database_code_depnum_ccdc_archive 'CCDC 725985' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_date 06-02-24 _audit_creation_method CRYSTALS_ver_12.18 _audit_update_record ; 2006-02-24 - Report on C74.5 H45 Au4 Cl9 F16 P4 by Anthony C. Willis for Neda Mirzadeh and Martin Bennett 2006-02-27 - passes checkcif tests with minor warnings ; _oxford_structure_analysis_title '2231446 ben0601' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 17.2172(1) _cell_length_b 21.7718(2) _cell_length_c 22.8310(2) _cell_angle_alpha 90 _cell_angle_beta 111.2521(5) _cell_angle_gamma 90 _cell_volume 7976.18(11) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Au -2.0133 8.8022 16.8819 0.4611 18.5913 8.6216 25.5582 1.4826 5.8600 36.3956 12.0658 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0171 0.0103 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' P 0.1023 0.0942 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C37 H22 Au2 Cl4 F8 P2 # Dc = 2.03 Fooo = 4660.00 Mu = 77.61 M = 2432.52 # Found Formula = C37.25 H22.50 Au2 Cl4.50 F8 P2 # Dc = 2.06 FOOO = 4660.00 Mu = 77.96 M = 2474.98 _chemical_formula_sum 'C74.5 H45 Au4 Cl9 F16 P4' _chemical_formula_moiety '2(C36 H20 Au2 Cl2 F8 P2), 2.5(C H2 Cl2) ' _chemical_compound_source ' from RMIT University ' _chemical_formula_weight 2474.98 # 1237.49 _cell_measurement_reflns_used 92194 _cell_measurement_theta_min 3 _cell_measurement_theta_max 27 _cell_measurement_temperature 200 _exptl_crystal_description rod _exptl_crystal_colour yellow _exptl_crystal_size_min 0.08 _exptl_crystal_size_mid 0.09 _exptl_crystal_size_max 0.30 _exptl_crystal_density_diffrn 2.061 _exptl_crystal_density_meas 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 4660 _exptl_absorpt_coefficient_mu 7.796 # Sheldrick geometric approximatio 0.50 0.54 # Absorption correction loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1 0 0 0.150 -1 0 0 0.150 0 1 1 0.065 0 -1 -1 0.020 0 -1 1 0.001 0 1 -1 0.090 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.219 _exptl_absorpt_correction_T_max 0.562 _exptl_absorpt_process_details ; via Gaussian method (Coppens, 1970) implemented in maXus (2000) ; #_diffrn_reflns_av_R_equivalents 0.046 # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method ' \f and \w scans with CCD ' _diffrn_special_details ; CCD data collecting conditions- phi and omega scans of width 1.5deg at rate 22 sec/frame, crystal-detector distance 40mm, multiple scan sets so over 95 percent of data collected with 4-fold redundancy or more. ; # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius BV, 1997)' _computing_data_reduction 'Denzo/Scalepack (Otwinowski & Minor, 1997)' _computing_cell_refinement 'Denzo/Scalepack ' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'CRYSTALS (Watkin et al 2003)' _computing_publication_material 'CRYSTALS ' _computing_molecular_graphics ; ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) ; _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 200 _diffrn_reflns_number 148657 _reflns_number_total 18243 _diffrn_reflns_av_R_equivalents 0.086 # Number of reflections with Friedels Law is 18243 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 18286 _diffrn_reflns_theta_min 2.566 _diffrn_reflns_theta_max 27.5 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.480 _diffrn_measured_fraction_theta_full 0.999 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _reflns_limit_h_min -22 _reflns_limit_h_max 20 _reflns_limit_k_min 0 _reflns_limit_k_max 28 _reflns_limit_l_min 0 _reflns_limit_l_max 29 _oxford_diffrn_Wilson_B_factor 2.14 _oxford_diffrn_Wilson_scale 660.28 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.15 _refine_diff_density_max 1.10 _refine_ls_number_reflns 8879 _refine_ls_number_restraints 62 _refine_ls_number_parameters 992 #_refine_ls_R_factor_ref 0.0246 _refine_ls_wR_factor_ref 0.0287 _refine_ls_goodness_of_fit_ref 1.1311 #_reflns_number_all 18188 _refine_ls_R_factor_all 0.0678 _refine_ls_wR_factor_all 0.0452 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.0\s(I) _reflns_number_gt 8879 _refine_ls_R_factor_gt 0.0246 _refine_ls_wR_factor_gt 0.0287 _refine_ls_shift/su_max 0.022840 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 0.658 0.0925 0.476 ; #============================================================================= _publ_section_comment ; The crystallographic asymmetric unit consists of two [Au{P(C~6~F~4~)(C~6~H~5~)~2~}Cl]~2~ molecules and 2.5 dichloromethane molecules of solvation. Within the unit cell there is a region of ill-defined solvate molecules. One dichloromethane molecule is clearly observed; the second has one site for each of one Cl and the C, but two sites for the other Cl; and a third molecule is proposed which is close to one of the previously mentioned disordered sites so can only be occupied if that site is unoccupied. Restraints were imposed upon distances, angles and displacement parameters for these latter two dichloromethane molecules, and the relative occupancies of the disordered Cl sites were refined. The largest features in the final difference electron density map are within the disordered solvent region of the cell and close to the Au atoms. ; _refine_special_details ; The crystallographic asymmetric unit consists of two [Au{P(C~6~F~4~)(C~6~H~5~)~2~}Cl]~2~ molecules and 2.5 dichloromethane molecules of solvation. Within the unit cell there is a region of ill-defined solvate molecules. One dichloromethane molecule is clearly observed; the second has one site for each of one Cl and the C, but two sites for the other Cl; and a third molecule is proposed which is close to one of the previously mentioned disordered sites so can only be occupied if that site is unoccupied. Restraints were imposed upon distances, angles and displacement parameters for these latter two dichloromethane molecules, and the relative occupancies of the disordered Cl sites were refined. The largest features in the final difference electron density map are within the disordered solvent region of the cell and close to the Au atoms. ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions #Captions to figures ; ? ; _publ_section_exptl_refinement # see also _refine_ls_hydrogen for refinement keywords. ; Hydrogen atoms were included at idealized positions and ride on the atom to which they are attached. ; _publ_section_exptl_prep ; The compound was prepared by NM and recrystallized from dichloromethane/hexane. The sample ID is ND2. ; #**************************************************************************** # Insert your own references if required - in alphabetical order _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (2000). maXus Computer Program for the Solution and Refinement of Crystal Structures. Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Coppens, P. (1970). The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis. Crystallographic Computing. F. R. Ahmed, S. R. Hall and C. P. Huber, eds., Munksgaard. Copenhagen. pp 255-270. Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius BV, COLLECT Software, 1997-2001) Otwinowski, Z. & Minor, W. (1996), Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods Enzymol. 276, 1997, 307-326. Ed Carter, C.W. & Sweet, R.M., Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994), Acta Cryst, A50, 411-437 Molecular Structure Corporation. (1992-1997). teXsan. Single Crystal Structure Analysis Software. Version 1.8. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Johnson, C.K. (1976) ORTEP-II, A Fortran Thermal-Ellipsoid Plot Program, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Au1 Au 0.358340(15) 0.254985(12) 0.737401(12) 0.0274 1.0000 Uani . . . . . . Au2 Au 0.221694(15) 0.198109(12) 0.684968(12) 0.0268 1.0000 Uani . . . . . . Au3 Au 0.303036(15) 0.726910(13) 0.367388(12) 0.0301 1.0000 Uani . . . . . . Au4 Au 0.162850(15) 0.673638(12) 0.324564(12) 0.0268 1.0000 Uani . . . . . . Cl1 Cl 0.47466(11) 0.32115(9) 0.76339(9) 0.0401 1.0000 Uani . . . . . . Cl2 Cl 0.08713(10) 0.16418(9) 0.61938(9) 0.0383 1.0000 Uani . . . . . . Cl3 Cl 0.42483(12) 0.78798(10) 0.39415(10) 0.0485 1.0000 Uani . . . . . . Cl4 Cl 0.02909(10) 0.63085(10) 0.27356(8) 0.0392 1.0000 Uani . . . . . . Cl51 Cl 0.9461(3) 0.54506(15) 0.58167(17) 0.0989 1.0000 Uani . . . . . . Cl52 Cl 0.8099(3) 0.5057(2) 0.6187(2) 0.1306 1.0000 Uani . . . . . . Cl61 Cl 0.6767(5) 0.5697(3) 0.7141(4) 0.2024 1.0000 Uani D U . . . . Cl62 Cl 0.5917(13) 0.6501(8) 0.6156(9) 0.2502 0.519(12) Uani D U P . . . Cl63 Cl 0.5555(15) 0.5767(10) 0.6055(11) 0.2917 0.481(12) Uani D U P . . . Cl71 Cl 0.3106(10) 0.6073(6) 0.5300(8) 0.2037 0.5 Uani D U . . . . Cl72 Cl 0.3946(8) 0.5201(6) 0.4863(7) 0.1864 0.5 Uani D U . . . . P1 P 0.27848(11) 0.32911(8) 0.76310(8) 0.0288 1.0000 Uani . . . . . . P2 P 0.28162(11) 0.17276(9) 0.61120(8) 0.0286 1.0000 Uani . . . . . . P3 P 0.23210(11) 0.80238(9) 0.40093(8) 0.0296 1.0000 Uani . . . . . . P4 P 0.20480(11) 0.65485(9) 0.23976(8) 0.0284 1.0000 Uani . . . . . . F113 F 0.1158(3) 0.1323(2) 0.7601(2) 0.0459 1.0000 Uani . . . . . . F114 F 0.0475(3) 0.1773(2) 0.8381(2) 0.0534 1.0000 Uani . . . . . . F115 F 0.0700(3) 0.2962(2) 0.8757(2) 0.0523 1.0000 Uani . . . . . . F116 F 0.1666(3) 0.3702(2) 0.8353(2) 0.0469 1.0000 Uani . . . . . . F213 F 0.5329(3) 0.1903(3) 0.8142(2) 0.0573 1.0000 Uani . . . . . . F214 F 0.6188(3) 0.1024(3) 0.7815(3) 0.0713 1.0000 Uani . . . . . . F215 F 0.5579(3) 0.0499(3) 0.6672(3) 0.0694 1.0000 Uani . . . . . . F216 F 0.4089(3) 0.0834(2) 0.5838(2) 0.0512 1.0000 Uani . . . . . . F313 F 0.0751(3) 0.6074(2) 0.4145(2) 0.0475 1.0000 Uani . . . . . . F314 F 0.0101(3) 0.6577(2) 0.4925(2) 0.0517 1.0000 Uani . . . . . . F315 F 0.0349(3) 0.7773(2) 0.5251(2) 0.0463 1.0000 Uani . . . . . . F316 F 0.1323(3) 0.8471(2) 0.4825(2) 0.0442 1.0000 Uani . . . . . . F413 F 0.4775(3) 0.6522(3) 0.4259(2) 0.0614 1.0000 Uani . . . . . . F414 F 0.5491(3) 0.5706(3) 0.3740(3) 0.0676 1.0000 Uani . . . . . . F415 F 0.4691(3) 0.5284(2) 0.2565(3) 0.0607 1.0000 Uani . . . . . . F416 F 0.3139(3) 0.5665(2) 0.1903(2) 0.0517 1.0000 Uani . . . . . . C111 C 0.1941(4) 0.2885(3) 0.7765(3) 0.0291 1.0000 Uani . . . . . . C112 C 0.1801(4) 0.2286(3) 0.7542(3) 0.0324 1.0000 Uani . . . . . . C113 C 0.1307(4) 0.1919(4) 0.7765(3) 0.0353 1.0000 Uani . . . . . . C114 C 0.0947(4) 0.2148(4) 0.8176(3) 0.0364 1.0000 Uani . . . . . . C115 C 0.1074(5) 0.2747(4) 0.8366(3) 0.0387 1.0000 Uani . . . . . . C116 C 0.1563(4) 0.3119(3) 0.8162(3) 0.0333 1.0000 Uani . . . . . . C121 C 0.3362(4) 0.3656(4) 0.8365(3) 0.0351 1.0000 Uani . . . . . . C122 C 0.3768(5) 0.3272(4) 0.8875(4) 0.0476 1.0000 Uani . . . . . . C123 C 0.4200(6) 0.3524(6) 0.9469(4) 0.0607 1.0000 Uani . . . . . . C124 C 0.4227(7) 0.4153(6) 0.9538(5) 0.0706 1.0000 Uani . . . . . . C125 C 0.3833(6) 0.4535(5) 0.9042(5) 0.0602 1.0000 Uani . . . . . . C126 C 0.3398(5) 0.4290(4) 0.8445(4) 0.0456 1.0000 Uani . . . . . . C131 C 0.2376(5) 0.3864(4) 0.7024(3) 0.0360 1.0000 Uani . . . . . . C132 C 0.2931(5) 0.4213(5) 0.6856(4) 0.0545 1.0000 Uani . . . . . . C133 C 0.2654(6) 0.4639(5) 0.6373(5) 0.0661 1.0000 Uani . . . . . . C134 C 0.1815(6) 0.4701(5) 0.6048(4) 0.0563 1.0000 Uani . . . . . . C135 C 0.1251(6) 0.4354(4) 0.6209(4) 0.0513 1.0000 Uani . . . . . . C136 C 0.1521(4) 0.3926(3) 0.6698(4) 0.0363 1.0000 Uani . . . . . . C211 C 0.3894(4) 0.1547(3) 0.6561(3) 0.0293 1.0000 Uani . . . . . . C212 C 0.4226(4) 0.1837(3) 0.7152(3) 0.0336 1.0000 Uani . . . . . . C213 C 0.4992(5) 0.1652(4) 0.7554(4) 0.0402 1.0000 Uani . . . . . . C214 C 0.5447(5) 0.1207(4) 0.7404(4) 0.0448 1.0000 Uani . . . . . . C215 C 0.5139(5) 0.0942(4) 0.6825(4) 0.0425 1.0000 Uani . . . . . . C216 C 0.4367(5) 0.1113(4) 0.6407(4) 0.0388 1.0000 Uani . . . . . . C221 C 0.2378(4) 0.1071(3) 0.5624(3) 0.0292 1.0000 Uani . . . . . . C222 C 0.2342(5) 0.0521(3) 0.5916(3) 0.0350 1.0000 Uani . . . . . . C223 C 0.2038(5) -0.0005(4) 0.5569(4) 0.0391 1.0000 Uani . . . . . . C224 C 0.1759(5) 0.0026(4) 0.4921(4) 0.0435 1.0000 Uani . . . . . . C225 C 0.1794(5) 0.0568(4) 0.4628(4) 0.0466 1.0000 Uani . . . . . . C226 C 0.2102(5) 0.1098(3) 0.4970(3) 0.0367 1.0000 Uani . . . . . . C231 C 0.2742(4) 0.2384(3) 0.5606(3) 0.0284 1.0000 Uani . . . . . . C232 C 0.1970(5) 0.2657(4) 0.5340(4) 0.0471 1.0000 Uani . . . . . . C233 C 0.1877(6) 0.3156(5) 0.4944(4) 0.0593 1.0000 Uani . . . . . . C234 C 0.2556(7) 0.3386(5) 0.4841(5) 0.0705 1.0000 Uani . . . . . . C235 C 0.3326(6) 0.3115(6) 0.5106(6) 0.0854 1.0000 Uani . . . . . . C236 C 0.3423(5) 0.2608(4) 0.5496(4) 0.0549 1.0000 Uani . . . . . . C311 C 0.1523(4) 0.7634(3) 0.4215(3) 0.0294 1.0000 Uani . . . . . . C312 C 0.1354(4) 0.7036(3) 0.4015(3) 0.0297 1.0000 Uani . . . . . . C313 C 0.0887(4) 0.6677(3) 0.4275(3) 0.0311 1.0000 Uani . . . . . . C314 C 0.0563(4) 0.6927(4) 0.4694(3) 0.0358 1.0000 Uani . . . . . . C315 C 0.0685(4) 0.7526(4) 0.4859(3) 0.0322 1.0000 Uani . . . . . . C316 C 0.1181(4) 0.7881(3) 0.4634(3) 0.0326 1.0000 Uani . . . . . . C321 C 0.3000(4) 0.8376(4) 0.4725(3) 0.0345 1.0000 Uani . . . . . . C322 C 0.3396(5) 0.8001(4) 0.5241(4) 0.0476 1.0000 Uani . . . . . . C323 C 0.3908(5) 0.8248(5) 0.5797(4) 0.0580 1.0000 Uani . . . . . . C324 C 0.4050(5) 0.8873(4) 0.5860(4) 0.0482 1.0000 Uani . . . . . . C325 C 0.3688(5) 0.9253(4) 0.5345(4) 0.0469 1.0000 Uani . . . . . . C326 C 0.3159(5) 0.9008(4) 0.4771(4) 0.0391 1.0000 Uani . . . . . . C331 C 0.1871(4) 0.8619(3) 0.3441(3) 0.0326 1.0000 Uani . . . . . . C332 C 0.2350(5) 0.8839(4) 0.3106(4) 0.0404 1.0000 Uani . . . . . . C333 C 0.2062(6) 0.9335(4) 0.2694(4) 0.0522 1.0000 Uani . . . . . . C334 C 0.1332(6) 0.9609(5) 0.2634(4) 0.0597 1.0000 Uani . . . . . . C335 C 0.0852(6) 0.9402(5) 0.2969(5) 0.0639 1.0000 Uani . . . . . . C336 C 0.1116(5) 0.8888(4) 0.3367(4) 0.0488 1.0000 Uani . . . . . . C411 C 0.3118(4) 0.6301(3) 0.2748(3) 0.0330 1.0000 Uani . . . . . . C412 C 0.3544(4) 0.6546(3) 0.3344(3) 0.0290 1.0000 Uani . . . . . . C413 C 0.4343(5) 0.6326(4) 0.3663(4) 0.0425 1.0000 Uani . . . . . . C414 C 0.4720(5) 0.5903(4) 0.3410(4) 0.0454 1.0000 Uani . . . . . . C415 C 0.4308(5) 0.5682(3) 0.2815(4) 0.0391 1.0000 Uani . . . . . . C416 C 0.3523(5) 0.5887(3) 0.2490(4) 0.0364 1.0000 Uani . . . . . . C421 C 0.1433(4) 0.5968(3) 0.1858(3) 0.0321 1.0000 Uani . . . . . . C422 C 0.0887(4) 0.6130(4) 0.1263(3) 0.0379 1.0000 Uani . . . . . . C423 C 0.0395(5) 0.5684(4) 0.0879(4) 0.0503 1.0000 Uani . . . . . . C424 C 0.0446(5) 0.5089(4) 0.1078(4) 0.0491 1.0000 Uani . . . . . . C425 C 0.0976(5) 0.4928(4) 0.1662(4) 0.0443 1.0000 Uani . . . . . . C426 C 0.1481(5) 0.5373(3) 0.2061(4) 0.0378 1.0000 Uani . . . . . . C431 C 0.2021(4) 0.7242(3) 0.1950(3) 0.0309 1.0000 Uani . . . . . . C432 C 0.1379(5) 0.7652(4) 0.1864(4) 0.0442 1.0000 Uani . . . . . . C433 C 0.1346(5) 0.8184(4) 0.1519(4) 0.0476 1.0000 Uani . . . . . . C434 C 0.1942(5) 0.8307(4) 0.1262(4) 0.0456 1.0000 Uani . . . . . . C435 C 0.2583(6) 0.7889(5) 0.1362(5) 0.0600 1.0000 Uani . . . . . . C436 C 0.2636(6) 0.7360(4) 0.1708(4) 0.0509 1.0000 Uani . . . . . . C501 C 0.9154(9) 0.5202(6) 0.6438(6) 0.1010 1.0000 Uani . . . . . . C601 C 0.6601(15) 0.5930(12) 0.6403(10) 0.2593 1.0000 Uani D U . . . . C701 C 0.4050(16) 0.5895(16) 0.527(3) 0.2087 0.5 Uani D U . . . . H1221 H 0.3750 0.2817 0.8816 0.0554 1.0000 Uiso R . . . . . H1231 H 0.4483 0.3252 0.9838 0.0725 1.0000 Uiso R . . . . . H1241 H 0.4543 0.4335 0.9959 0.0907 1.0000 Uiso R . . . . . H1251 H 0.3855 0.4990 0.9107 0.0779 1.0000 Uiso R . . . . . H1261 H 0.3118 0.4568 0.8080 0.0579 1.0000 Uiso R . . . . . H1321 H 0.3544 0.4159 0.7086 0.0647 1.0000 Uiso R . . . . . H1331 H 0.3061 0.4897 0.6263 0.0828 1.0000 Uiso R . . . . . H1341 H 0.1609 0.4999 0.5692 0.0691 1.0000 Uiso R . . . . . H1351 H 0.0641 0.4410 0.5972 0.0579 1.0000 Uiso R . . . . . H1361 H 0.1112 0.3672 0.6810 0.0443 1.0000 Uiso R . . . . . H2221 H 0.2539 0.0503 0.6386 0.0415 1.0000 Uiso R . . . . . H2231 H 0.2019 -0.0402 0.5784 0.0483 1.0000 Uiso R . . . . . H2241 H 0.1531 -0.0350 0.4665 0.0504 1.0000 Uiso R . . . . . H2251 H 0.1595 0.0582 0.4159 0.0538 1.0000 Uiso R . . . . . H2261 H 0.2124 0.1492 0.4752 0.0421 1.0000 Uiso R . . . . . H2321 H 0.1483 0.2497 0.5432 0.0611 1.0000 Uiso R . . . . . H2331 H 0.1316 0.3347 0.4735 0.0702 1.0000 Uiso R . . . . . H2341 H 0.2491 0.3757 0.4569 0.0797 1.0000 Uiso R . . . . . H2351 H 0.3814 0.3282 0.5018 0.0982 1.0000 Uiso R . . . . . H2361 H 0.3980 0.2408 0.5694 0.0660 1.0000 Uiso R . . . . . H3221 H 0.3305 0.7547 0.5205 0.0557 1.0000 Uiso R . . . . . H3231 H 0.4184 0.7972 0.6164 0.0662 1.0000 Uiso R . . . . . H3241 H 0.4411 0.9051 0.6273 0.0577 1.0000 Uiso R . . . . . H3251 H 0.3804 0.9704 0.5383 0.0574 1.0000 Uiso R . . . . . H3261 H 0.2898 0.9281 0.4400 0.0467 1.0000 Uiso R . . . . . H3321 H 0.2897 0.8643 0.3160 0.0498 1.0000 Uiso R . . . . . H3331 H 0.2396 0.9487 0.2445 0.0658 1.0000 Uiso R . . . . . H3341 H 0.1134 0.9967 0.2343 0.0677 1.0000 Uiso R . . . . . H3351 H 0.0321 0.9617 0.2929 0.0778 1.0000 Uiso R . . . . . H3361 H 0.0761 0.8720 0.3592 0.0581 1.0000 Uiso R . . . . . H4221 H 0.0851 0.6566 0.1116 0.0437 1.0000 Uiso R . . . . . H4231 H -0.0003 0.5796 0.0450 0.0570 1.0000 Uiso R . . . . . H4241 H 0.0091 0.4768 0.0792 0.0570 1.0000 Uiso R . . . . . H4251 H 0.1003 0.4492 0.1806 0.0582 1.0000 Uiso R . . . . . H4261 H 0.1874 0.5258 0.2491 0.0472 1.0000 Uiso R . . . . . H4321 H 0.0943 0.7567 0.2047 0.0558 1.0000 Uiso R . . . . . H4331 H 0.0881 0.8483 0.1456 0.0577 1.0000 Uiso R . . . . . H4341 H 0.1911 0.8688 0.1010 0.0527 1.0000 Uiso R . . . . . H4351 H 0.3020 0.7972 0.1179 0.0779 1.0000 Uiso R . . . . . H4361 H 0.3110 0.7067 0.1781 0.0679 1.0000 Uiso R . . . . . H5011 H 0.9296 0.5529 0.6768 0.1086 1.0000 Uiso R . . . . . H5012 H 0.9463 0.4817 0.6621 0.1086 1.0000 Uiso R . . . . . H6011 H 0.7145 0.6069 0.6383 0.3149 0.52 Uiso R . . . . . H6012 H 0.6388 0.5572 0.6115 0.3149 0.52 Uiso R . . . . . H6013 H 0.6718 0.6378 0.6385 0.3149 0.48 Uiso R . . . . . H6014 H 0.6941 0.5689 0.6209 0.3149 0.48 Uiso R . . . . . H7011 H 0.4470 0.5850 0.571 0.2623 0.50 Uiso R . . . . . H7012 H 0.4232 0.6226 0.504 0.2623 0.50 Uiso R . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02396(12) 0.02982(15) 0.02956(13) -0.00102(11) 0.01104(10) 0.00139(10) Au2 0.02525(12) 0.02705(14) 0.03003(13) 0.00021(11) 0.01230(10) 0.00115(10) Au3 0.02505(12) 0.03684(16) 0.03001(13) -0.00451(11) 0.01191(10) -0.00384(11) Au4 0.02395(12) 0.03147(14) 0.02630(12) -0.00242(11) 0.01063(10) -0.00131(10) Cl1 0.0291(8) 0.0452(11) 0.0432(10) -0.0020(8) 0.0099(7) -0.0068(8) Cl2 0.0265(8) 0.0436(11) 0.0400(9) 0.0010(8) 0.0064(7) -0.0031(7) Cl3 0.0325(9) 0.0570(13) 0.0599(12) -0.0149(10) 0.0213(9) -0.0163(8) Cl4 0.0241(8) 0.0560(12) 0.0359(9) -0.0056(8) 0.0090(7) -0.0083(8) Cl51 0.128(3) 0.0630(19) 0.096(2) 0.0099(17) 0.029(2) 0.0265(19) Cl52 0.115(3) 0.177(4) 0.104(3) 0.036(3) 0.045(2) 0.067(3) Cl61 0.245(7) 0.134(5) 0.269(8) -0.019(5) 0.142(6) -0.005(5) Cl62 0.302(12) 0.193(10) 0.292(12) -0.004(10) 0.151(10) -0.017(10) Cl63 0.321(13) 0.205(11) 0.325(13) 0.001(11) 0.089(12) -0.021(11) Cl71 0.223(11) 0.154(9) 0.272(13) -0.068(9) 0.134(10) 0.006(8) Cl72 0.185(10) 0.141(8) 0.253(12) -0.023(8) 0.103(9) 0.045(7) P1 0.0294(9) 0.0279(9) 0.0322(9) -0.0006(7) 0.0149(7) 0.0021(7) P2 0.0289(8) 0.0297(9) 0.0293(9) -0.0005(7) 0.0131(7) 0.0014(7) P3 0.0293(9) 0.0320(9) 0.0297(9) -0.0039(8) 0.0132(7) -0.0060(7) P4 0.0274(8) 0.0331(10) 0.0266(8) -0.0008(7) 0.0122(7) 0.0012(7) F113 0.057(3) 0.029(2) 0.062(3) 0.000(2) 0.035(2) -0.008(2) F114 0.053(3) 0.058(3) 0.065(3) 0.008(2) 0.041(2) -0.006(2) F115 0.051(3) 0.067(3) 0.056(3) -0.011(2) 0.040(2) 0.002(2) F116 0.045(3) 0.046(3) 0.059(3) -0.015(2) 0.029(2) -0.001(2) F213 0.041(3) 0.070(4) 0.046(3) -0.008(2) -0.003(2) 0.015(2) F214 0.041(3) 0.078(4) 0.077(4) 0.000(3) 0.000(3) 0.033(3) F215 0.051(3) 0.067(4) 0.093(4) -0.019(3) 0.029(3) 0.024(3) F216 0.048(3) 0.063(3) 0.049(3) -0.018(2) 0.025(2) 0.004(2) F313 0.063(3) 0.038(3) 0.051(3) -0.009(2) 0.032(2) -0.016(2) F314 0.061(3) 0.060(3) 0.050(3) -0.006(2) 0.039(2) -0.023(2) F315 0.051(3) 0.060(3) 0.040(2) -0.015(2) 0.032(2) -0.009(2) F316 0.054(3) 0.037(2) 0.052(3) -0.015(2) 0.032(2) -0.005(2) F413 0.037(3) 0.088(4) 0.047(3) -0.004(3) 0.000(2) 0.007(3) F414 0.033(3) 0.083(4) 0.080(4) 0.011(3) 0.013(3) 0.025(3) F415 0.054(3) 0.055(3) 0.086(4) -0.006(3) 0.041(3) 0.015(2) F416 0.050(3) 0.061(3) 0.052(3) -0.022(2) 0.027(2) -0.002(2) C111 0.029(3) 0.032(4) 0.027(3) 0.001(3) 0.010(3) 0.003(3) C112 0.027(3) 0.037(4) 0.037(4) -0.001(3) 0.015(3) 0.006(3) C113 0.031(4) 0.040(4) 0.040(4) 0.005(3) 0.020(3) 0.005(3) C114 0.026(3) 0.048(5) 0.036(4) 0.006(3) 0.012(3) 0.005(3) C115 0.038(4) 0.048(5) 0.033(4) -0.005(3) 0.015(3) -0.001(3) C116 0.026(3) 0.034(4) 0.041(4) -0.005(3) 0.015(3) 0.001(3) C121 0.035(4) 0.039(4) 0.035(4) -0.003(3) 0.018(3) -0.006(3) C122 0.049(5) 0.050(5) 0.039(4) -0.003(4) 0.011(4) -0.003(4) C123 0.054(5) 0.092(8) 0.036(5) 0.002(5) 0.015(4) -0.023(5) C124 0.069(7) 0.113(10) 0.045(5) -0.025(6) 0.039(5) -0.047(6) C125 0.077(7) 0.055(6) 0.062(6) -0.024(5) 0.042(5) -0.025(5) C126 0.051(5) 0.050(5) 0.044(4) -0.011(4) 0.027(4) -0.013(4) C131 0.038(4) 0.036(4) 0.038(4) -0.001(3) 0.018(3) 0.006(3) C132 0.031(4) 0.064(6) 0.067(6) 0.021(5) 0.016(4) -0.001(4) C133 0.058(6) 0.066(7) 0.082(7) 0.031(6) 0.036(5) 0.006(5) C134 0.064(6) 0.055(6) 0.053(5) 0.017(4) 0.026(5) 0.012(5) C135 0.046(5) 0.050(5) 0.050(5) 0.007(4) 0.006(4) 0.011(4) C136 0.033(4) 0.033(4) 0.045(4) 0.000(3) 0.016(3) -0.001(3) C211 0.033(3) 0.027(4) 0.031(3) -0.003(3) 0.016(3) -0.001(3) C212 0.034(4) 0.030(4) 0.040(4) 0.003(3) 0.017(3) 0.006(3) C213 0.031(4) 0.051(5) 0.037(4) -0.002(4) 0.010(3) 0.006(3) C214 0.036(4) 0.048(5) 0.048(5) 0.000(4) 0.012(4) 0.011(4) C215 0.031(4) 0.037(4) 0.064(5) -0.003(4) 0.023(4) 0.008(3) C216 0.040(4) 0.047(5) 0.039(4) -0.006(3) 0.026(3) 0.007(3) C221 0.025(3) 0.028(4) 0.037(4) 0.000(3) 0.015(3) 0.000(3) C222 0.039(4) 0.033(4) 0.032(4) -0.002(3) 0.011(3) 0.001(3) C223 0.044(4) 0.032(4) 0.045(4) 0.003(3) 0.020(4) 0.000(3) C224 0.038(4) 0.034(4) 0.054(5) -0.007(4) 0.011(4) -0.002(3) C225 0.060(5) 0.045(5) 0.030(4) 0.001(3) 0.010(4) -0.005(4) C226 0.045(4) 0.031(4) 0.029(4) 0.007(3) 0.008(3) -0.006(3) C231 0.034(4) 0.026(4) 0.026(3) -0.003(3) 0.012(3) -0.001(3) C232 0.049(5) 0.049(5) 0.055(5) 0.017(4) 0.033(4) 0.007(4) C233 0.046(5) 0.070(7) 0.059(6) 0.026(5) 0.016(4) 0.014(5) C234 0.069(7) 0.054(6) 0.076(7) 0.038(5) 0.012(5) -0.006(5) C235 0.046(6) 0.103(9) 0.096(8) 0.059(7) 0.013(5) -0.021(6) C236 0.035(4) 0.064(6) 0.065(6) 0.022(5) 0.018(4) -0.006(4) C311 0.027(3) 0.037(4) 0.027(3) -0.005(3) 0.014(3) 0.001(3) C312 0.031(3) 0.033(4) 0.027(3) -0.002(3) 0.013(3) 0.004(3) C313 0.034(4) 0.036(4) 0.026(3) 0.000(3) 0.014(3) -0.006(3) C314 0.036(4) 0.049(5) 0.026(3) -0.004(3) 0.015(3) -0.012(3) C315 0.026(3) 0.043(4) 0.031(3) -0.008(3) 0.014(3) -0.004(3) C316 0.026(3) 0.040(4) 0.031(4) -0.010(3) 0.009(3) -0.008(3) C321 0.029(3) 0.043(4) 0.033(4) -0.008(3) 0.014(3) -0.005(3) C322 0.050(5) 0.050(5) 0.039(4) 0.004(4) 0.012(4) -0.010(4) C323 0.043(5) 0.086(8) 0.036(4) 0.011(5) 0.004(4) -0.003(5) C324 0.041(4) 0.054(6) 0.048(5) -0.012(4) 0.016(4) -0.013(4) C325 0.045(5) 0.042(5) 0.057(5) -0.014(4) 0.022(4) -0.008(4) C326 0.037(4) 0.044(5) 0.035(4) -0.006(3) 0.013(3) -0.009(3) C331 0.038(4) 0.032(4) 0.026(3) -0.008(3) 0.009(3) -0.009(3) C332 0.043(4) 0.043(5) 0.039(4) 0.008(3) 0.019(3) 0.000(4) C333 0.050(5) 0.062(6) 0.053(5) 0.009(4) 0.028(4) -0.003(4) C334 0.055(6) 0.073(7) 0.041(5) 0.018(5) 0.005(4) -0.005(5) C335 0.054(6) 0.081(8) 0.059(6) 0.018(5) 0.024(5) 0.013(5) C336 0.037(4) 0.063(6) 0.045(5) 0.010(4) 0.014(4) 0.001(4) C411 0.034(4) 0.037(4) 0.030(4) 0.001(3) 0.014(3) 0.002(3) C412 0.026(3) 0.035(4) 0.031(3) 0.003(3) 0.016(3) 0.000(3) C413 0.031(4) 0.059(5) 0.036(4) 0.007(4) 0.011(3) 0.000(4) C414 0.033(4) 0.046(5) 0.062(5) 0.010(4) 0.023(4) 0.012(4) C415 0.040(4) 0.033(4) 0.054(5) 0.002(3) 0.029(4) 0.011(3) C416 0.037(4) 0.033(4) 0.045(4) -0.008(3) 0.022(3) -0.001(3) C421 0.028(3) 0.034(4) 0.036(4) -0.002(3) 0.015(3) 0.002(3) C422 0.036(4) 0.045(5) 0.028(4) 0.001(3) 0.006(3) 0.004(3) C423 0.045(5) 0.055(6) 0.042(5) -0.009(4) 0.006(4) -0.003(4) C424 0.042(4) 0.056(6) 0.044(5) -0.017(4) 0.010(4) -0.013(4) C425 0.060(5) 0.030(4) 0.055(5) -0.009(4) 0.036(4) -0.006(4) C426 0.044(4) 0.035(4) 0.039(4) 0.005(3) 0.021(3) 0.004(3) C431 0.035(4) 0.035(4) 0.022(3) -0.003(3) 0.010(3) -0.002(3) C432 0.045(4) 0.036(5) 0.057(5) 0.004(4) 0.027(4) 0.003(4) C433 0.046(5) 0.039(5) 0.059(5) 0.008(4) 0.021(4) 0.005(4) C434 0.051(5) 0.037(5) 0.044(4) 0.013(4) 0.011(4) -0.012(4) C435 0.055(5) 0.073(7) 0.066(6) 0.020(5) 0.040(5) 0.003(5) C436 0.051(5) 0.054(6) 0.065(5) 0.017(4) 0.041(4) 0.010(4) C501 0.139(12) 0.067(8) 0.065(7) -0.008(6) -0.001(8) 0.043(8) C601 0.300(14) 0.190(12) 0.296(14) 0.018(12) 0.118(13) -0.019(12) C701 0.224(16) 0.167(15) 0.265(17) -0.034(15) 0.124(15) 0.021(14) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.05751(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Au1 . Au2 . 2.5416(4) yes Au1 . Cl1 . 2.3615(18) yes Au1 . P1 . 2.3290(17) yes Au1 . C212 . 2.072(7) yes Au2 . Cl2 . 2.3749(17) yes Au2 . P2 . 2.3378(17) yes Au2 . C112 . 2.067(7) yes Au3 . Au4 . 2.5330(4) yes Au3 . Cl3 . 2.3685(18) yes Au3 . P3 . 2.3358(18) yes Au3 . C412 . 2.076(7) yes Au4 . Cl4 . 2.3628(17) yes Au4 . P4 . 2.3347(17) yes Au4 . C312 . 2.082(6) yes Cl51 . C501 . 1.770(15) yes Cl52 . C501 . 1.723(16) yes Cl61 . C601 . 1.681(16) yes Cl62 . C601 . 1.665(17) yes Cl63 . C601 . 1.722(17) yes Cl71 . C701 . 1.696(18) yes Cl72 . C701 . 1.748(18) yes P1 . C111 . 1.819(7) yes P1 . C121 . 1.795(7) yes P1 . C131 . 1.806(8) yes P2 . C211 . 1.808(7) yes P2 . C221 . 1.802(7) yes P2 . C231 . 1.813(7) yes P3 . C311 . 1.817(7) yes P3 . C321 . 1.801(7) yes P3 . C331 . 1.798(8) yes P4 . C411 . 1.804(7) yes P4 . C421 . 1.815(7) yes P4 . C431 . 1.815(7) yes F113 . C113 . 1.350(9) yes F114 . C114 . 1.351(8) yes F115 . C115 . 1.359(8) yes F116 . C116 . 1.333(8) yes F213 . C213 . 1.368(9) yes F214 . C214 . 1.341(9) yes F215 . C215 . 1.347(9) yes F216 . C216 . 1.354(9) yes F313 . C313 . 1.348(8) yes F314 . C314 . 1.341(8) yes F315 . C315 . 1.341(7) yes F316 . C316 . 1.350(8) yes F413 . C413 . 1.362(9) yes F414 . C414 . 1.338(9) yes F415 . C415 . 1.336(8) yes F416 . C416 . 1.350(9) yes C111 . C112 . 1.388(10) yes C111 . C116 . 1.389(9) yes C112 . C113 . 1.391(10) yes C113 . C114 . 1.391(10) yes C114 . C115 . 1.368(11) yes C115 . C116 . 1.365(10) yes C121 . C122 . 1.397(11) yes C121 . C126 . 1.392(11) yes C122 . C123 . 1.401(12) yes C122 . H1221 . 1.000 no C123 . C124 . 1.376(16) yes C123 . H1231 . 1.000 no C124 . C125 . 1.369(15) yes C124 . H1241 . 1.000 no C125 . C126 . 1.402(12) yes C125 . H1251 . 1.000 no C126 . H1261 . 1.000 no C131 . C132 . 1.380(11) yes C131 . C136 . 1.396(10) yes C132 . C133 . 1.385(13) yes C132 . H1321 . 1.000 no C133 . C134 . 1.371(13) yes C133 . H1331 . 1.000 no C134 . C135 . 1.380(13) yes C134 . H1341 . 1.000 no C135 . C136 . 1.397(11) yes C135 . H1351 . 1.000 no C136 . H1361 . 1.000 no C211 . C212 . 1.409(10) yes C211 . C216 . 1.375(10) yes C212 . C213 . 1.368(10) yes C213 . C214 . 1.365(11) yes C214 . C215 . 1.362(11) yes C215 . C216 . 1.377(11) yes C221 . C222 . 1.383(10) yes C221 . C226 . 1.393(10) yes C222 . C223 . 1.384(11) yes C222 . H2221 . 1.000 no C223 . C224 . 1.382(11) yes C223 . H2231 . 1.000 no C224 . C225 . 1.369(12) yes C224 . H2241 . 1.000 no C225 . C226 . 1.387(11) yes C225 . H2251 . 1.000 no C226 . H2261 . 1.000 no C231 . C232 . 1.379(10) yes C231 . C236 . 1.374(10) yes C232 . C233 . 1.383(12) yes C232 . H2321 . 1.000 no C233 . C234 . 1.369(13) yes C233 . H2331 . 1.000 no C234 . C235 . 1.375(15) yes C234 . H2341 . 1.000 no C235 . C236 . 1.391(13) yes C235 . H2351 . 1.000 no C236 . H2361 . 1.000 no C311 . C312 . 1.375(10) yes C311 . C316 . 1.399(9) yes C312 . C313 . 1.398(9) yes C313 . C314 . 1.382(9) yes C314 . C315 . 1.352(11) yes C315 . C316 . 1.382(10) yes C321 . C322 . 1.393(11) yes C321 . C326 . 1.398(11) yes C322 . C323 . 1.366(12) yes C322 . H3221 . 1.000 no C323 . C324 . 1.381(13) yes C323 . H3231 . 1.000 no C324 . C325 . 1.387(12) yes C324 . H3241 . 1.000 no C325 . C326 . 1.402(11) yes C325 . H3251 . 1.000 no C326 . H3261 . 1.000 no C331 . C332 . 1.397(10) yes C331 . C336 . 1.379(11) yes C332 . C333 . 1.400(12) yes C332 . H3321 . 1.000 no C333 . C334 . 1.353(13) yes C333 . H3331 . 1.000 no C334 . C335 . 1.390(13) yes C334 . H3341 . 1.000 no C335 . C336 . 1.408(13) yes C335 . H3351 . 1.000 no C336 . H3361 . 1.000 no C411 . C412 . 1.396(10) yes C411 . C416 . 1.396(10) yes C412 . C413 . 1.388(10) yes C413 . C414 . 1.371(11) yes C414 . C415 . 1.371(12) yes C415 . C416 . 1.360(10) yes C421 . C422 . 1.388(10) yes C421 . C426 . 1.369(10) yes C422 . C423 . 1.376(11) yes C422 . H4221 . 1.000 no C423 . C424 . 1.365(13) yes C423 . H4231 . 1.000 no C424 . C425 . 1.360(12) yes C424 . H4241 . 1.000 no C425 . C426 . 1.397(11) yes C425 . H4251 . 1.000 no C426 . H4261 . 1.000 no C431 . C432 . 1.376(11) yes C431 . C436 . 1.386(10) yes C432 . C433 . 1.391(11) yes C432 . H4321 . 1.000 no C433 . C434 . 1.381(11) yes C433 . H4331 . 1.000 no C434 . C435 . 1.384(13) yes C434 . H4341 . 1.000 no C435 . C436 . 1.380(12) yes C435 . H4351 . 1.000 no C436 . H4361 . 1.000 no C501 . H5011 . 1.000 no C501 . H5012 . 1.000 no C601 . H6011 . 1.000 no C601 . H6012 . 1.000 no C601 . H6013 . 1.000 no C601 . H6014 . 1.000 no C701 . H7011 . 1.000 no C701 . H7012 . 1.000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag Au2 . Au1 . Cl1 . 166.28(5) yes Au2 . Au1 . P1 . 85.76(5) yes Cl1 . Au1 . P1 . 92.20(7) yes Au2 . Au1 . C212 . 90.3(2) yes Cl1 . Au1 . C212 . 92.2(2) yes P1 . Au1 . C212 . 175.3(2) yes Au1 . Au2 . Cl2 . 166.75(5) yes Au1 . Au2 . P2 . 83.08(4) yes Cl2 . Au2 . P2 . 93.25(6) yes Au1 . Au2 . C112 . 90.09(19) yes Cl2 . Au2 . C112 . 93.0(2) yes P2 . Au2 . C112 . 172.9(2) yes Au4 . Au3 . Cl3 . 170.86(6) yes Au4 . Au3 . P3 . 84.85(4) yes Cl3 . Au3 . P3 . 92.28(7) yes Au4 . Au3 . C412 . 89.09(18) yes Cl3 . Au3 . C412 . 93.77(19) yes P3 . Au3 . C412 . 173.93(18) yes Au3 . Au4 . Cl4 . 173.16(5) yes Au3 . Au4 . P4 . 82.09(4) yes Cl4 . Au4 . P4 . 93.52(6) yes Au3 . Au4 . C312 . 90.39(19) yes Cl4 . Au4 . C312 . 93.48(19) yes P4 . Au4 . C312 . 170.9(2) yes Au1 . P1 . C111 . 106.6(2) yes Au1 . P1 . C121 . 111.4(3) yes C111 . P1 . C121 . 105.2(3) yes Au1 . P1 . C131 . 112.7(2) yes C111 . P1 . C131 . 110.6(3) yes C121 . P1 . C131 . 110.0(4) yes Au2 . P2 . C211 . 105.8(2) yes Au2 . P2 . C221 . 116.0(2) yes C211 . P2 . C221 . 107.0(3) yes Au2 . P2 . C231 . 109.0(2) yes C211 . P2 . C231 . 110.7(3) yes C221 . P2 . C231 . 108.3(3) yes Au3 . P3 . C311 . 106.9(2) yes Au3 . P3 . C321 . 110.7(2) yes C311 . P3 . C321 . 105.5(3) yes Au3 . P3 . C331 . 114.2(2) yes C311 . P3 . C331 . 110.9(3) yes C321 . P3 . C331 . 108.4(3) yes Au4 . P4 . C411 . 104.9(2) yes Au4 . P4 . C421 . 113.9(2) yes C411 . P4 . C421 . 110.1(3) yes Au4 . P4 . C431 . 111.6(2) yes C411 . P4 . C431 . 108.2(3) yes C421 . P4 . C431 . 107.9(3) yes P1 . C111 . C112 . 116.0(5) yes P1 . C111 . C116 . 121.5(5) yes C112 . C111 . C116 . 121.5(6) yes C111 . C112 . Au2 . 121.3(5) yes C111 . C112 . C113 . 116.9(6) yes Au2 . C112 . C113 . 121.5(5) yes C112 . C113 . F113 . 122.1(6) yes C112 . C113 . C114 . 121.5(7) yes F113 . C113 . C114 . 116.5(6) yes C113 . C114 . F114 . 119.3(7) yes C113 . C114 . C115 . 119.7(7) yes F114 . C114 . C115 . 121.0(6) yes F115 . C115 . C114 . 118.5(7) yes F115 . C115 . C116 . 121.2(7) yes C114 . C115 . C116 . 120.3(7) yes C111 . C116 . F116 . 121.6(6) yes C111 . C116 . C115 . 119.9(7) yes F116 . C116 . C115 . 118.5(6) yes P1 . C121 . C122 . 117.0(6) yes P1 . C121 . C126 . 123.0(6) yes C122 . C121 . C126 . 120.0(7) yes C121 . C122 . C123 . 120.1(9) yes C121 . C122 . H1221 . 119.9 no C123 . C122 . H1221 . 119.9 no C122 . C123 . C124 . 119.0(9) yes C122 . C123 . H1231 . 120.5 no C124 . C123 . H1231 . 120.5 no C123 . C124 . C125 . 121.6(9) yes C123 . C124 . H1241 . 119.2 no C125 . C124 . H1241 . 119.2 no C124 . C125 . C126 . 120.2(9) yes C124 . C125 . H1251 . 119.9 no C126 . C125 . H1251 . 119.9 no C125 . C126 . C121 . 119.1(9) yes C125 . C126 . H1261 . 120.4 no C121 . C126 . H1261 . 120.4 no P1 . C131 . C132 . 118.5(6) yes P1 . C131 . C136 . 121.3(6) yes C132 . C131 . C136 . 120.0(7) yes C131 . C132 . C133 . 121.1(8) yes C131 . C132 . H1321 . 119.5 no C133 . C132 . H1321 . 119.5 no C132 . C133 . C134 . 119.3(9) yes C132 . C133 . H1331 . 120.4 no C134 . C133 . H1331 . 120.4 no C133 . C134 . C135 . 120.4(8) yes C133 . C134 . H1341 . 119.8 no C135 . C134 . H1341 . 119.8 no C134 . C135 . C136 . 121.0(8) yes C134 . C135 . H1351 . 119.5 no C136 . C135 . H1351 . 119.5 no C135 . C136 . C131 . 118.2(7) yes C135 . C136 . H1361 . 120.9 no C131 . C136 . H1361 . 120.9 no P2 . C211 . C212 . 115.0(5) yes P2 . C211 . C216 . 125.8(6) yes C212 . C211 . C216 . 118.7(7) yes C211 . C212 . Au1 . 120.2(5) yes C211 . C212 . C213 . 118.0(7) yes Au1 . C212 . C213 . 121.8(6) yes F213 . C213 . C212 . 120.2(7) yes F213 . C213 . C214 . 117.0(7) yes C212 . C213 . C214 . 122.8(7) yes F214 . C214 . C213 . 121.4(7) yes F214 . C214 . C215 . 119.3(7) yes C213 . C214 . C215 . 119.3(7) yes F215 . C215 . C214 . 119.8(7) yes F215 . C215 . C216 . 120.5(7) yes C214 . C215 . C216 . 119.7(7) yes F216 . C216 . C215 . 117.3(6) yes F216 . C216 . C211 . 121.2(7) yes C215 . C216 . C211 . 121.5(7) yes P2 . C221 . C222 . 118.0(5) yes P2 . C221 . C226 . 122.2(5) yes C222 . C221 . C226 . 119.8(7) yes C221 . C222 . C223 . 120.9(7) yes C221 . C222 . H2221 . 119.5 no C223 . C222 . H2221 . 119.5 no C222 . C223 . C224 . 119.0(7) yes C222 . C223 . H2231 . 120.5 no C224 . C223 . H2231 . 120.5 no C223 . C224 . C225 . 120.4(8) yes C223 . C224 . H2241 . 119.8 no C225 . C224 . H2241 . 119.8 no C224 . C225 . C226 . 121.1(7) yes C224 . C225 . H2251 . 119.4 no C226 . C225 . H2251 . 119.4 no C221 . C226 . C225 . 118.7(7) yes C221 . C226 . H2261 . 120.6 no C225 . C226 . H2261 . 120.6 no P2 . C231 . C232 . 117.1(5) yes P2 . C231 . C236 . 121.9(6) yes C232 . C231 . C236 . 121.1(7) yes C231 . C232 . C233 . 119.4(7) yes C231 . C232 . H2321 . 120.3 no C233 . C232 . H2321 . 120.3 no C232 . C233 . C234 . 119.7(8) yes C232 . C233 . H2331 . 120.2 no C234 . C233 . H2331 . 120.2 no C233 . C234 . C235 . 121.0(9) yes C233 . C234 . H2341 . 119.5 no C235 . C234 . H2341 . 119.5 no C234 . C235 . C236 . 119.6(9) yes C234 . C235 . H2351 . 120.2 no C236 . C235 . H2351 . 120.2 no C235 . C236 . C231 . 119.1(8) yes C235 . C236 . H2361 . 120.4 no C231 . C236 . H2361 . 120.4 no P3 . C311 . C312 . 116.4(5) yes P3 . C311 . C316 . 122.8(5) yes C312 . C311 . C316 . 120.1(6) yes C311 . C312 . Au4 . 119.5(5) yes C311 . C312 . C313 . 118.1(6) yes Au4 . C312 . C313 . 121.7(5) yes C312 . C313 . F313 . 122.1(6) yes C312 . C313 . C314 . 120.9(7) yes F313 . C313 . C314 . 117.0(6) yes C313 . C314 . F314 . 119.6(7) yes C313 . C314 . C315 . 120.8(6) yes F314 . C314 . C315 . 119.6(6) yes F315 . C315 . C314 . 120.8(6) yes F315 . C315 . C316 . 119.8(7) yes C314 . C315 . C316 . 119.3(6) yes C311 . C316 . F316 . 121.0(6) yes C311 . C316 . C315 . 120.6(7) yes F316 . C316 . C315 . 118.5(6) yes P3 . C321 . C322 . 118.4(6) yes P3 . C321 . C326 . 122.2(6) yes C322 . C321 . C326 . 119.4(7) yes C321 . C322 . C323 . 120.6(9) yes C321 . C322 . H3221 . 119.7 no C323 . C322 . H3221 . 119.7 no C322 . C323 . C324 . 121.0(9) yes C322 . C323 . H3231 . 119.5 no C324 . C323 . H3231 . 119.5 no C323 . C324 . C325 . 119.4(8) yes C323 . C324 . H3241 . 120.3 no C325 . C324 . H3241 . 120.3 no C324 . C325 . C326 . 120.3(8) yes C324 . C325 . H3251 . 119.8 no C326 . C325 . H3251 . 119.8 no C325 . C326 . C321 . 119.2(8) yes C325 . C326 . H3261 . 120.4 no C321 . C326 . H3261 . 120.4 no P3 . C331 . C332 . 117.2(6) yes P3 . C331 . C336 . 122.3(6) yes C332 . C331 . C336 . 120.3(7) yes C331 . C332 . C333 . 119.7(7) yes C331 . C332 . H3321 . 120.1 no C333 . C332 . H3321 . 120.1 no C332 . C333 . C334 . 119.9(8) yes C332 . C333 . H3331 . 120.0 no C334 . C333 . H3331 . 120.0 no C333 . C334 . C335 . 121.1(9) yes C333 . C334 . H3341 . 119.4 no C335 . C334 . H3341 . 119.4 no C334 . C335 . C336 . 119.7(9) yes C334 . C335 . H3351 . 120.2 no C336 . C335 . H3351 . 120.2 no C335 . C336 . C331 . 119.1(8) yes C335 . C336 . H3361 . 120.4 no C331 . C336 . H3361 . 120.4 no P4 . C411 . C412 . 114.2(5) yes P4 . C411 . C416 . 126.3(6) yes C412 . C411 . C416 . 119.5(7) yes C411 . C412 . Au3 . 120.1(5) yes C411 . C412 . C413 . 116.7(7) yes Au3 . C412 . C413 . 122.9(5) yes F413 . C413 . C412 . 119.7(7) yes F413 . C413 . C414 . 117.4(7) yes C412 . C413 . C414 . 122.8(7) yes F414 . C414 . C413 . 120.2(8) yes F414 . C414 . C415 . 119.8(7) yes C413 . C414 . C415 . 120.0(7) yes F415 . C415 . C414 . 119.6(7) yes F415 . C415 . C416 . 121.7(7) yes C414 . C415 . C416 . 118.7(7) yes C411 . C416 . F416 . 120.7(7) yes C411 . C416 . C415 . 122.1(7) yes F416 . C416 . C415 . 117.2(6) yes P4 . C421 . C422 . 120.6(6) yes P4 . C421 . C426 . 118.7(6) yes C422 . C421 . C426 . 120.7(7) yes C421 . C422 . C423 . 119.1(8) yes C421 . C422 . H4221 . 120.5 no C423 . C422 . H4221 . 120.5 no C422 . C423 . C424 . 120.5(8) yes C422 . C423 . H4231 . 119.8 no C424 . C423 . H4231 . 119.8 no C423 . C424 . C425 . 120.7(8) yes C423 . C424 . H4241 . 119.6 no C425 . C424 . H4241 . 119.6 no C424 . C425 . C426 . 119.9(8) yes C424 . C425 . H4251 . 120.0 no C426 . C425 . H4251 . 120.0 no C425 . C426 . C421 . 119.2(7) yes C425 . C426 . H4261 . 120.4 no C421 . C426 . H4261 . 120.4 no P4 . C431 . C432 . 118.3(5) yes P4 . C431 . C436 . 120.8(6) yes C432 . C431 . C436 . 120.9(7) yes C431 . C432 . C433 . 119.2(7) yes C431 . C432 . H4321 . 120.4 no C433 . C432 . H4321 . 120.4 no C432 . C433 . C434 . 121.1(8) yes C432 . C433 . H4331 . 119.4 no C434 . C433 . H4331 . 119.4 no C433 . C434 . C435 . 118.3(7) yes C433 . C434 . H4341 . 120.9 no C435 . C434 . H4341 . 120.8 no C434 . C435 . C436 . 121.8(7) yes C434 . C435 . H4351 . 119.1 no C436 . C435 . H4351 . 119.1 no C431 . C436 . C435 . 118.7(8) yes C431 . C436 . H4361 . 120.6 no C435 . C436 . H4361 . 120.6 no Cl51 . C501 . Cl52 . 112.0(7) yes Cl51 . C501 . H5011 . 108.8 no Cl52 . C501 . H5011 . 108.8 no Cl51 . C501 . H5012 . 108.8 no Cl52 . C501 . H5012 . 108.8 no H5011 . C501 . H5012 . 109.5 no Cl63 . C601 . Cl61 . 99.8(12) yes Cl61 . C601 . Cl62 . 114.1(13) yes Cl61 . C601 . H6011 . 108.4 no Cl62 . C601 . H6011 . 108.4 no Cl61 . C601 . H6012 . 108.2 no Cl62 . C601 . H6012 . 108.2 no H6011 . C601 . H6012 . 109.5 no Cl63 . C601 . H6013 . 112.0 no Cl61 . C601 . H6013 . 111.9 no Cl63 . C601 . H6014 . 111.7 no Cl61 . C601 . H6014 . 111.8 no H6013 . C601 . H6014 . 109.5 no Cl72 . C701 . Cl71 . 107.7(12) yes Cl72 . C701 . H7011 . 110.0 no Cl71 . C701 . H7011 . 110.0 no Cl72 . C701 . H7012 . 109.9 no Cl71 . C701 . H7012 . 109.9 no H7011 . C701 . H7012 . 109.5 no #------------------------------------------------------------------------------ loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Cl1 C415 3.273(9) . 2_666 no Cl1 C414 3.44(1) . 2_666 no Cl1 C323 3.491(8) . 3_646 no Cl1 F415 3.492(5) . 2_666 no Cl2 C315 3.402(7) . 2_566 no Cl2 F315 3.449(4) . 2_566 no Cl2 C316 3.507(6) . 2_566 no Cl2 C425 3.566(9) . 4 no Cl3 C215 3.48(1) . 2_666 no Cl3 C216 3.54(1) . 2_666 no Cl4 C116 3.347(6) . 2_566 no Cl4 F116 3.385(4) . 2_566 no Cl4 C115 3.434(7) . 2_566 no Cl4 F115 3.582(4) . 2_566 no Cl51 F313 3.344(5) . 2_666 no Cl51 F114 3.393(6) . 3_656 no Cl52 C601 3.38(3) . . no Cl52 F313 3.413(7) . 2_666 no Cl52 Cl72 3.51(1) . 2_666 no Cl61 F415 3.54(1) . 2_666 no Cl61 C415 3.55(1) . 2_666 no Cl62 F213 3.23(3) . 3_656 no Cl62 C701 3.38(4) . . no Cl63 C701 2.58(4) . . no Cl63 Cl72 3.30(3) . 2_666 no Cl63 Cl72 3.34(2) . . no Cl72 Cl72 3.56(3) . 2_666 no Cl72 F414 3.57(2) . 2_666 no F113 C425 3.41(1) . 4 no F113 C501 3.45(2) . 3_646 no F113 C335 3.59(1) . 2_566 no F114 C433 3.23(1) . 2_566 no F114 C432 3.28(1) . 2_566 no F114 C501 3.48(1) . 3_646 no F114 C233 3.513(9) . 4 no F115 C422 3.359(9) . 2_566 no F115 F315 3.395(8) . 3_546 no F115 C226 3.583(7) . 4 no F115 C432 3.596(9) . 2_566 no F116 C225 3.25(1) . 4 no F116 C226 3.518(8) . 4 no F213 C435 3.39(1) . 2_666 no F214 C435 3.28(1) . 2_666 no F214 C434 3.466(9) . 2_666 no F215 C125 3.05(1) . 3_646 no F215 C126 3.23(1) . 3_646 no F215 F415 3.41(1) . 4 no F216 C124 3.06(1) . 4_554 no F216 C123 3.49(1) . 4_554 no F313 C501 3.11(1) . 2_666 no F313 C135 3.37(1) . 2_566 no F314 C135 3.444(9) . 2_566 no F314 C434 3.523(8) . 4_565 no F314 C433 3.529(9) . 4_565 no F314 C233 3.57(1) . 2_566 no F315 C422 3.217(9) . 4_565 no F315 C433 3.474(9) . 4_565 no F315 C432 3.582(9) . 4_565 no F316 C224 3.46(1) . 1_565 no F413 C235 3.16(1) . 2_666 no F413 C701 3.29(6) . . no F413 C236 3.50(1) . 2_666 no F414 C133 3.38(1) . 2_666 no F414 C132 3.46(1) . 2_666 no F415 C215 3.39(1) . 4_554 no F415 C214 3.57(1) . 4_554 no F416 C223 3.279(9) . 4_554 no F416 C222 3.374(8) . 4_554 no F416 C324 3.44(1) . 4_564 no C123 C324 3.44(1) . 3_646 no C123 C323 3.57(1) . 3_646 no C124 C324 3.46(2) . 3_646 no C124 C325 3.51(2) . 3_646 no C222 C425 3.51(1) . 4 no C223 C424 3.35(1) . 4 no C223 C325 3.46(1) . 1_545 no C223 C423 3.48(1) . 4 no C223 C425 3.59(1) . 4 no C224 C326 3.38(1) . 1_545 no C224 C325 3.53(1) . 1_545 no C225 C423 3.53(1) . 3_545 no C314 C434 3.543(9) . 4_565 no #------------------------------------------------------------------------------ loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion _geom_torsion_publ_flag Au1 Au2 P2 C211 . . . . 41.7(2) no Au1 Au2 P2 C221 . . . . 160.1(2) no Au1 Au2 P2 C231 . . . . -77.4(2) no Au1 Au2 C112 C111 . . . . 41.6(5) no Au1 Au2 C112 C113 . . . . -144.2(5) no Au1 P1 C111 C112 . . . . -15.9(5) no Au1 P1 C111 C116 . . . . 152.9(4) no Au1 P1 C121 C122 . . . . -50.1(7) no Au1 P1 C121 C126 . . . . 131.8(7) no Au1 P1 C131 C132 . . . . -60.1(7) no Au1 P1 C131 C136 . . . . 115.3(7) no Au1 C212 C211 P2 . . . . -12.6(8) no Au1 C212 C211 C216 . . . . 174.4(6) no Au1 C212 C213 F213 . . . . 5(1) no Au1 C212 C213 C214 . . . . -176.3(7) no Au2 Au1 P1 C111 . . . . 33.6(2) no Au2 Au1 P1 C121 . . . . 148.0(3) no Au2 Au1 P1 C131 . . . . -87.9(3) no Au2 Au1 C212 C211 . . . . 40.6(6) no Au2 Au1 C212 C213 . . . . -142.4(7) no Au2 P2 C211 C212 . . . . -26.7(6) no Au2 P2 C211 C216 . . . . 145.7(7) no Au2 P2 C221 C222 . . . . -54.8(7) no Au2 P2 C221 C226 . . . . 127.2(6) no Au2 P2 C231 C232 . . . . -50.2(6) no Au2 P2 C231 C236 . . . . 128.9(6) no Au2 C112 C111 P1 . . . . -20.5(6) no Au2 C112 C111 C116 . . . . 170.6(4) no Au2 C112 C113 F113 . . . . 8.3(8) no Au2 C112 C113 C114 . . . . -172.4(4) no Au3 Au4 P4 C411 . . . . 45.1(2) no Au3 Au4 P4 C421 . . . . 165.6(2) no Au3 Au4 P4 C431 . . . . -71.9(2) no Au3 Au4 C312 C311 . . . . 44.4(5) no Au3 Au4 C312 C313 . . . . -145.6(5) no Au3 P3 C311 C312 . . . . -14.0(5) no Au3 P3 C311 C316 . . . . 156.3(4) no Au3 P3 C321 C322 . . . . -56.3(7) no Au3 P3 C321 C326 . . . . 121.8(7) no Au3 P3 C331 C332 . . . . -41.5(6) no Au3 P3 C331 C336 . . . . 143.7(5) no Au3 C412 C411 P4 . . . . -12.5(8) no Au3 C412 C411 C416 . . . . 169.6(6) no Au3 C412 C413 F413 . . . . 10(1) no Au3 C412 C413 C414 . . . . -171.6(7) no Au4 Au3 P3 C311 . . . . 33.7(2) no Au4 Au3 P3 C321 . . . . 148.1(3) no Au4 Au3 P3 C331 . . . . -89.2(2) no Au4 Au3 C412 C411 . . . . 42.9(6) no Au4 Au3 C412 C413 . . . . -143.8(7) no Au4 P4 C411 C412 . . . . -29.3(6) no Au4 P4 C411 C416 . . . . 148.5(6) no Au4 P4 C421 C422 . . . . 109.1(6) no Au4 P4 C421 C426 . . . . -67.2(7) no Au4 P4 C431 C432 . . . . -38.1(6) no Au4 P4 C431 C436 . . . . 141.0(5) no Au4 C312 C311 P3 . . . . -23.5(6) no Au4 C312 C311 C316 . . . . 165.9(4) no Au4 C312 C313 F313 . . . . 15.4(8) no Au4 C312 C313 C314 . . . . -166.4(4) no CL1 Au1 P1 C111 . . . . -160.0(2) no CL1 Au1 P1 C121 . . . . -45.6(3) no CL1 Au1 P1 C131 . . . . 78.5(3) no CL1 Au1 C212 C211 . . . . -125.9(6) no CL1 Au1 C212 C213 . . . . 51.0(7) no CL2 Au2 P2 C211 . . . . -151.0(2) no CL2 Au2 P2 C221 . . . . -32.7(2) no CL2 Au2 P2 C231 . . . . 89.9(2) no CL2 Au2 C112 C111 . . . . -125.5(5) no CL2 Au2 C112 C113 . . . . 48.7(5) no CL3 Au3 P3 C311 . . . . -155.0(2) no CL3 Au3 P3 C321 . . . . -40.6(3) no CL3 Au3 P3 C331 . . . . 82.1(2) no CL3 Au3 C412 C411 . . . . -128.4(6) no CL3 Au3 C412 C413 . . . . 44.9(7) no CL4 Au4 P4 C411 . . . . -140.2(2) no CL4 Au4 P4 C421 . . . . -19.7(2) no CL4 Au4 P4 C431 . . . . 102.9(2) no CL4 Au4 C312 C311 . . . . -129.9(5) no CL4 Au4 C312 C313 . . . . 40.1(5) no P1 Au1 Au2 P2 . . . . 143.05(6) no P1 Au1 Au2 C112 . . . . -35.2(2) no P1 C111 C112 C113 . . . . 165.0(4) no P1 C111 C116 F116 . . . . 14.9(8) no P1 C111 C116 C115 . . . . -164.9(5) no P1 C121 C122 C123 . . . . -177.2(8) no P1 C121 C126 C125 . . . . 177.1(8) no P1 C131 C132 C133 . . . . 176.9(8) no P1 C131 C136 C135 . . . . -176.2(7) no P2 Au2 Au1 C212 . . . . -39.5(2) no P2 C211 C212 C213 . . . . 170.4(6) no P2 C211 C216 F216 . . . . 10(1) no P2 C211 C216 C215 . . . . -169.8(7) no P2 C221 C222 C223 . . . . -177.9(7) no P2 C221 C226 C225 . . . . 178.2(7) no P2 C231 C232 C233 . . . . -179.3(7) no P2 C231 C236 C235 . . . . -179.6(8) no P3 Au3 Au4 P4 . . . . 138.47(6) no P3 Au3 Au4 C312 . . . . -36.4(2) no P3 C311 C312 C313 . . . . 166.1(4) no P3 C311 C316 F316 . . . . 11.6(8) no P3 C311 C316 C315 . . . . -168.8(5) no P3 C321 C322 C323 . . . . -179.1(8) no P3 C321 C326 C325 . . . . 179.4(7) no P3 C331 C332 C333 . . . . -174.9(6) no P3 C331 C336 C335 . . . . 172.2(6) no P4 Au4 Au3 C412 . . . . -42.0(2) no P4 C411 C412 C413 . . . . 173.9(6) no P4 C411 C416 F416 . . . . 5(1) no P4 C411 C416 C415 . . . . -173.5(6) no P4 C421 C422 C423 . . . . -176.3(7) no P4 C421 C426 C425 . . . . 176.5(7) no P4 C431 C432 C433 . . . . -179.6(6) no P4 C431 C436 C435 . . . . 179.0(6) no F113 C113 C112 C111 . . . . -177.2(5) no F113 C113 C114 F114 . . . . -0.4(8) no F113 C113 C114 C115 . . . . 179.6(5) no F114 C114 C113 C112 . . . . -179.8(5) no F114 C114 C115 F115 . . . . -1.3(9) no F114 C114 C115 C116 . . . . 179.0(5) no F115 C115 C114 C113 . . . . 178.6(5) no F115 C115 C116 F116 . . . . -0.2(9) no F115 C115 C116 C111 . . . . 179.6(5) no F116 C116 C111 C112 . . . . -176.8(5) no F116 C116 C115 C114 . . . . 179.4(5) no F213 C213 C212 C211 . . . . -177.6(7) no F213 C213 C214 F214 . . . . 0(1) no F213 C213 C214 C215 . . . . 179.9(8) no F214 C214 C213 C212 . . . . -178.2(8) no F214 C214 C215 F215 . . . . 0(1) no F214 C214 C215 C216 . . . . 178.0(9) no F215 C215 C214 C213 . . . . -179.5(9) no F215 C215 C216 F216 . . . . -2(1) no F215 C215 C216 C211 . . . . 177.6(8) no F216 C216 C211 C212 . . . . -177.9(7) no F216 C216 C215 C214 . . . . -179.8(8) no F313 C313 C312 C311 . . . . -174.4(5) no F313 C313 C314 F314 . . . . -3.3(8) no F313 C313 C314 C315 . . . . 178.7(5) no F314 C314 C313 C312 . . . . 178.4(5) no F314 C314 C315 F315 . . . . 0.0(8) no F314 C314 C315 C316 . . . . 178.2(5) no F315 C315 C314 C313 . . . . 178.0(5) no F315 C315 C316 F316 . . . . 0.9(8) no F315 C315 C316 C311 . . . . -178.7(5) no F316 C316 C311 C312 . . . . -178.5(5) no F316 C316 C315 C314 . . . . -177.3(5) no F413 C413 C412 C411 . . . . -176.6(7) no F413 C413 C414 F414 . . . . -1(1) no F413 C413 C414 C415 . . . . 178.9(8) no F414 C414 C413 C412 . . . . -179.8(8) no F414 C414 C415 F415 . . . . -2(1) no F414 C414 C415 C416 . . . . 179.7(8) no F415 C415 C414 C413 . . . . 177.9(8) no F415 C415 C416 F416 . . . . 1(1) no F415 C415 C416 C411 . . . . 179.8(7) no F416 C416 C411 C412 . . . . -176.9(7) no F416 C416 C415 C414 . . . . 179.3(8) no C111 P1 C121 C122 . . . . 65.1(7) no C111 P1 C121 C126 . . . . -113.1(8) no C111 P1 C131 C132 . . . . -179.3(7) no C111 P1 C131 C136 . . . . -3.9(8) no C111 C112 C113 C114 . . . . 2.1(8) no C111 C116 C115 C114 . . . . -0.7(9) no C112 Au2 Au1 C212 . . . . 142.3(3) no C112 C111 P1 C121 . . . . -134.4(5) no C112 C111 P1 C131 . . . . 107.0(5) no C112 C111 C116 C115 . . . . 3.3(9) no C112 C113 C114 C115 . . . . 0.3(9) no C113 C112 C111 C116 . . . . -3.9(8) no C113 C114 C115 C116 . . . . -1.0(9) no C116 C111 P1 C121 . . . . 34.5(6) no C116 C111 P1 C131 . . . . -84.2(6) no C121 P1 C131 C132 . . . . 64.8(8) no C121 P1 C131 C136 . . . . -119.8(7) no C121 C122 C123 C124 . . . . -1(2) no C121 C126 C125 C124 . . . . 1(2) no C122 C121 P1 C131 . . . . -175.8(7) no C122 C121 C126 C125 . . . . -1(1) no C122 C123 C124 C125 . . . . 1(2) no C123 C122 C121 C126 . . . . 1(1) no C123 C124 C125 C126 . . . . -1(2) no C126 C121 P1 C131 . . . . 6.1(9) no C131 C132 C133 C134 . . . . -2(2) no C131 C136 C135 C134 . . . . 1(1) no C132 C131 C136 C135 . . . . -1(1) no C132 C133 C134 C135 . . . . 2(2) no C133 C132 C131 C136 . . . . 1(1) no C133 C134 C135 C136 . . . . -1(2) no C211 P2 C221 C222 . . . . 63.0(7) no C211 P2 C221 C226 . . . . -115.0(7) no C211 P2 C231 C232 . . . . -166.3(6) no C211 P2 C231 C236 . . . . 12.9(7) no C211 C212 C213 C214 . . . . 1(1) no C211 C216 C215 C214 . . . . -0(1) no C212 C211 P2 C221 . . . . -150.9(5) no C212 C211 P2 C231 . . . . 91.2(6) no C212 C211 C216 C215 . . . . 2(1) no C212 C213 C214 C215 . . . . 1(2) no C213 C212 C211 C216 . . . . -3(1) no C213 C214 C215 C216 . . . . -2(1) no C216 C211 P2 C221 . . . . 21.5(8) no C216 C211 P2 C231 . . . . -96.3(8) no C221 P2 C231 C232 . . . . 76.7(7) no C221 P2 C231 C236 . . . . -104.1(7) no C221 C222 C223 C224 . . . . -1(1) no C221 C226 C225 C224 . . . . -0(1) no C222 C221 P2 C231 . . . . -177.6(6) no C222 C221 C226 C225 . . . . 0(1) no C222 C223 C224 C225 . . . . 1(1) no C223 C222 C221 C226 . . . . 0(1) no C223 C224 C225 C226 . . . . -0(1) no C226 C221 P2 C231 . . . . 4.4(8) no C231 C232 C233 C234 . . . . -3(1) no C231 C236 C235 C234 . . . . 0(2) no C232 C231 C236 C235 . . . . -1(1) no C232 C233 C234 C235 . . . . 2(2) no C233 C232 C231 C236 . . . . 2(1) no C233 C234 C235 C236 . . . . -1(2) no C311 P3 C321 C322 . . . . 59.0(8) no C311 P3 C321 C326 . . . . -122.9(7) no C311 P3 C331 C332 . . . . -162.2(5) no C311 P3 C331 C336 . . . . 22.9(7) no C311 C312 C313 C314 . . . . 3.7(8) no C311 C316 C315 C314 . . . . 3.1(9) no C312 C311 P3 C321 . . . . -131.8(5) no C312 C311 P3 C331 . . . . 111.0(5) no C312 C311 C316 C315 . . . . 1.2(9) no C312 C313 C314 C315 . . . . 0.5(9) no C313 C312 C311 C316 . . . . -4.5(8) no C313 C314 C315 C316 . . . . -3.9(9) no C316 C311 P3 C321 . . . . 38.5(6) no C316 C311 P3 C331 . . . . -78.7(6) no C321 P3 C331 C332 . . . . 82.4(6) no C321 P3 C331 C336 . . . . -92.5(6) no C321 C322 C323 C324 . . . . -0(2) no C321 C326 C325 C324 . . . . 0(2) no C322 C321 P3 C331 . . . . 177.8(7) no C322 C321 C326 C325 . . . . -3(1) no C322 C323 C324 C325 . . . . -2(2) no C323 C322 C321 C326 . . . . 3(1) no C323 C324 C325 C326 . . . . 2(2) no C326 C321 P3 C331 . . . . -4.2(8) no C331 C332 C333 C334 . . . . 2(1) no C331 C336 C335 C334 . . . . 3(1) no C332 C331 C336 C335 . . . . -3(1) no C332 C333 C334 C335 . . . . -1(1) no C333 C332 C331 C336 . . . . 0(1) no C333 C334 C335 C336 . . . . -2(1) no C411 P4 C421 C422 . . . . -133.4(7) no C411 P4 C421 C426 . . . . 50.4(8) no C411 P4 C431 C432 . . . . -153.1(5) no C411 P4 C431 C436 . . . . 26.1(7) no C411 C412 C413 C414 . . . . 2(1) no C411 C416 C415 C414 . . . . -2(1) no C412 C411 P4 C421 . . . . -152.2(5) no C412 C411 P4 C431 . . . . 90.0(6) no C412 C411 C416 C415 . . . . 4(1) no C412 C413 C414 C415 . . . . 0(1) no C413 C412 C411 C416 . . . . -4(1) no C413 C414 C415 C416 . . . . -1(1) no C416 C411 P4 C421 . . . . 25.5(8) no C416 C411 P4 C431 . . . . -92.2(7) no C421 P4 C431 C432 . . . . 87.8(6) no C421 P4 C431 C436 . . . . -93.0(6) no C421 C422 C423 C424 . . . . -0(1) no C421 C426 C425 C424 . . . . 0(2) no C422 C421 P4 C431 . . . . -15.5(8) no C422 C421 C426 C425 . . . . 0(1) no C422 C423 C424 C425 . . . . 1(2) no C423 C422 C421 C426 . . . . -0(1) no C423 C424 C425 C426 . . . . -1(2) no C426 C421 P4 C431 . . . . 168.3(7) no C431 C432 C433 C434 . . . . 0(1) no C431 C436 C435 C434 . . . . 1(1) no C432 C431 C436 C435 . . . . -2(1) no C432 C433 C434 C435 . . . . -1(1) no C433 C432 C431 C436 . . . . 1(1) no C433 C434 C435 C436 . . . . 0(1) no #------------------------------------------------------------------------------ # start Validation Reply Form _vrf_PLAT432_ben0601 ; PROBLEM: Short Inter X...Y Contact C701 .. Cl63 .. 2.58 Ang. RESPONSE: ... These are sites for disordered atoms and have occupancies less than 0.5. If site 1 is occupied then site 2 will not be occupied. ; # end Validation Reply Form #===END # Attachment 'ben0602mod.cif.txt' data_ben0602 _database_code_depnum_ccdc_archive 'CCDC 725986' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_date 06-02-27 _audit_creation_method CRYSTALS_ver_12.18 _audit_update_record ; 2006-02-27 - Report on C37 H22 Au2 Cl4 F8 P2 by Anthony C. Willis for Neda Mirzadeh and Martin Bennett 2006-02-27 - passes checkcif tests with minor warnings ; _oxford_structure_analysis_title '2271404 ben0602' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 10.1958(1) _cell_length_b 16.5651(2) _cell_length_c 22.7112(3) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3835.80(8) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz x,y,z x+1/2,-y+1/2,-z -x,y+1/2,-z+1/2 -x+1/2,-y,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Au -2.0133 8.8022 16.8819 0.4611 18.5913 8.6216 25.5582 1.4826 5.8600 36.3956 12.0658 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0171 0.0103 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' P 0.1023 0.0942 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C37 H22 Au2 Cl4 F8 P2 # Dc = 2.11 Fooo = 2288.00 Mu = 80.70 M = 1216.26 # Found Formula = C37 H22 Au2 Cl4 F8 P2 # Dc = 2.11 FOOO = 2288.00 Mu = 80.70 M = 1216.26 _chemical_formula_sum 'C37 H22 Au2 Cl4 F8 P2' _chemical_formula_moiety 'C36 H20 Au2 Cl2 F8 P2, C H2 Cl2' _chemical_compound_source ' from RMIT University ' _chemical_formula_weight 1216.26 _cell_measurement_reflns_used 50588 _cell_measurement_theta_min 2.6 _cell_measurement_theta_max 27.5 _cell_measurement_temperature 200 _exptl_crystal_description rod _exptl_crystal_colour colourless _exptl_crystal_size_min 0.08 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_max 0.40 _exptl_crystal_density_diffrn 2.106 _exptl_crystal_density_meas 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 2288 _exptl_absorpt_coefficient_mu 8.070 # Sheldrick geometric approximatio 0.45 0.52 # Absorption correction loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1 0 0 0.200 -1 0 0 0.200 0 -1 1 0.050 0 1 -1 0.040 0 1 1 0.060 0 -1 -1 0.040 0 0 1 0.070 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.245 _exptl_absorpt_correction_T_max 0.538 _exptl_absorpt_process_details ; via Gaussian method (Coppens, 1970) implemented in maXus (2000) ; #_diffrn_reflns_av_R_equivalents 0.033 # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method ' \f and \w scans with CCD ' _diffrn_special_details ; CCD data collecting conditions- phi and omega scans of width 1.3deg at rate 104 sec/frame, crystal-detector distance 40mm, multiple scan sets so over 95 percent of data collected with 4-fold redundancy or more. ; # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius BV, 1997)' _computing_data_reduction 'Denzo/Scalepack (Otwinowski & Minor, 1997)' _computing_cell_refinement 'Denzo/Scalepack ' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'CRYSTALS (Watkin et al 2003)' _computing_publication_material 'CRYSTALS ' _computing_molecular_graphics ; ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) ; _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 200 _diffrn_reflns_number 48101 _reflns_number_total 8801 _diffrn_reflns_av_R_equivalents 0.042 # Number of reflections with Friedels Law is 48101 # Number of reflections without Friedels Law is 8801 # Theoretical number of reflections is about 4402 _diffrn_reflns_theta_min 2.618 _diffrn_reflns_theta_max 27.5 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.491 _diffrn_measured_fraction_theta_full 0.998 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 28 _reflns_limit_h_min -13 _reflns_limit_h_max 13 _reflns_limit_k_min 0 _reflns_limit_k_max 21 _reflns_limit_l_min 0 _reflns_limit_l_max 29 _oxford_diffrn_Wilson_B_factor 2.56 _oxford_diffrn_Wilson_scale 43.08 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -2.05 _refine_diff_density_max 5.22 _refine_ls_number_reflns 7309 _refine_ls_number_restraints 28 _refine_ls_number_parameters 507 #_refine_ls_R_factor_ref 0.0261 _refine_ls_wR_factor_ref 0.0302 _refine_ls_goodness_of_fit_ref 1.1014 #_reflns_number_all 8782 _refine_ls_R_factor_all 0.0332 _refine_ls_wR_factor_all 0.0333 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.0\s(I) _reflns_number_gt 7309 _refine_ls_R_factor_gt 0.0261 _refine_ls_wR_factor_gt 0.0302 _refine_ls_shift/su_max 0.008642 _refine_ls_abs_structure_Flack -0.005(6) _refine_ls_abs_structure_details 'Flack (1983), 3891 Friedel-pairs' # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration ad _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 1.18 -0.137 0.802 ; #============================================================================= _publ_section_comment ; The crystallographic asymmetric unit consists of one [Au~2~{P(C~6~F~4~)(C~6~H~5~)~2~}~2~Cl~2~] molecule and one dichloromethane molecule of solvation. The dichloromethane molecule is disordered. There are two sites for each atom, corresponding to two images of the molecule. Restraints were imposed upon distances, angles and displacement parameters for each image, and the relative occupancies were refined. Crystals of the compound come from a racemic solution. Upon crystallisation it appears to have spontaneously resolved to give a racemic conglomerate. The absolute configuration of molecules in the crystal used to collect the X-ray diffraction data has been determined by refinement of the Flack parameter. The largest peaks in the final difference electron density map are close to the Au atoms. ; _refine_special_details ; The dichloromethane molecule is disordered. There are two sites for each atom, corresponding to two images of the molecule. Restraints were imposed upon distances, angles and displacement parameters for each image, and the relative occupancies were refined. Crystals of the compound come from a racemic solution. Upon crystallisation it appears to have spontaneously resolved to give a racemic conglomerate. The absolute configuration of molecules in the crystal used to collect the X-ray diffraction data has been determined by refinement of the Flack parameter. The largest peaks in the final difference electron density map are close to the Au atoms. ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions #Captions to figures ; ? ; _publ_section_exptl_refinement # see also _refine_ls_hydrogen for refinement keywords. ; Hydrogen atoms were included at idealized positions and ride on the atom to which they are attached. ; _publ_section_exptl_prep ; The compound was prepared by NM and recrystallized from dichloromethane/hexane. The sample ID is ND3. ; #**************************************************************************** # Insert your own references if required - in alphabetical order _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (2000). maXus Computer Program for the Solution and Refinement of Crystal Structures. Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Coppens, P. (1970). The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis. Crystallographic Computing. F. R. Ahmed, S. R. Hall and C. P. Huber, eds., Munksgaard. Copenhagen. pp 255-270. Flack, H.D. (1983) Acta Cryst., A39, 876-881. Flack, H.D. & Bernardinelli, G. (1999) Acta Cryst., A55, 908-915. Flack, H.D. & Bernardinelli, G. (2000) J. Appl. Cryst., 33, 1143-1148. Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius BV, COLLECT Software, 1997-2001) Otwinowski, Z. & Minor, W. (1996), Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods Enzymol. 276, 1997, 307-326. Ed Carter, C.W. & Sweet, R.M., Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994), Acta Cryst, A50, 411-437 Molecular Structure Corporation. (1992-1997). teXsan. Single Crystal Structure Analysis Software. Version 1.8. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Johnson, C.K. (1976) ORTEP-II, A Fortran Thermal-Ellipsoid Plot Program, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Au1 Au 0.520294(18) 0.482896(14) 0.584412(8) 0.0279 1.0000 Uani . . . . . . Au2 Au 0.61918(2) 0.479822(19) 0.713077(9) 0.0387 1.0000 Uani . . . . . . Cl1 Cl 0.42722(14) 0.35392(9) 0.59053(8) 0.0402 1.0000 Uani . . . . . . Cl2 Cl 0.83996(15) 0.47980(18) 0.69699(8) 0.0657 1.0000 Uani . . . . . . Cl51 Cl 0.0268(6) 0.8512(3) 0.5988(3) 0.0789 0.597(9) Uani D U P . . . Cl52 Cl 0.2702(6) 0.8111(4) 0.6550(4) 0.1181 0.597(9) Uani D U P . . . Cl61 Cl 0.1065(16) 0.8379(6) 0.6090(4) 0.1068 0.403(9) Uani D U P . . . Cl62 Cl 0.2369(8) 0.7851(4) 0.7177(6) 0.1134 0.403(9) Uani D U P . . . P1 P 0.70479(14) 0.45652(9) 0.52565(6) 0.0280 1.0000 Uani . . . . . . P2 P 0.40516(13) 0.48415(12) 0.73416(6) 0.0340 1.0000 Uani . . . . . . F113 F 0.5017(4) 0.6931(2) 0.61231(18) 0.0469 1.0000 Uani . . . . . . F114 F 0.6758(5) 0.8011(2) 0.5714(2) 0.0554 1.0000 Uani . . . . . . F115 F 0.8761(4) 0.7567(3) 0.5006(2) 0.0551 1.0000 Uani . . . . . . F116 F 0.9100(4) 0.5982(3) 0.47256(18) 0.0482 1.0000 Uani . . . . . . F213 F 0.3141(4) 0.5765(2) 0.52097(15) 0.0421 1.0000 Uani . . . . . . F214 F 0.0963(4) 0.6562(3) 0.5511(2) 0.0536 1.0000 Uani . . . . . . F215 F 0.0103(4) 0.6549(3) 0.6638(2) 0.0612 1.0000 Uani . . . . . . F216 F 0.1433(4) 0.5744(3) 0.74613(18) 0.0573 1.0000 Uani . . . . . . C111 C 0.7294(6) 0.5642(4) 0.5324(2) 0.0298 1.0000 Uani . . . . . . C112 C 0.6227(6) 0.5865(4) 0.5680(2) 0.0320 1.0000 Uani . . . . . . C113 C 0.6030(6) 0.6667(4) 0.5796(3) 0.0363 1.0000 Uani . . . . . . C114 C 0.6922(7) 0.7229(4) 0.5579(3) 0.0397 1.0000 Uani . . . . . . C115 C 0.7947(6) 0.6997(4) 0.5227(3) 0.0393 1.0000 Uani . . . . . . C116 C 0.8127(6) 0.6196(4) 0.5093(3) 0.0345 1.0000 Uani . . . . . . C121 C 0.6657(5) 0.4328(3) 0.4501(2) 0.0288 1.0000 Uani . . . . . . C122 C 0.5354(6) 0.4436(4) 0.4302(3) 0.0385 1.0000 Uani . . . . . . C123 C 0.5060(7) 0.4320(5) 0.3724(3) 0.0473 1.0000 Uani . . . . . . C124 C 0.6043(8) 0.4083(6) 0.3328(3) 0.0550 1.0000 Uani . . . . . . C125 C 0.7301(7) 0.3983(6) 0.3523(3) 0.0580 1.0000 Uani . . . . . . C126 C 0.7605(6) 0.4106(5) 0.4102(3) 0.0455 1.0000 Uani . . . . . . C131 C 0.8456(6) 0.3980(4) 0.5461(3) 0.0335 1.0000 Uani . . . . . . C132 C 0.8362(9) 0.3153(5) 0.5447(6) 0.0819 1.0000 Uani . . . . . . C133 C 0.9413(13) 0.2699(6) 0.5608(7) 0.1098 1.0000 Uani . . . . . . C134 C 1.0577(8) 0.3048(6) 0.5776(4) 0.0657 1.0000 Uani . . . . . . C135 C 1.0679(7) 0.3848(5) 0.5773(4) 0.0483 1.0000 Uani . . . . . . C136 C 0.9626(6) 0.4322(4) 0.5617(3) 0.0431 1.0000 Uani . . . . . . C211 C 0.3107(5) 0.5369(4) 0.6784(3) 0.0346 1.0000 Uani . . . . . . C212 C 0.3541(5) 0.5370(3) 0.6195(3) 0.0319 1.0000 Uani . . . . . . C213 C 0.2777(6) 0.5767(4) 0.5783(3) 0.0349 1.0000 Uani . . . . . . C214 C 0.1645(6) 0.6160(4) 0.5917(3) 0.0383 1.0000 Uani . . . . . . C215 C 0.1204(6) 0.6150(4) 0.6492(3) 0.0432 1.0000 Uani . . . . . . C216 C 0.1935(6) 0.5757(4) 0.6914(3) 0.0403 1.0000 Uani . . . . . . C221 C 0.3288(7) 0.3866(4) 0.7452(3) 0.0386 1.0000 Uani . . . . . . C222 C 0.4065(8) 0.3222(5) 0.7608(3) 0.0505 1.0000 Uani . . . . . . C223 C 0.3524(10) 0.2471(5) 0.7738(3) 0.0586 1.0000 Uani . . . . . . C224 C 0.2201(10) 0.2371(5) 0.7695(4) 0.0639 1.0000 Uani . . . . . . C225 C 0.1400(10) 0.2995(7) 0.7523(6) 0.0839 1.0000 Uani . . . . . . C226 C 0.1949(8) 0.3770(6) 0.7397(5) 0.0648 1.0000 Uani . . . . . . C231 C 0.3827(6) 0.5378(4) 0.8038(3) 0.0399 1.0000 Uani . . . . . . C232 C 0.3999(8) 0.6206(5) 0.8052(4) 0.0555 1.0000 Uani . . . . . . C233 C 0.3927(10) 0.6629(6) 0.8582(4) 0.0669 1.0000 Uani . . . . . . C234 C 0.3692(8) 0.6206(6) 0.9094(4) 0.0634 1.0000 Uani . . . . . . C235 C 0.3578(8) 0.5384(6) 0.9084(3) 0.0590 1.0000 Uani . . . . . . C236 C 0.3629(6) 0.4969(4) 0.8556(3) 0.0461 1.0000 Uani . . . . . . C501 C 0.1443(16) 0.8808(9) 0.6518(9) 0.0783 0.597(9) Uani D U P . . . C601 C 0.215(4) 0.8648(13) 0.6663(12) 0.1067 0.403(9) Uani D U P . . . H1221 H 0.4650 0.4596 0.4586 0.0462 1.0000 Uiso R . . . . . H1231 H 0.4142 0.4405 0.3581 0.0567 1.0000 Uiso R . . . . . H1241 H 0.5825 0.3988 0.2905 0.0661 1.0000 Uiso R . . . . . H1251 H 0.8003 0.3819 0.3240 0.0695 1.0000 Uiso R . . . . . H1261 H 0.8530 0.4033 0.4238 0.0546 1.0000 Uiso R . . . . . H1321 H 0.7527 0.2887 0.5321 0.0983 1.0000 Uiso R . . . . . H1331 H 0.9338 0.2097 0.5605 0.1318 1.0000 Uiso R . . . . . H1341 H 1.1336 0.2705 0.5898 0.0788 1.0000 Uiso R . . . . . H1351 H 1.1529 0.4108 0.5884 0.0579 1.0000 Uiso R . . . . . H1361 H 0.9718 0.4923 0.5619 0.0516 1.0000 Uiso R . . . . . H2221 H 0.5038 0.3294 0.7627 0.0607 1.0000 Uiso R . . . . . H2231 H 0.4098 0.2011 0.7862 0.0704 1.0000 Uiso R . . . . . H2241 H 0.1806 0.1834 0.7791 0.0767 1.0000 Uiso R . . . . . H2251 H 0.0433 0.2907 0.7485 0.1006 1.0000 Uiso R . . . . . H2261 H 0.1378 0.4230 0.7272 0.0778 1.0000 Uiso R . . . . . H2321 H 0.4178 0.6505 0.7678 0.0667 1.0000 Uiso R . . . . . H2331 H 0.4043 0.7228 0.8591 0.0802 1.0000 Uiso R . . . . . H2341 H 0.3604 0.6502 0.9475 0.0760 1.0000 Uiso R . . . . . H2351 H 0.3458 0.5081 0.9460 0.0707 1.0000 Uiso R . . . . . H2361 H 0.3521 0.4369 0.8552 0.0552 1.0000 Uiso R . . . . . H5011 H 0.1013 0.8845 0.6913 0.0942 0.597 Uiso R . . . . . H5012 H 0.1810 0.9347 0.6408 0.0942 0.597 Uiso R . . . . . H6011 H 0.178 0.9128 0.6874 0.1287 0.403 Uiso R . . . . . H6012 H 0.302 0.8790 0.6488 0.1287 0.403 Uiso R . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02452(8) 0.03224(9) 0.02681(8) 0.00042(9) 0.00149(7) 0.00066(9) Au2 0.02778(10) 0.05692(14) 0.03148(10) -0.00046(12) -0.00029(8) -0.00333(12) Cl1 0.0324(6) 0.0345(7) 0.0538(9) 0.0011(6) 0.0060(6) -0.0051(5) Cl2 0.0275(6) 0.1181(16) 0.0514(9) -0.0153(12) 0.0041(6) -0.0091(10) Cl51 0.093(4) 0.066(2) 0.078(3) 0.0022(19) -0.021(3) -0.019(3) Cl52 0.088(4) 0.096(4) 0.170(7) -0.041(4) -0.033(4) 0.022(3) Cl61 0.164(10) 0.086(5) 0.070(5) -0.002(4) 0.019(6) -0.030(7) Cl62 0.071(4) 0.062(4) 0.207(11) -0.014(5) -0.036(6) -0.006(3) P1 0.0226(6) 0.0327(7) 0.0287(6) -0.0001(5) 0.0005(5) -0.0001(5) P2 0.0285(6) 0.0443(7) 0.0291(6) 0.0003(7) 0.0013(5) -0.0041(7) F113 0.046(2) 0.0401(19) 0.054(2) -0.0123(17) 0.0113(18) 0.0078(17) F114 0.072(3) 0.0294(18) 0.065(3) -0.0039(18) 0.002(2) -0.0030(18) F115 0.055(2) 0.041(2) 0.069(3) 0.0132(19) 0.012(2) -0.0141(19) F116 0.040(2) 0.055(2) 0.050(2) 0.0029(18) 0.0152(17) -0.0043(17) F213 0.044(2) 0.053(2) 0.0294(17) 0.0063(16) 0.0016(15) 0.0108(16) F214 0.042(2) 0.060(3) 0.059(3) 0.011(2) -0.0054(19) 0.0148(19) F215 0.036(2) 0.078(3) 0.070(3) 0.008(2) 0.016(2) 0.021(2) F216 0.037(2) 0.094(3) 0.040(2) -0.002(2) 0.0160(17) 0.012(2) C111 0.030(3) 0.033(3) 0.027(3) -0.002(2) -0.004(2) 0.007(2) C112 0.030(3) 0.035(3) 0.031(3) 0.001(2) 0.002(2) -0.003(2) C113 0.044(3) 0.034(3) 0.031(3) -0.008(2) 0.005(3) 0.007(2) C114 0.045(3) 0.029(3) 0.046(3) -0.002(3) -0.005(3) 0.000(3) C115 0.036(3) 0.034(3) 0.048(4) 0.007(3) 0.000(3) -0.007(2) C116 0.029(3) 0.041(3) 0.033(3) 0.001(2) -0.004(2) -0.002(2) C121 0.023(2) 0.032(3) 0.032(3) -0.001(2) -0.002(2) -0.003(2) C122 0.029(3) 0.051(3) 0.035(3) -0.004(3) -0.001(2) 0.007(3) C123 0.037(3) 0.068(4) 0.038(3) -0.003(3) -0.004(3) 0.002(3) C124 0.049(4) 0.087(6) 0.030(3) -0.002(3) -0.001(3) -0.005(4) C125 0.040(4) 0.104(7) 0.030(3) -0.018(4) 0.010(3) 0.004(4) C126 0.031(3) 0.069(4) 0.037(3) -0.011(3) -0.001(3) 0.002(3) C131 0.028(3) 0.036(3) 0.036(3) 0.002(2) 0.002(2) -0.001(2) C132 0.056(5) 0.035(4) 0.154(11) 0.017(5) -0.041(6) -0.006(4) C133 0.097(8) 0.049(5) 0.184(15) 0.016(7) -0.062(9) 0.007(5) C134 0.051(4) 0.073(5) 0.073(6) 0.006(5) -0.012(4) 0.026(4) C135 0.034(3) 0.057(4) 0.054(4) 0.002(3) -0.008(3) 0.006(3) C136 0.030(3) 0.042(3) 0.057(4) 0.000(3) -0.012(3) 0.007(3) C211 0.026(2) 0.046(4) 0.032(3) 0.000(2) 0.006(2) -0.001(2) C212 0.022(2) 0.036(3) 0.038(3) 0.003(2) 0.002(2) 0.0053(19) C213 0.032(3) 0.040(3) 0.033(3) -0.005(2) -0.002(2) -0.003(2) C214 0.033(3) 0.042(3) 0.040(3) -0.002(3) -0.006(3) -0.002(2) C215 0.025(3) 0.049(4) 0.056(4) 0.001(3) 0.012(3) 0.006(3) C216 0.028(3) 0.053(4) 0.040(3) -0.003(3) 0.012(2) 0.000(3) C221 0.041(3) 0.047(4) 0.028(3) -0.003(3) 0.003(2) -0.005(3) C222 0.051(4) 0.052(4) 0.048(4) -0.002(3) -0.003(3) -0.007(3) C223 0.080(6) 0.050(4) 0.047(4) 0.001(3) 0.007(4) -0.003(4) C224 0.084(6) 0.048(4) 0.060(5) -0.008(4) 0.024(5) -0.019(4) C225 0.050(5) 0.081(7) 0.120(9) -0.008(6) 0.025(5) -0.029(5) C226 0.035(4) 0.075(6) 0.084(6) 0.000(5) 0.002(4) -0.010(4) C231 0.033(3) 0.057(4) 0.030(3) -0.002(2) 0.002(2) -0.007(3) C232 0.062(5) 0.051(4) 0.053(4) 0.000(3) -0.002(4) -0.015(4) C233 0.072(6) 0.064(5) 0.064(5) -0.022(4) -0.002(4) -0.009(4) C234 0.047(4) 0.089(6) 0.053(5) -0.023(4) -0.008(4) 0.010(4) C235 0.054(4) 0.080(6) 0.042(4) -0.007(3) -0.002(3) 0.008(4) C236 0.044(3) 0.059(5) 0.035(3) -0.005(3) 0.001(2) 0.004(3) C501 0.090(12) 0.050(8) 0.095(11) -0.017(8) -0.026(9) 0.013(7) C601 0.124(19) 0.061(12) 0.136(15) -0.030(9) -0.008(13) 0.001(14) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.22881(19) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Au1 . Au2 . 3.0916(3) yes Au1 . Cl1 . 2.3418(14) yes Au1 . P1 . 2.3474(14) yes Au1 . C112 . 2.044(6) yes Au1 . C212 . 2.076(5) yes Au2 . Cl2 . 2.2805(15) yes Au2 . P2 . 2.2351(13) yes Cl51 . C501 . 1.769(13) yes Cl52 . C501 . 1.727(13) yes Cl61 . C601 . 1.762(17) yes Cl62 . C601 . 1.777(17) yes P1 . C111 . 1.808(6) yes P1 . C121 . 1.805(6) yes P1 . C131 . 1.793(6) yes P2 . C211 . 1.815(6) yes P2 . C221 . 1.811(7) yes P2 . C231 . 1.829(6) yes F113 . C113 . 1.346(7) yes F114 . C114 . 1.342(7) yes F115 . C115 . 1.353(7) yes F116 . C116 . 1.344(7) yes F213 . C213 . 1.355(7) yes F214 . C214 . 1.333(7) yes F215 . C215 . 1.343(7) yes F216 . C216 . 1.344(7) yes C111 . C112 . 1.405(8) yes C111 . C116 . 1.356(9) yes C112 . C113 . 1.369(8) yes C113 . C114 . 1.391(9) yes C114 . C115 . 1.370(10) yes C115 . C116 . 1.375(9) yes C121 . C122 . 1.414(8) yes C121 . C126 . 1.375(8) yes C122 . C123 . 1.360(9) yes C122 . H1221 . 1.000 no C123 . C124 . 1.403(10) yes C123 . H1231 . 1.000 no C124 . C125 . 1.366(11) yes C124 . H1241 . 1.000 no C125 . C126 . 1.367(9) yes C125 . H1251 . 1.000 no C126 . H1261 . 1.000 no C131 . C132 . 1.375(10) yes C131 . C136 . 1.368(9) yes C132 . C133 . 1.360(13) yes C132 . H1321 . 1.000 no C133 . C134 . 1.373(15) yes C133 . H1331 . 1.000 no C134 . C135 . 1.330(12) yes C134 . H1341 . 1.000 no C135 . C136 . 1.377(9) yes C135 . H1351 . 1.000 no C136 . H1361 . 1.000 no C211 . C212 . 1.408(8) yes C211 . C216 . 1.389(8) yes C212 . C213 . 1.383(8) yes C213 . C214 . 1.360(9) yes C214 . C215 . 1.382(9) yes C215 . C216 . 1.378(10) yes C221 . C222 . 1.375(11) yes C221 . C226 . 1.380(10) yes C222 . C223 . 1.394(11) yes C222 . H2221 . 1.000 no C223 . C224 . 1.363(13) yes C223 . H2231 . 1.000 no C224 . C225 . 1.375(16) yes C224 . H2241 . 1.000 no C225 . C226 . 1.429(13) yes C225 . H2251 . 1.000 no C226 . H2261 . 1.000 no C231 . C232 . 1.382(10) yes C231 . C236 . 1.373(9) yes C232 . C233 . 1.395(11) yes C232 . H2321 . 1.000 no C233 . C234 . 1.377(14) yes C233 . H2331 . 1.000 no C234 . C235 . 1.366(13) yes C234 . H2341 . 1.000 no C235 . C236 . 1.383(10) yes C235 . H2351 . 1.000 no C236 . H2361 . 1.000 no C501 . H5011 . 1.000 no C501 . H5012 . 1.000 no C601 . H6011 . 1.000 no C601 . H6012 . 1.000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag Au2 . Au1 . Cl1 . 93.50(4) yes Au2 . Au1 . P1 . 105.84(4) yes Cl1 . Au1 . P1 . 100.87(5) yes Au2 . Au1 . C112 . 91.10(16) yes Cl1 . Au1 . C112 . 169.82(17) yes P1 . Au1 . C112 . 69.11(17) yes Au2 . Au1 . C212 . 84.86(16) yes Cl1 . Au1 . C212 . 92.31(16) yes P1 . Au1 . C212 . 162.31(16) yes C112 . Au1 . C212 . 97.1(2) yes Au1 . Au2 . Cl2 . 99.82(5) yes Au1 . Au2 . P2 . 83.31(4) yes Cl2 . Au2 . P2 . 176.35(7) yes Au1 . P1 . C111 . 83.1(2) yes Au1 . P1 . C121 . 113.82(18) yes C111 . P1 . C121 . 109.0(3) yes Au1 . P1 . C131 . 126.5(2) yes C111 . P1 . C131 . 113.6(3) yes C121 . P1 . C131 . 107.8(3) yes Au2 . P2 . C211 . 112.58(18) yes Au2 . P2 . C221 . 114.9(2) yes C211 . P2 . C221 . 107.3(3) yes Au2 . P2 . C231 . 108.8(2) yes C211 . P2 . C231 . 107.6(3) yes C221 . P2 . C231 . 105.1(3) yes P1 . C111 . C112 . 101.6(4) yes P1 . C111 . C116 . 136.2(5) yes C112 . C111 . C116 . 122.0(6) yes C111 . C112 . Au1 . 106.2(4) yes C111 . C112 . C113 . 118.6(5) yes Au1 . C112 . C113 . 134.9(5) yes F113 . C113 . C112 . 122.3(6) yes F113 . C113 . C114 . 118.7(5) yes C112 . C113 . C114 . 119.0(6) yes C113 . C114 . F114 . 118.9(6) yes C113 . C114 . C115 . 121.2(6) yes F114 . C114 . C115 . 119.9(6) yes F115 . C115 . C114 . 119.3(6) yes F115 . C115 . C116 . 120.6(6) yes C114 . C115 . C116 . 120.1(6) yes F116 . C116 . C115 . 119.4(5) yes F116 . C116 . C111 . 121.7(6) yes C115 . C116 . C111 . 118.9(6) yes P1 . C121 . C122 . 119.0(4) yes P1 . C121 . C126 . 121.9(4) yes C122 . C121 . C126 . 118.9(5) yes C121 . C122 . C123 . 119.9(6) yes C121 . C122 . H1221 . 120.1 no C123 . C122 . H1221 . 120.1 no C122 . C123 . C124 . 120.0(6) yes C122 . C123 . H1231 . 120.0 no C124 . C123 . H1231 . 120.0 no C123 . C124 . C125 . 119.9(6) yes C123 . C124 . H1241 . 120.1 no C125 . C124 . H1241 . 120.1 no C124 . C125 . C126 . 120.4(6) yes C124 . C125 . H1251 . 119.8 no C126 . C125 . H1251 . 119.8 no C121 . C126 . C125 . 121.0(6) yes C121 . C126 . H1261 . 119.5 no C125 . C126 . H1261 . 119.5 no P1 . C131 . C132 . 118.5(5) yes P1 . C131 . C136 . 122.8(5) yes C132 . C131 . C136 . 118.7(6) yes C131 . C132 . C133 . 119.4(8) yes C131 . C132 . H1321 . 120.3 no C133 . C132 . H1321 . 120.3 no C132 . C133 . C134 . 121.5(9) yes C132 . C133 . H1331 . 119.3 no C134 . C133 . H1331 . 119.3 no C133 . C134 . C135 . 119.1(7) yes C133 . C134 . H1341 . 120.4 no C135 . C134 . H1341 . 120.4 no C134 . C135 . C136 . 120.6(7) yes C134 . C135 . H1351 . 119.7 no C136 . C135 . H1351 . 119.7 no C135 . C136 . C131 . 120.7(6) yes C135 . C136 . H1361 . 119.7 no C131 . C136 . H1361 . 119.7 no P2 . C211 . C212 . 119.8(4) yes P2 . C211 . C216 . 122.0(5) yes C212 . C211 . C216 . 118.2(5) yes C211 . C212 . Au1 . 128.4(4) yes C211 . C212 . C213 . 117.7(5) yes Au1 . C212 . C213 . 113.9(4) yes F213 . C213 . C212 . 119.6(5) yes F213 . C213 . C214 . 116.7(6) yes C212 . C213 . C214 . 123.7(6) yes F214 . C214 . C213 . 121.8(6) yes F214 . C214 . C215 . 119.4(6) yes C213 . C214 . C215 . 118.8(6) yes F215 . C215 . C214 . 120.0(6) yes F215 . C215 . C216 . 120.8(6) yes C214 . C215 . C216 . 119.1(6) yes C211 . C216 . F216 . 121.2(6) yes C211 . C216 . C215 . 122.4(6) yes F216 . C216 . C215 . 116.4(5) yes P2 . C221 . C222 . 118.7(5) yes P2 . C221 . C226 . 121.0(6) yes C222 . C221 . C226 . 120.3(7) yes C221 . C222 . C223 . 121.3(8) yes C221 . C222 . H2221 . 119.3 no C223 . C222 . H2221 . 119.3 no C222 . C223 . C224 . 119.0(9) yes C222 . C223 . H2231 . 120.5 no C224 . C223 . H2231 . 120.5 no C223 . C224 . C225 . 121.2(8) yes C223 . C224 . H2241 . 119.4 no C225 . C224 . H2241 . 119.4 no C224 . C225 . C226 . 120.0(9) yes C224 . C225 . H2251 . 120.0 no C226 . C225 . H2251 . 120.0 no C225 . C226 . C221 . 118.2(9) yes C225 . C226 . H2261 . 120.9 no C221 . C226 . H2261 . 120.9 no P2 . C231 . C232 . 119.1(5) yes P2 . C231 . C236 . 121.3(5) yes C232 . C231 . C236 . 119.3(6) yes C231 . C232 . C233 . 120.7(8) yes C231 . C232 . H2321 . 119.6 no C233 . C232 . H2321 . 119.7 no C232 . C233 . C234 . 118.8(9) yes C232 . C233 . H2331 . 120.6 no C234 . C233 . H2331 . 120.6 no C233 . C234 . C235 . 120.5(8) yes C233 . C234 . H2341 . 119.8 no C235 . C234 . H2341 . 119.8 no C234 . C235 . C236 . 120.5(8) yes C234 . C235 . H2351 . 119.8 no C236 . C235 . H2351 . 119.8 no C235 . C236 . C231 . 120.2(7) yes C235 . C236 . H2361 . 119.9 no C231 . C236 . H2361 . 119.9 no Cl51 . C501 . Cl52 . 110.3(8) yes Cl51 . C501 . H5011 . 109.3 no Cl52 . C501 . H5011 . 109.3 no Cl51 . C501 . H5012 . 109.3 no Cl52 . C501 . H5012 . 109.3 no H5011 . C501 . H5012 . 109.5 no Cl62 . C601 . Cl61 . 112.2(11) yes Cl62 . C601 . H6011 . 108.9 no Cl61 . C601 . H6011 . 108.9 no Cl62 . C601 . H6012 . 108.7 no Cl61 . C601 . H6012 . 108.7 no H6011 . C601 . H6012 . 109.5 no #------------------------------------------------------------------------------ loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Cl2 F215 3.464(5) . 1_655 no Cl51 F115 3.128(8) . 1_455 no Cl51 C122 3.464(8) . 2_466 no Cl51 F214 3.480(7) . . no Cl51 F215 3.575(7) . . no Cl52 F113 3.214(8) . . no Cl52 F116 3.561(9) . 2_466 no Cl52 C215 3.592(9) . . no Cl61 F214 3.29(1) . . no Cl61 F215 3.42(1) . . no Cl61 C116 3.48(1) . 2_466 no Cl62 F215 3.39(1) . . no Cl62 C215 3.43(1) . . no Cl62 C216 3.55(1) . . no F113 F115 2.984(6) . 2_466 no F113 C223 3.115(9) . 3_656 no F114 F214 2.983(6) . 2_566 no F114 F213 3.240(5) . 2_566 no F114 F116 3.335(6) . 2_466 no F114 F115 3.595(7) . 2_466 no F115 F213 2.876(6) . 2_566 no F115 F214 3.021(6) . 1_655 no F115 C113 3.206(8) . 2_566 no F115 F214 3.406(6) . 2_566 no F115 C213 3.440(8) . 2_566 no F115 C114 3.502(8) . 2_566 no F116 F214 2.777(6) . 1_655 no F116 C235 3.58(1) . 4_664 no F214 C116 3.103(7) . 1_455 no F214 C115 3.224(7) . 1_455 no F214 C114 3.331(8) . 2_466 no F214 C115 3.549(8) . 2_466 no F215 C224 3.11(1) . 3_556 no F215 C225 3.42(1) . 3_556 no F216 C124 3.214(9) . 4_565 no F216 C123 3.248(8) . 4_565 no C123 C501 3.45(2) . 2_566 no C124 C501 3.53(2) . 2_566 no C124 C224 3.55(1) . 2_556 no C125 C224 3.56(1) . 2_556 no #------------------------------------------------------------------------------ loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion _geom_torsion_publ_flag Au1 Au2 P2 C211 . . . . -29.8(2) no Au1 Au2 P2 C221 . . . . 93.5(2) no Au1 Au2 P2 C231 . . . . -149.1(2) no Au1 P1 C111 C112 . . . . 0.5(3) no Au1 P1 C111 C116 . . . . -173.8(7) no Au1 P1 C121 C122 . . . . 9.4(5) no Au1 P1 C121 C126 . . . . -175.7(5) no Au1 P1 C131 C132 . . . . 78.5(8) no Au1 P1 C131 C136 . . . . -103.0(6) no Au1 C112 C111 P1 . . . . -0.6(4) no Au1 C112 C111 C116 . . . . 174.8(5) no Au1 C112 C113 F113 . . . . 6(1) no Au1 C112 C113 C114 . . . . -175.8(5) no Au1 C212 C211 P2 . . . . -0.2(7) no Au1 C212 C211 C216 . . . . -178.2(4) no Au1 C212 C213 F213 . . . . 0.8(7) no Au1 C212 C213 C214 . . . . 179.8(5) no Au2 Au1 P1 C111 . . . . -85.4(2) no Au2 Au1 P1 C121 . . . . 166.8(2) no Au2 Au1 P1 C131 . . . . 28.9(3) no Au2 Au1 C112 C111 . . . . 107.1(3) no Au2 Au1 C112 C113 . . . . -79.3(6) no Au2 Au1 C212 C211 . . . . -18.8(5) no Au2 Au1 C212 C213 . . . . 162.2(4) no Au2 P2 C211 C212 . . . . 29.1(6) no Au2 P2 C211 C216 . . . . -152.9(5) no Au2 P2 C221 C222 . . . . 22.7(6) no Au2 P2 C221 C226 . . . . -159.0(7) no Au2 P2 C231 C232 . . . . 72.8(6) no Au2 P2 C231 C236 . . . . -100.2(5) no Cl1 Au1 Au2 Cl2 . . . . 113.93(8) no Cl1 Au1 Au2 P2 . . . . -67.96(6) no Cl1 Au1 P1 C111 . . . . 177.7(2) no Cl1 Au1 P1 C121 . . . . 70.0(2) no Cl1 Au1 P1 C131 . . . . -68.0(3) no Cl1 Au1 C212 C211 . . . . 74.5(5) no Cl1 Au1 C212 C213 . . . . -104.5(4) no Cl2 Au2 Au1 P1 . . . . 11.58(9) no Cl2 Au2 Au1 C112 . . . . -57.0(2) no Cl2 Au2 Au1 C212 . . . . -154.1(2) no P1 Au1 Au2 P2 . . . . -170.31(6) no P1 Au1 C112 C111 . . . . 0.5(3) no P1 Au1 C112 C113 . . . . 174.2(6) no P1 C111 C112 C113 . . . . -175.5(5) no P1 C111 C116 F116 . . . . -3(1) no P1 C111 C116 C115 . . . . 175.7(5) no P1 C121 C122 C123 . . . . 175.0(5) no P1 C121 C126 C125 . . . . -175.5(6) no P1 C131 C132 C133 . . . . -179(1) no P1 C131 C136 C135 . . . . 179.7(6) no P2 Au2 Au1 C112 . . . . 121.1(2) no P2 Au2 Au1 C212 . . . . 24.0(1) no P2 C211 C212 C213 . . . . 178.8(5) no P2 C211 C216 F216 . . . . -1.4(9) no P2 C211 C216 C215 . . . . -179.2(5) no P2 C221 C222 C223 . . . . 175.6(5) no P2 C221 C226 C225 . . . . -176.5(8) no P2 C231 C232 C233 . . . . -175.5(7) no P2 C231 C236 C235 . . . . 174.2(5) no F113 C113 C112 C111 . . . . 178.7(5) no F113 C113 C114 F114 . . . . 1.5(9) no F113 C113 C114 C115 . . . . -177.8(6) no F114 C114 C113 C112 . . . . -177.2(6) no F114 C114 C115 F115 . . . . -2(1) no F114 C114 C115 C116 . . . . 179.3(6) no F115 C115 C114 C113 . . . . 177.4(6) no F115 C115 C116 F116 . . . . -1.9(9) no F115 C115 C116 C111 . . . . 179.8(6) no F116 C116 C111 C112 . . . . -176.1(5) no F116 C116 C115 C114 . . . . 177.0(6) no F213 C213 C212 C211 . . . . -178.3(5) no F213 C213 C214 F214 . . . . -3.6(9) no F213 C213 C214 C215 . . . . 177.3(6) no F214 C214 C213 C212 . . . . 177.4(6) no F214 C214 C215 F215 . . . . -0.6(9) no F214 C214 C215 C216 . . . . -177.8(6) no F215 C215 C214 C213 . . . . 178.5(6) no F215 C215 C216 F216 . . . . 5.0(9) no F215 C215 C216 C211 . . . . -177.1(6) no F216 C216 C211 C212 . . . . 176.7(5) no F216 C216 C215 C214 . . . . -177.8(6) no C111 P1 Au1 C112 . . . . -0.4(2) no C111 P1 C121 C122 . . . . -81.3(5) no C111 P1 C121 C126 . . . . 93.5(6) no C111 P1 C131 C132 . . . . 177.7(7) no C111 P1 C131 C136 . . . . -3.9(7) no C111 C112 Au1 C212 . . . . -168.0(4) no C111 C112 C113 C114 . . . . -2.7(9) no C111 C116 C115 C114 . . . . -1(1) no C112 Au1 P1 C121 . . . . -108.2(2) no C112 Au1 P1 C131 . . . . 113.9(3) no C112 Au1 C212 C211 . . . . -109.3(5) no C112 Au1 C212 C213 . . . . 71.7(4) no C112 C111 P1 C121 . . . . 113.4(4) no C112 C111 P1 C131 . . . . -126.4(4) no C112 C111 C116 C115 . . . . 2.2(9) no C112 C113 C114 C115 . . . . 4(1) no C113 C112 Au1 C212 . . . . 5.7(6) no C113 C112 C111 C116 . . . . -0.1(8) no C113 C114 C115 C116 . . . . -1(1) no C116 C111 P1 C121 . . . . -61.0(7) no C116 C111 P1 C131 . . . . 59.2(7) no C121 P1 Au1 C212 . . . . -67.5(6) no C121 P1 C131 C132 . . . . -61.4(8) no C121 P1 C131 C136 . . . . 117.0(6) no C121 C122 C123 C124 . . . . 1(1) no C121 C126 C125 C124 . . . . 0(1) no C122 C121 P1 C131 . . . . 155.0(5) no C122 C121 C126 C125 . . . . -1(1) no C122 C123 C124 C125 . . . . -1(1) no C123 C122 C121 C126 . . . . -0(1) no C123 C124 C125 C126 . . . . 1(1) no C126 C121 P1 C131 . . . . -30.2(6) no C131 P1 Au1 C212 . . . . 154.6(6) no C131 C132 C133 C134 . . . . -1(2) no C131 C136 C135 C134 . . . . -0(1) no C132 C131 C136 C135 . . . . -2(1) no C132 C133 C134 C135 . . . . -1(2) no C133 C132 C131 C136 . . . . 2(2) no C133 C134 C135 C136 . . . . 1(2) no C211 P2 C221 C222 . . . . 148.7(5) no C211 P2 C221 C226 . . . . -33.0(8) no C211 P2 C231 C232 . . . . -49.5(6) no C211 P2 C231 C236 . . . . 137.5(5) no C211 C212 C213 C214 . . . . 0.7(9) no C211 C216 C215 C214 . . . . 0(1) no C212 C211 P2 C221 . . . . -98.3(5) no C212 C211 P2 C231 . . . . 149.1(5) no C212 C211 C216 C215 . . . . -1(1) no C212 C213 C214 C215 . . . . -2(1) no C213 C212 C211 C216 . . . . 0.7(8) no C213 C214 C215 C216 . . . . 1(1) no C216 C211 P2 C221 . . . . 79.7(6) no C216 C211 P2 C231 . . . . -33.0(6) no C221 P2 C231 C232 . . . . -163.6(6) no C221 P2 C231 C236 . . . . 23.3(6) no C221 C222 C223 C224 . . . . 2(1) no C221 C226 C225 C224 . . . . 0(2) no C222 C221 P2 C231 . . . . -96.9(6) no C222 C221 C226 C225 . . . . 2(1) no C222 C223 C224 C225 . . . . 0(1) no C223 C222 C221 C226 . . . . -3(1) no C223 C224 C225 C226 . . . . -1(2) no C226 C221 P2 C231 . . . . 81.4(8) no C231 C232 C233 C234 . . . . 1(1) no C231 C236 C235 C234 . . . . 2(1) no C232 C231 C236 C235 . . . . 1(1) no C232 C233 C234 C235 . . . . 2(1) no C233 C232 C231 C236 . . . . -2(1) no C233 C234 C235 C236 . . . . -3(1) no #------------------------------------------------------------------------------ #===END # Attachment 'ben0605mod.cif.txt' data_ben0605 _database_code_depnum_ccdc_archive 'CCDC 725987' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_date 06-06-06 _audit_creation_method CRYSTALS_ver_12.18 _oxford_structure_analysis_title '6020923 ben0605' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 17.4374(1) _cell_length_b 21.6957(2) _cell_length_c 22.8416(2) _cell_angle_alpha 90 _cell_angle_beta 109.8587(5) _cell_angle_gamma 90 _cell_volume 8127.48(12) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 1 21/c 1 ' _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x,y+1/2,-z+1/2 x,-y+1/2,z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Au -2.0133 8.8022 16.8819 0.4611 18.5913 8.6216 25.5582 1.4826 5.8600 36.3956 12.0658 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Br -0.2901 2.4595 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328 2.9557 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0171 0.0103 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' P 0.1023 0.0942 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C37 H22 Au2 Br2 Cl2 F8 P2 # Dc = 2.13 Fooo = 4953.09 Mu = 94.52 M = 2610.32 # Found Formula = C37.27 H22.53 Au2 Br2 Cl2.53 F8 P2 # Dc = 2.17 FOOO = 4953.09 Mu = 94.88 M = 2655.36 _chemical_formula_sum 'C74.53 H45.06 Au4 Br4 Cl5.06 F16 P4' _chemical_formula_moiety '2(C36 H20 Au2 Br2 F8 P2), 2.53(C H2 Cl2) ' _chemical_compound_source ' from RMIT University ' _chemical_formula_weight 2655.36 # 1327.68 _cell_measurement_reflns_used 157431 _cell_measurement_theta_min 3 _cell_measurement_theta_max 27 _cell_measurement_temperature 200 _exptl_crystal_description rod _exptl_crystal_colour orange _exptl_crystal_size_min 0.08 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_max 0.40 _exptl_crystal_density_diffrn 2.170 _exptl_crystal_density_meas 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 4953.090 _exptl_absorpt_coefficient_mu 9.488 # Sheldrick geometric approximatio 0.18 0.47 # Absorption correction loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1 0 0 0.200 0 1 0 0.070 0 -1 0 0.010 0 0 1 0.100 0 0 -1 0.080 -15 0 9 0.184 0 -1 1 0.050 0 1 -1 0.090 0 1 1 0.100 0 -1 -1 0.050 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.132 _exptl_absorpt_correction_T_max 0.497 _exptl_absorpt_process_details ; via Gaussian method (Coppens, 1970) implemented in maXus (2000) ; #_diffrn_reflns_av_R_equivalents 0.036 # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method ' \f and \w scans with CCD ' _diffrn_special_details ; CCD data collecting conditions- phi and omega scans of width 1.4deg at rate 39 sec/frame, crystal-detector distance 32mm, multiple scan sets so over 95 percent of data collected with 4-fold redundancy or more. ; # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius BV, 1997)' _computing_data_reduction 'Denzo/Scalepack (Otwinowski & Minor, 1997)' _computing_cell_refinement 'Denzo/Scalepack ' _computing_structure_solution 'SIR92 (Altomare et al, 1994)' _computing_structure_refinement 'CRYSTALS (Watkin et al 2003)' _computing_publication_material 'CRYSTALS ' _computing_molecular_graphics ; ORTEP-II (Johnson 1976) in teXsan (MSC, 1992-1997) ; _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 200 _diffrn_reflns_number 173896 _reflns_number_total 18591 _diffrn_reflns_av_R_equivalents 0.052 # Number of reflections with Friedels Law is 18591 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 18618 _diffrn_reflns_theta_min 2.562 _diffrn_reflns_theta_max 27.471 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.471 _diffrn_measured_fraction_theta_full 0.999 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _reflns_limit_h_min -22 _reflns_limit_h_max 21 _reflns_limit_k_min 0 _reflns_limit_k_max 28 _reflns_limit_l_min 0 _reflns_limit_l_max 29 _oxford_diffrn_Wilson_B_factor 2.41 _oxford_diffrn_Wilson_scale 243.49 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.04 _refine_diff_density_max 1.16 _refine_ls_number_reflns 10971 _refine_ls_number_restraints 62 _refine_ls_number_parameters 992 #_refine_ls_R_factor_ref 0.0229 _refine_ls_wR_factor_ref 0.0269 _refine_ls_goodness_of_fit_ref 1.0901 #_reflns_number_all 18535 _refine_ls_R_factor_all 0.0485 _refine_ls_wR_factor_all 0.0350 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.0\s(I) _reflns_number_gt 10971 _refine_ls_R_factor_gt 0.0229 _refine_ls_wR_factor_gt 0.0269 _refine_ls_shift/su_max 0.013670 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment noref # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 1.40 0.0451 1.15 ; #============================================================================= # 4. TEXT _publ_section_comment ; The crystallographic asymmetric unit consists of two [Au{P(C~6~F~4~)(C~6~H~5~)~2~}Br]~2~ molecules and 2.53 dichloromethane molecules of solvation. Within the unit cell there is a region of ill-defined solvate molecules. One dichloromethane molecule is clearly observed; the second has one site for each of one Cl and the C, but two sites for the other Cl; and a third molecule is proposed which is close to one of these latter disordered sites so can only be occupied if that site is unoccupied. Restraints were imposed upon distances, angles and displacement parameters for these latter two dichloromethane molecules, and the relative occupancies of the disordered Cl sites were refined. The structure is isomorphous with its chloro analogue, the structure of which was determined previously [locally identified as ben0601]. The largest features in the final difference electron density map are within the disordered solvent region of the cell. ; _refine_special_details ; The crystallographic asymmetric unit consists of two [Au{P(C~6~F~4~)(C~6~H~5~)~2~}Br]~2~ molecules and 2.53 dichloromethane molecules of solvation. Within the unit cell there is a region of ill-defined solvate molecules. One dichloromethane molecule is clearly observed; the second has one site for each of one Cl and the C, but two sites for the other Cl; and a third molecule is proposed which is close to one of these latter disordered sites so can only be occupied if that site is unoccupied. Restraints were imposed upon distances, angles and displacement parameters for these latter two dichloromethane molecules, and the relative occupancies of the disordered Cl sites were refined. The structure is isomorphous with its chloro analogue, the structure of which was determined previously [locally identified as ben0601]. The largest features in the final difference electron density map are within the disordered solvent region of the cell. ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions #Captions to figures ; ? ; _publ_section_exptl_refinement # see also _refine_ls_hydrogen for refinement keywords. ; Hydrogen atoms were included at idealized positions and ride on the atom to which they are attached. ; _publ_section_exptl_prep ; The compound was prepared by NM and recrystallized from dichloromethane/hexane. The sample ID is ND3. ; #**************************************************************************** # Insert your own references if required - in alphabetical order _publ_section_references ; Mackay, S., Gilmore, C. J.,Edwards, C., Stewart, N. & Shankland, K. (2000). maXus Computer Program for the Solution and Refinement of Crystal Structures. Nonius, The Netherlands, MacScience, Japan & The University of Glasgow. Coppens, P. (1970). The Evaluation of Absorption and Extinction in Single-Crystal Structure Analysis. Crystallographic Computing. F. R. Ahmed, S. R. Hall and C. P. Huber, eds., Munksgaard. Copenhagen. pp 255-270. Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. (27), 435-435 Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius BV, COLLECT Software, 1997-2001) Otwinowski, Z. & Minor, W. (1996), Processing of X-ray Diffraction Data Collected in Oscillation Mode. Methods Enzymol. 276, 1997, 307-326. Ed Carter, C.W. & Sweet, R.M., Academic Press. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Watkin D.J. (1994), Acta Cryst, A50, 411-437 Molecular Structure Corporation. (1992-1997). teXsan. Single Crystal Structure Analysis Software. Version 1.8. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA. Johnson, C.K. (1976) ORTEP-II, A Fortran Thermal-Ellipsoid Plot Program, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Au1 Au 0.356367(11) 0.252606(9) 0.737479(9) 0.0306 1.0000 Uani . . . . . . Au2 Au 0.220272(11) 0.197976(9) 0.686953(9) 0.0296 1.0000 Uani . . . . . . Au3 Au 0.304455(11) 0.722766(10) 0.371011(9) 0.0321 1.0000 Uani . . . . . . Au4 Au 0.164858(11) 0.672326(9) 0.328984(8) 0.0288 1.0000 Uani . . . . . . Br1 Br 0.47743(3) 0.32095(3) 0.75924(3) 0.0462 1.0000 Uani . . . . . . Br2 Br 0.07992(3) 0.16834(3) 0.61891(3) 0.0438 1.0000 Uani . . . . . . Br3 Br 0.43126(4) 0.78546(3) 0.39595(3) 0.0540 1.0000 Uani . . . . . . Br4 Br 0.02427(3) 0.63384(3) 0.27506(3) 0.0449 1.0000 Uani . . . . . . Cl51 Cl 0.95836(18) 0.54658(11) 0.57922(13) 0.0958 1.0000 Uani . . . . . . Cl52 Cl 0.82192(19) 0.51189(17) 0.61749(15) 0.1205 1.0000 Uani . . . . . . Cl61 Cl 0.6828(4) 0.5712(2) 0.7104(3) 0.2039 1.0000 Uani D U . . . . Cl62 Cl 0.5846(11) 0.6462(7) 0.6059(8) 0.2692 0.530(7) Uani D U P . . . Cl63 Cl 0.5870(12) 0.5720(8) 0.5954(9) 0.2964 0.470(7) Uani D U P . . . Cl71 Cl 0.3073(6) 0.6097(4) 0.5287(5) 0.1815 0.530(7) Uani D U P . . . Cl72 Cl 0.3832(5) 0.5135(3) 0.4843(4) 0.1424 0.530(7) Uani D U P . . . P1 P 0.27972(8) 0.32849(6) 0.76458(6) 0.0320 1.0000 Uani . . . . . . P2 P 0.27835(8) 0.17242(6) 0.61166(6) 0.0314 1.0000 Uani . . . . . . P3 P 0.23525(8) 0.79996(6) 0.40447(6) 0.0320 1.0000 Uani . . . . . . P4 P 0.20696(8) 0.65350(6) 0.24390(6) 0.0304 1.0000 Uani . . . . . . F113 F 0.1154(2) 0.13358(15) 0.76400(18) 0.0503 1.0000 Uani . . . . . . F114 F 0.0491(2) 0.17999(18) 0.84329(19) 0.0569 1.0000 Uani . . . . . . F115 F 0.0749(2) 0.29889(19) 0.88098(17) 0.0549 1.0000 Uani . . . . . . F116 F 0.1716(2) 0.37124(16) 0.83937(17) 0.0508 1.0000 Uani . . . . . . F213 F 0.5249(2) 0.1831(2) 0.81004(17) 0.0607 1.0000 Uani . . . . . . F214 F 0.6062(2) 0.0950(2) 0.7735(2) 0.0774 1.0000 Uani . . . . . . F215 F 0.5451(3) 0.0456(2) 0.6589(2) 0.0783 1.0000 Uani . . . . . . F216 F 0.4009(2) 0.08219(19) 0.57958(18) 0.0588 1.0000 Uani . . . . . . F313 F 0.0768(2) 0.60673(15) 0.41999(16) 0.0494 1.0000 Uani . . . . . . F314 F 0.0141(2) 0.65818(18) 0.49958(17) 0.0560 1.0000 Uani . . . . . . F315 F 0.0406(2) 0.77772(18) 0.53155(15) 0.0510 1.0000 Uani . . . . . . F316 F 0.1377(2) 0.84656(15) 0.48770(16) 0.0483 1.0000 Uani . . . . . . F413 F 0.4721(2) 0.6423(2) 0.42623(17) 0.0627 1.0000 Uani . . . . . . F414 F 0.5398(2) 0.5605(2) 0.3716(2) 0.0760 1.0000 Uani . . . . . . F415 F 0.4604(3) 0.52166(19) 0.2542(2) 0.0682 1.0000 Uani . . . . . . F416 F 0.3111(2) 0.56433(19) 0.19066(17) 0.0559 1.0000 Uani . . . . . . C111 C 0.1973(3) 0.2888(2) 0.7800(2) 0.0335 1.0000 Uani . . . . . . C112 C 0.1807(3) 0.2278(2) 0.7577(2) 0.0332 1.0000 Uani . . . . . . C113 C 0.1316(3) 0.1932(3) 0.7806(3) 0.0391 1.0000 Uani . . . . . . C114 C 0.0973(3) 0.2161(3) 0.8217(3) 0.0416 1.0000 Uani . . . . . . C115 C 0.1106(3) 0.2763(3) 0.8421(3) 0.0397 1.0000 Uani . . . . . . C116 C 0.1607(3) 0.3122(3) 0.8210(2) 0.0367 1.0000 Uani . . . . . . C121 C 0.3371(3) 0.3656(3) 0.8369(3) 0.0390 1.0000 Uani . . . . . . C122 C 0.3790(4) 0.3273(4) 0.8864(3) 0.0559 1.0000 Uani . . . . . . C123 C 0.4205(5) 0.3526(5) 0.9444(3) 0.0735 1.0000 Uani . . . . . . C124 C 0.4220(5) 0.4146(5) 0.9524(4) 0.0783 1.0000 Uani . . . . . . C125 C 0.3819(5) 0.4523(4) 0.9049(4) 0.0719 1.0000 Uani . . . . . . C126 C 0.3383(5) 0.4280(3) 0.8460(3) 0.0552 1.0000 Uani . . . . . . C131 C 0.2400(3) 0.3852(3) 0.7040(3) 0.0389 1.0000 Uani . . . . . . C132 C 0.2943(4) 0.4245(3) 0.6892(3) 0.0562 1.0000 Uani . . . . . . C133 C 0.2654(5) 0.4654(4) 0.6406(4) 0.0667 1.0000 Uani . . . . . . C134 C 0.1820(5) 0.4678(3) 0.6062(3) 0.0613 1.0000 Uani . . . . . . C135 C 0.1287(4) 0.4302(3) 0.6220(3) 0.0524 1.0000 Uani . . . . . . C136 C 0.1567(4) 0.3887(3) 0.6705(3) 0.0440 1.0000 Uani . . . . . . C211 C 0.3832(3) 0.1528(2) 0.6541(2) 0.0331 1.0000 Uani . . . . . . C212 C 0.4161(3) 0.1803(3) 0.7127(3) 0.0364 1.0000 Uani . . . . . . C213 C 0.4919(3) 0.1601(3) 0.7524(3) 0.0442 1.0000 Uani . . . . . . C214 C 0.5334(4) 0.1147(3) 0.7349(3) 0.0501 1.0000 Uani . . . . . . C215 C 0.5030(4) 0.0896(3) 0.6768(4) 0.0539 1.0000 Uani . . . . . . C216 C 0.4283(4) 0.1088(3) 0.6364(3) 0.0424 1.0000 Uani . . . . . . C221 C 0.2342(3) 0.1071(2) 0.5630(2) 0.0341 1.0000 Uani . . . . . . C222 C 0.2306(4) 0.0514(3) 0.5926(3) 0.0418 1.0000 Uani . . . . . . C223 C 0.2010(4) -0.0011(3) 0.5578(3) 0.0460 1.0000 Uani . . . . . . C224 C 0.1728(4) 0.0022(3) 0.4935(3) 0.0458 1.0000 Uani . . . . . . C225 C 0.1755(4) 0.0573(3) 0.4643(3) 0.0541 1.0000 Uani . . . . . . C226 C 0.2067(4) 0.1101(3) 0.4990(3) 0.0468 1.0000 Uani . . . . . . C231 C 0.2733(3) 0.2381(3) 0.5627(2) 0.0363 1.0000 Uani . . . . . . C232 C 0.1990(4) 0.2658(3) 0.5344(3) 0.0551 1.0000 Uani . . . . . . C233 C 0.1923(5) 0.3177(3) 0.4977(4) 0.0641 1.0000 Uani . . . . . . C234 C 0.2607(5) 0.3423(4) 0.4898(4) 0.0812 1.0000 Uani . . . . . . C235 C 0.3346(5) 0.3148(5) 0.5184(5) 0.1057 1.0000 Uani . . . . . . C236 C 0.3414(4) 0.2624(4) 0.5544(4) 0.0759 1.0000 Uani . . . . . . C311 C 0.1567(3) 0.7622(2) 0.4268(2) 0.0329 1.0000 Uani . . . . . . C312 C 0.1382(3) 0.7011(2) 0.4063(2) 0.0306 1.0000 Uani . . . . . . C313 C 0.0921(3) 0.6673(3) 0.4331(2) 0.0355 1.0000 Uani . . . . . . C314 C 0.0602(3) 0.6920(3) 0.4755(2) 0.0398 1.0000 Uani . . . . . . C315 C 0.0744(3) 0.7534(3) 0.4922(2) 0.0371 1.0000 Uani . . . . . . C316 C 0.1233(3) 0.7877(2) 0.4691(3) 0.0361 1.0000 Uani . . . . . . C321 C 0.3007(3) 0.8369(3) 0.4746(3) 0.0369 1.0000 Uani . . . . . . C322 C 0.3385(4) 0.8002(3) 0.5257(3) 0.0556 1.0000 Uani . . . . . . C323 C 0.3877(4) 0.8253(4) 0.5801(3) 0.0624 1.0000 Uani . . . . . . C324 C 0.4015(4) 0.8890(4) 0.5848(3) 0.0543 1.0000 Uani . . . . . . C325 C 0.3654(4) 0.9253(3) 0.5342(3) 0.0563 1.0000 Uani . . . . . . C326 C 0.3143(4) 0.8997(3) 0.4777(3) 0.0449 1.0000 Uani . . . . . . C331 C 0.1924(3) 0.8593(3) 0.3471(2) 0.0352 1.0000 Uani . . . . . . C332 C 0.2395(4) 0.8812(3) 0.3129(3) 0.0455 1.0000 Uani . . . . . . C333 C 0.2111(4) 0.9294(3) 0.2717(3) 0.0541 1.0000 Uani . . . . . . C334 C 0.1378(4) 0.9566(3) 0.2653(3) 0.0573 1.0000 Uani . . . . . . C335 C 0.0894(5) 0.9339(4) 0.2975(4) 0.0726 1.0000 Uani . . . . . . C336 C 0.1166(4) 0.8850(3) 0.3382(3) 0.0541 1.0000 Uani . . . . . . C411 C 0.3111(3) 0.6266(2) 0.2771(3) 0.0343 1.0000 Uani . . . . . . C412 C 0.3532(3) 0.6498(3) 0.3367(2) 0.0345 1.0000 Uani . . . . . . C413 C 0.4291(3) 0.6254(3) 0.3678(3) 0.0440 1.0000 Uani . . . . . . C414 C 0.4644(3) 0.5825(3) 0.3401(3) 0.0509 1.0000 Uani . . . . . . C415 C 0.4248(4) 0.5623(3) 0.2808(3) 0.0491 1.0000 Uani . . . . . . C416 C 0.3480(3) 0.5846(3) 0.2491(3) 0.0405 1.0000 Uani . . . . . . C421 C 0.1461(3) 0.5969(3) 0.1902(2) 0.0330 1.0000 Uani . . . . . . C422 C 0.0935(3) 0.6136(3) 0.1319(3) 0.0395 1.0000 Uani . . . . . . C423 C 0.0420(4) 0.5702(3) 0.0937(3) 0.0532 1.0000 Uani . . . . . . C424 C 0.0447(4) 0.5095(3) 0.1136(3) 0.0537 1.0000 Uani . . . . . . C425 C 0.0973(4) 0.4933(3) 0.1715(3) 0.0473 1.0000 Uani . . . . . . C426 C 0.1481(4) 0.5361(3) 0.2106(3) 0.0418 1.0000 Uani . . . . . . C431 C 0.2067(3) 0.7236(2) 0.2012(2) 0.0329 1.0000 Uani . . . . . . C432 C 0.1408(3) 0.7634(3) 0.1889(3) 0.0428 1.0000 Uani . . . . . . C433 C 0.1382(4) 0.8168(3) 0.1548(3) 0.0487 1.0000 Uani . . . . . . C434 C 0.2007(4) 0.8312(3) 0.1336(3) 0.0527 1.0000 Uani . . . . . . C435 C 0.2680(4) 0.7920(3) 0.1472(4) 0.0603 1.0000 Uani . . . . . . C436 C 0.2706(4) 0.7385(3) 0.1804(3) 0.0538 1.0000 Uani . . . . . . C501 C 0.9268(6) 0.5226(4) 0.6413(4) 0.0811 1.0000 Uani . . . . . . C601 C 0.6723(12) 0.6120(10) 0.6448(9) 0.2517 1.0000 Uani D U . . . . C701 C 0.3977(13) 0.5739(13) 0.5402(14) 0.1882 0.530(7) Uani D U P . . . H1221 H 0.3793 0.2817 0.8802 0.0671 1.0000 Uiso R . . . . . H1231 H 0.4492 0.3251 0.9803 0.0879 1.0000 Uiso R . . . . . H1241 H 0.4532 0.4326 0.9940 0.0983 1.0000 Uiso R . . . . . H1251 H 0.3832 0.4979 0.9117 0.0930 1.0000 Uiso R . . . . . H1261 H 0.3084 0.4561 0.8110 0.0706 1.0000 Uiso R . . . . . H1321 H 0.3539 0.4229 0.7139 0.0678 1.0000 Uiso R . . . . . H1331 H 0.3041 0.4934 0.6298 0.0814 1.0000 Uiso R . . . . . H1341 H 0.1613 0.4968 0.5703 0.0724 1.0000 Uiso R . . . . . H1351 H 0.0690 0.4329 0.5981 0.0616 1.0000 Uiso R . . . . . H1361 H 0.1174 0.3613 0.6815 0.0532 1.0000 Uiso R . . . . . H2221 H 0.2495 0.0494 0.6390 0.0507 1.0000 Uiso R . . . . . H2231 H 0.1999 -0.0413 0.5790 0.0557 1.0000 Uiso R . . . . . H2241 H 0.1505 -0.0355 0.4681 0.0540 1.0000 Uiso R . . . . . H2251 H 0.1548 0.0595 0.4178 0.0627 1.0000 Uiso R . . . . . H2261 H 0.2090 0.1499 0.4776 0.0553 1.0000 Uiso R . . . . . H2321 H 0.1491 0.2483 0.5404 0.0687 1.0000 Uiso R . . . . . H2331 H 0.1378 0.3373 0.4770 0.0754 1.0000 Uiso R . . . . . H2341 H 0.2566 0.3798 0.4635 0.0917 1.0000 Uiso R . . . . . H2351 H 0.3846 0.3330 0.5133 0.1191 1.0000 Uiso R . . . . . H2361 H 0.3958 0.2424 0.5741 0.0899 1.0000 Uiso R . . . . . H3221 H 0.3294 0.7546 0.5227 0.0630 1.0000 Uiso R . . . . . H3231 H 0.4142 0.7981 0.6168 0.0722 1.0000 Uiso R . . . . . H3241 H 0.4373 0.9076 0.6248 0.0656 1.0000 Uiso R . . . . . H3251 H 0.3753 0.9708 0.5371 0.0673 1.0000 Uiso R . . . . . H3261 H 0.2884 0.9265 0.4407 0.0532 1.0000 Uiso R . . . . . H3321 H 0.2936 0.8621 0.3182 0.0567 1.0000 Uiso R . . . . . H3331 H 0.2442 0.9445 0.2465 0.0667 1.0000 Uiso R . . . . . H3341 H 0.1191 0.9930 0.2372 0.0657 1.0000 Uiso R . . . . . H3351 H 0.0349 0.9528 0.2913 0.0871 1.0000 Uiso R . . . . . H3361 H 0.0814 0.8682 0.3611 0.0669 1.0000 Uiso R . . . . . H4221 H 0.0926 0.6571 0.1173 0.0460 1.0000 Uiso R . . . . . H4231 H 0.0030 0.5825 0.0521 0.0591 1.0000 Uiso R . . . . . H4241 H 0.0086 0.4777 0.0860 0.0622 1.0000 Uiso R . . . . . H4251 H 0.0988 0.4495 0.1857 0.0590 1.0000 Uiso R . . . . . H4261 H 0.1857 0.5238 0.2527 0.0513 1.0000 Uiso R . . . . . H4321 H 0.0952 0.7536 0.2046 0.0525 1.0000 Uiso R . . . . . H4331 H 0.0902 0.8450 0.1456 0.0594 1.0000 Uiso R . . . . . H4341 H 0.1980 0.8694 0.1085 0.0621 1.0000 Uiso R . . . . . H4351 H 0.3145 0.8029 0.1330 0.0761 1.0000 Uiso R . . . . . H4361 H 0.3186 0.7103 0.1894 0.0686 1.0000 Uiso R . . . . . H5011 H 0.9428 0.5547 0.6747 0.0899 1.0000 Uiso R . . . . . H5012 H 0.9544 0.4828 0.6582 0.0899 1.0000 Uiso R . . . . . H6011 H 0.7153 0.6447 0.6562 0.3044 0.530 Uiso R . . . . . H6012 H 0.6833 0.5825 0.6150 0.3044 0.530 Uiso R . . . . . H6013 H 0.6612 0.6568 0.6487 0.3044 0.470 Uiso R . . . . . H6014 H 0.7209 0.6075 0.6313 0.3044 0.470 Uiso R . . . . . H7011 H 0.4381 0.6042 0.5351 0.2243 0.530 Uiso R . . . . . H7012 H 0.4184 0.5561 0.5831 0.2243 0.530 Uiso R . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02478(9) 0.03344(10) 0.03468(10) -0.00051(8) 0.01153(7) 0.00136(7) Au2 0.02586(9) 0.02906(9) 0.03580(10) 0.00115(8) 0.01307(7) 0.00130(7) Au3 0.02562(9) 0.03714(11) 0.03468(10) -0.00489(8) 0.01177(7) -0.00428(8) Au4 0.02521(8) 0.03208(10) 0.03047(9) -0.00242(8) 0.01104(7) -0.00242(7) Br1 0.0317(3) 0.0536(4) 0.0534(3) -0.0058(3) 0.0146(2) -0.0098(2) Br2 0.0283(2) 0.0486(3) 0.0513(3) 0.0042(3) 0.0094(2) -0.0024(2) Br3 0.0329(3) 0.0614(4) 0.0713(4) -0.0176(3) 0.0224(3) -0.0164(3) Br4 0.0273(2) 0.0643(4) 0.0420(3) -0.0056(3) 0.0104(2) -0.0081(2) Cl51 0.120(2) 0.0606(13) 0.1074(18) 0.0163(12) 0.0398(16) 0.0165(13) Cl52 0.107(2) 0.150(3) 0.110(2) 0.031(2) 0.0435(17) 0.053(2) Cl61 0.241(6) 0.117(3) 0.301(7) -0.042(4) 0.154(5) -0.028(3) Cl62 0.303(11) 0.210(10) 0.328(11) -0.043(9) 0.152(9) -0.022(9) Cl63 0.313(11) 0.201(10) 0.341(12) 0.012(10) 0.065(10) -0.059(10) Cl71 0.211(8) 0.131(6) 0.234(9) -0.050(6) 0.116(7) 0.011(5) Cl72 0.142(6) 0.105(5) 0.183(7) -0.016(4) 0.058(5) 0.034(4) P1 0.0308(6) 0.0301(6) 0.0385(7) -0.0006(5) 0.0162(5) 0.0011(5) P2 0.0302(6) 0.0321(6) 0.0343(6) 0.0004(5) 0.0141(5) 0.0012(5) P3 0.0306(6) 0.0329(7) 0.0357(6) -0.0046(5) 0.0155(5) -0.0061(5) P4 0.0291(6) 0.0327(7) 0.0304(6) -0.0020(5) 0.0114(5) -0.0014(5) F113 0.062(2) 0.0335(18) 0.069(2) 0.0009(16) 0.0395(19) -0.0067(15) F114 0.061(2) 0.057(2) 0.070(2) 0.0076(19) 0.046(2) -0.0032(18) F115 0.052(2) 0.069(2) 0.059(2) -0.0119(18) 0.0390(18) 0.0005(18) F116 0.0497(19) 0.045(2) 0.067(2) -0.0182(17) 0.0317(17) -0.0027(15) F213 0.0424(19) 0.078(3) 0.050(2) -0.0036(19) 0.0003(16) 0.0174(18) F214 0.041(2) 0.081(3) 0.096(3) 0.007(3) 0.006(2) 0.032(2) F215 0.059(3) 0.066(3) 0.118(4) -0.013(3) 0.041(3) 0.029(2) F216 0.058(2) 0.065(2) 0.064(2) -0.0219(19) 0.0353(19) 0.0042(18) F313 0.066(2) 0.0383(18) 0.054(2) -0.0073(15) 0.0326(17) -0.0179(16) F314 0.066(2) 0.063(2) 0.054(2) -0.0066(17) 0.0403(18) -0.0246(19) F315 0.057(2) 0.064(2) 0.0444(18) -0.0137(17) 0.0326(16) -0.0080(17) F316 0.059(2) 0.0372(18) 0.059(2) -0.0181(16) 0.0325(17) -0.0079(15) F413 0.0404(19) 0.090(3) 0.046(2) -0.005(2) -0.0007(15) 0.0083(19) F414 0.042(2) 0.083(3) 0.095(3) 0.009(3) 0.011(2) 0.028(2) F415 0.062(2) 0.054(2) 0.099(3) -0.010(2) 0.043(2) 0.0190(19) F416 0.051(2) 0.070(3) 0.052(2) -0.0206(18) 0.0236(17) 0.0010(18) C111 0.029(2) 0.031(3) 0.042(3) 0.001(2) 0.014(2) 0.005(2) C112 0.028(2) 0.036(3) 0.038(3) 0.004(2) 0.013(2) 0.001(2) C113 0.034(3) 0.041(3) 0.045(3) 0.003(2) 0.018(2) 0.000(2) C114 0.038(3) 0.044(3) 0.051(3) 0.009(3) 0.025(2) -0.002(2) C115 0.032(3) 0.048(3) 0.045(3) -0.002(3) 0.021(2) 0.008(2) C116 0.036(3) 0.039(3) 0.037(3) -0.004(2) 0.015(2) 0.004(2) C121 0.038(3) 0.046(3) 0.041(3) -0.005(2) 0.023(2) -0.005(2) C122 0.057(4) 0.065(4) 0.046(3) 0.006(3) 0.017(3) 0.003(3) C123 0.065(5) 0.109(7) 0.045(4) -0.005(4) 0.018(3) -0.020(5) C124 0.067(5) 0.128(8) 0.051(4) -0.024(5) 0.034(4) -0.045(5) C125 0.084(6) 0.070(5) 0.078(5) -0.036(4) 0.050(5) -0.040(4) C126 0.073(4) 0.044(4) 0.060(4) -0.010(3) 0.037(4) -0.014(3) C131 0.037(3) 0.039(3) 0.044(3) 0.006(2) 0.018(2) 0.008(2) C132 0.040(3) 0.060(4) 0.069(4) 0.020(3) 0.020(3) -0.002(3) C133 0.059(4) 0.063(5) 0.082(5) 0.032(4) 0.028(4) 0.006(4) C134 0.071(5) 0.053(4) 0.057(4) 0.020(3) 0.018(3) 0.010(3) C135 0.045(3) 0.053(4) 0.056(4) 0.011(3) 0.013(3) 0.008(3) C136 0.041(3) 0.038(3) 0.054(3) 0.002(3) 0.017(3) 0.005(2) C211 0.031(2) 0.032(3) 0.039(3) -0.001(2) 0.015(2) 0.002(2) C212 0.029(2) 0.041(3) 0.043(3) 0.005(2) 0.016(2) 0.006(2) C213 0.035(3) 0.047(3) 0.046(3) -0.001(3) 0.007(2) 0.006(2) C214 0.033(3) 0.050(4) 0.067(4) 0.010(3) 0.016(3) 0.018(3) C215 0.045(3) 0.045(4) 0.086(5) 0.002(3) 0.040(3) 0.013(3) C216 0.042(3) 0.038(3) 0.054(3) -0.002(3) 0.026(3) 0.005(2) C221 0.033(2) 0.036(3) 0.037(3) 0.003(2) 0.017(2) 0.000(2) C222 0.047(3) 0.042(3) 0.038(3) 0.002(2) 0.016(2) -0.004(3) C223 0.053(3) 0.034(3) 0.052(3) 0.010(3) 0.019(3) -0.001(3) C224 0.043(3) 0.038(3) 0.054(3) -0.004(3) 0.013(3) -0.003(2) C225 0.069(4) 0.052(4) 0.036(3) 0.002(3) 0.011(3) -0.009(3) C226 0.058(4) 0.038(3) 0.042(3) 0.000(3) 0.014(3) -0.009(3) C231 0.035(3) 0.035(3) 0.036(3) 0.000(2) 0.009(2) -0.001(2) C232 0.052(4) 0.054(4) 0.066(4) 0.019(3) 0.028(3) 0.008(3) C233 0.063(4) 0.056(4) 0.070(5) 0.023(4) 0.018(4) 0.019(3) C234 0.078(5) 0.057(5) 0.094(6) 0.043(4) 0.011(5) -0.012(4) C235 0.047(4) 0.126(9) 0.125(8) 0.076(7) 0.004(5) -0.030(5) C236 0.035(3) 0.096(6) 0.093(6) 0.057(5) 0.017(3) 0.001(3) C311 0.032(2) 0.037(3) 0.032(2) 0.002(2) 0.014(2) -0.005(2) C312 0.033(2) 0.032(3) 0.028(2) 0.001(2) 0.0124(19) -0.001(2) C313 0.037(3) 0.038(3) 0.032(2) -0.004(2) 0.013(2) -0.007(2) C314 0.040(3) 0.048(3) 0.038(3) 0.005(2) 0.021(2) -0.007(2) C315 0.034(3) 0.050(3) 0.030(2) -0.009(2) 0.014(2) -0.003(2) C316 0.036(3) 0.036(3) 0.040(3) -0.005(2) 0.017(2) -0.004(2) C321 0.033(3) 0.040(3) 0.042(3) -0.005(2) 0.017(2) -0.004(2) C322 0.064(4) 0.054(4) 0.039(3) -0.003(3) 0.006(3) -0.020(3) C323 0.061(4) 0.080(5) 0.040(3) 0.005(3) 0.008(3) -0.006(4) C324 0.047(3) 0.075(5) 0.042(3) -0.024(3) 0.016(3) -0.018(3) C325 0.046(4) 0.054(4) 0.068(4) -0.020(3) 0.018(3) -0.013(3) C326 0.040(3) 0.042(3) 0.051(3) -0.015(3) 0.013(2) -0.007(2) C331 0.039(3) 0.034(3) 0.033(2) -0.007(2) 0.014(2) -0.010(2) C332 0.052(3) 0.043(3) 0.047(3) 0.001(3) 0.023(3) -0.007(3) C333 0.062(4) 0.047(4) 0.057(4) 0.008(3) 0.026(3) -0.009(3) C334 0.061(4) 0.053(4) 0.050(4) 0.016(3) 0.009(3) 0.003(3) C335 0.048(4) 0.103(7) 0.067(5) 0.029(5) 0.020(3) 0.023(4) C336 0.041(3) 0.072(5) 0.054(4) 0.023(3) 0.023(3) 0.005(3) C411 0.029(2) 0.033(3) 0.044(3) -0.001(2) 0.016(2) -0.001(2) C412 0.029(2) 0.038(3) 0.037(3) 0.000(2) 0.012(2) 0.003(2) C413 0.036(3) 0.048(3) 0.048(3) 0.004(3) 0.013(2) 0.000(2) C414 0.029(3) 0.053(4) 0.069(4) 0.006(3) 0.014(3) 0.011(3) C415 0.040(3) 0.036(3) 0.081(5) -0.003(3) 0.034(3) 0.008(2) C416 0.039(3) 0.042(3) 0.046(3) -0.006(2) 0.022(2) -0.002(2) C421 0.031(2) 0.039(3) 0.034(2) -0.003(2) 0.017(2) -0.001(2) C422 0.042(3) 0.032(3) 0.040(3) -0.003(2) 0.009(2) 0.000(2) C423 0.046(3) 0.057(4) 0.044(3) -0.004(3) 0.000(3) -0.005(3) C424 0.045(3) 0.045(4) 0.065(4) -0.010(3) 0.011(3) -0.010(3) C425 0.049(3) 0.035(3) 0.063(4) -0.002(3) 0.026(3) -0.007(3) C426 0.045(3) 0.036(3) 0.047(3) -0.001(2) 0.019(3) -0.004(2) C431 0.027(2) 0.032(3) 0.038(3) -0.005(2) 0.0092(19) -0.001(2) C432 0.033(3) 0.043(3) 0.055(3) 0.002(3) 0.019(2) -0.003(2) C433 0.047(3) 0.045(4) 0.057(4) 0.007(3) 0.021(3) 0.005(3) C434 0.053(4) 0.047(4) 0.055(4) 0.012(3) 0.015(3) -0.004(3) C435 0.051(4) 0.062(5) 0.078(5) 0.026(4) 0.034(3) 0.003(3) C436 0.045(3) 0.058(4) 0.069(4) 0.017(3) 0.033(3) 0.005(3) C501 0.106(7) 0.052(5) 0.066(5) -0.004(4) 0.005(5) 0.016(4) C601 0.290(13) 0.160(11) 0.307(13) -0.020(11) 0.103(12) -0.039(11) C701 0.192(14) 0.148(13) 0.221(14) 0.003(13) 0.066(13) -0.006(13) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.10952(7) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Au1 . Au2 . 2.5510(3) yes Au1 . Br1 . 2.4878(6) yes Au1 . P1 . 2.3329(13) yes Au1 . C212 . 2.066(5) yes Au2 . Br2 . 2.4968(6) yes Au2 . P2 . 2.3396(12) yes Au2 . C112 . 2.064(5) yes Au3 . Au4 . 2.5411(3) yes Au3 . Br3 . 2.4915(6) yes Au3 . P3 . 2.3392(13) yes Au3 . C412 . 2.072(5) yes Au4 . Br4 . 2.4844(5) yes Au4 . P4 . 2.3349(12) yes Au4 . C312 . 2.070(5) yes Cl51 . C501 . 1.765(10) yes Cl52 . C501 . 1.737(10) yes Cl61 . C601 . 1.696(15) yes Cl62 . C601 . 1.659(16) yes Cl63 . C601 . 1.760(16) yes Cl71 . C701 . 1.695(17) yes Cl72 . C701 . 1.785(17) yes P1 . C111 . 1.809(5) yes P1 . C121 . 1.803(6) yes P1 . C131 . 1.805(6) yes P2 . C211 . 1.805(5) yes P2 . C221 . 1.804(6) yes P2 . C231 . 1.795(6) yes P3 . C311 . 1.811(5) yes P3 . C321 . 1.808(5) yes P3 . C331 . 1.809(6) yes P4 . C411 . 1.810(5) yes P4 . C421 . 1.804(5) yes P4 . C431 . 1.806(6) yes F113 . C113 . 1.350(7) yes F114 . C114 . 1.357(6) yes F115 . C115 . 1.338(6) yes F116 . C116 . 1.341(6) yes F213 . C213 . 1.341(7) yes F214 . C214 . 1.345(7) yes F215 . C215 . 1.350(7) yes F216 . C216 . 1.350(7) yes F313 . C313 . 1.355(6) yes F314 . C314 . 1.338(6) yes F315 . C315 . 1.340(6) yes F316 . C316 . 1.342(6) yes F413 . C413 . 1.340(7) yes F414 . C414 . 1.353(7) yes F415 . C415 . 1.339(7) yes F416 . C416 . 1.343(7) yes C111 . C112 . 1.412(7) yes C111 . C116 . 1.398(7) yes C112 . C113 . 1.369(7) yes C113 . C114 . 1.368(8) yes C114 . C115 . 1.379(9) yes C115 . C116 . 1.373(8) yes C121 . C122 . 1.394(9) yes C121 . C126 . 1.370(9) yes C122 . C123 . 1.388(10) yes C122 . H1221 . 1.000 no C123 . C124 . 1.356(13) yes C123 . H1231 . 1.000 no C124 . C125 . 1.348(13) yes C124 . H1241 . 1.000 no C125 . C126 . 1.404(10) yes C125 . H1251 . 1.000 no C126 . H1261 . 1.000 no C131 . C132 . 1.397(8) yes C131 . C136 . 1.396(8) yes C132 . C133 . 1.376(9) yes C132 . H1321 . 1.000 no C133 . C134 . 1.399(10) yes C133 . H1331 . 1.000 no C134 . C135 . 1.373(10) yes C134 . H1341 . 1.000 no C135 . C136 . 1.382(9) yes C135 . H1351 . 1.000 no C136 . H1361 . 1.000 no C211 . C212 . 1.398(8) yes C211 . C216 . 1.383(7) yes C212 . C213 . 1.396(7) yes C213 . C214 . 1.360(8) yes C214 . C215 . 1.364(10) yes C215 . C216 . 1.381(9) yes C221 . C222 . 1.397(8) yes C221 . C226 . 1.375(8) yes C222 . C223 . 1.384(8) yes C222 . H2221 . 1.000 no C223 . C224 . 1.383(9) yes C223 . H2231 . 1.000 no C224 . C225 . 1.377(9) yes C224 . H2241 . 1.000 no C225 . C226 . 1.395(9) yes C225 . H2251 . 1.000 no C226 . H2261 . 1.000 no C231 . C232 . 1.376(8) yes C231 . C236 . 1.370(8) yes C232 . C233 . 1.386(9) yes C232 . H2321 . 1.000 no C233 . C234 . 1.373(11) yes C233 . H2331 . 1.000 no C234 . C235 . 1.367(12) yes C234 . H2341 . 1.000 no C235 . C236 . 1.384(11) yes C235 . H2351 . 1.000 no C236 . H2361 . 1.000 no C311 . C312 . 1.407(7) yes C311 . C316 . 1.401(7) yes C312 . C313 . 1.375(7) yes C313 . C314 . 1.376(7) yes C314 . C315 . 1.383(8) yes C315 . C316 . 1.366(7) yes C321 . C322 . 1.383(9) yes C321 . C326 . 1.380(8) yes C322 . C323 . 1.361(9) yes C322 . H3221 . 1.000 no C323 . C324 . 1.402(11) yes C323 . H3231 . 1.000 no C324 . C325 . 1.364(10) yes C324 . H3241 . 1.000 no C325 . C326 . 1.408(9) yes C325 . H3251 . 1.000 no C326 . H3261 . 1.000 no C331 . C332 . 1.394(7) yes C331 . C336 . 1.385(8) yes C332 . C333 . 1.380(9) yes C332 . H3321 . 1.000 no C333 . C334 . 1.370(10) yes C333 . H3331 . 1.000 no C334 . C335 . 1.383(10) yes C334 . H3341 . 1.000 no C335 . C336 . 1.383(10) yes C335 . H3351 . 1.000 no C336 . H3361 . 1.000 no C411 . C412 . 1.402(7) yes C411 . C416 . 1.391(7) yes C412 . C413 . 1.378(8) yes C413 . C414 . 1.382(9) yes C414 . C415 . 1.367(10) yes C415 . C416 . 1.376(8) yes C421 . C422 . 1.384(7) yes C421 . C426 . 1.395(8) yes C422 . C423 . 1.387(8) yes C422 . H4221 . 1.000 no C423 . C424 . 1.388(10) yes C423 . H4231 . 1.000 no C424 . C425 . 1.375(9) yes C424 . H4241 . 1.000 no C425 . C426 . 1.381(8) yes C425 . H4251 . 1.000 no C426 . H4261 . 1.000 no C431 . C432 . 1.387(8) yes C431 . C436 . 1.391(7) yes C432 . C433 . 1.388(8) yes C432 . H4321 . 1.000 no C433 . C434 . 1.370(9) yes C433 . H4331 . 1.000 no C434 . C435 . 1.396(9) yes C434 . H4341 . 1.000 no C435 . C436 . 1.378(9) yes C435 . H4351 . 1.000 no C436 . H4361 . 1.000 no C501 . H5011 . 1.000 no C501 . H5012 . 1.000 no C601 . H6011 . 1.000 no C601 . H6012 . 1.000 no C601 . H6013 . 1.000 no C601 . H6014 . 1.000 no C701 . H7011 . 1.000 no C701 . H7012 . 1.000 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag Au2 . Au1 . Br1 . 164.393(17) yes Au2 . Au1 . P1 . 85.36(3) yes Br1 . Au1 . P1 . 92.88(4) yes Au2 . Au1 . C212 . 90.10(15) yes Br1 . Au1 . C212 . 91.97(15) yes P1 . Au1 . C212 . 175.13(15) yes Au1 . Au2 . Br2 . 164.957(17) yes Au1 . Au2 . P2 . 82.77(3) yes Br2 . Au2 . P2 . 93.38(4) yes Au1 . Au2 . C112 . 90.44(14) yes Br2 . Au2 . C112 . 92.86(14) yes P2 . Au2 . C112 . 173.09(15) yes Au4 . Au3 . Br3 . 169.52(2) yes Au4 . Au3 . P3 . 84.11(3) yes Br3 . Au3 . P3 . 92.90(4) yes Au4 . Au3 . C412 . 89.50(14) yes Br3 . Au3 . C412 . 93.31(14) yes P3 . Au3 . C412 . 173.60(14) yes Au3 . Au4 . Br4 . 171.612(17) yes Au3 . Au4 . P4 . 81.84(3) yes Br4 . Au4 . P4 . 93.72(3) yes Au3 . Au4 . C312 . 90.69(13) yes Br4 . Au4 . C312 . 93.12(13) yes P4 . Au4 . C312 . 171.28(14) yes Au1 . P1 . C111 . 106.24(17) yes Au1 . P1 . C121 . 111.60(19) yes C111 . P1 . C121 . 105.4(2) yes Au1 . P1 . C131 . 112.50(18) yes C111 . P1 . C131 . 110.5(2) yes C121 . P1 . C131 . 110.3(3) yes Au2 . P2 . C211 . 105.85(17) yes Au2 . P2 . C221 . 116.00(16) yes C211 . P2 . C221 . 106.8(2) yes Au2 . P2 . C231 . 109.16(18) yes C211 . P2 . C231 . 110.3(2) yes C221 . P2 . C231 . 108.6(2) yes Au3 . P3 . C311 . 106.95(18) yes Au3 . P3 . C321 . 111.50(18) yes C311 . P3 . C321 . 105.2(2) yes Au3 . P3 . C331 . 113.88(17) yes C311 . P3 . C331 . 111.1(2) yes C321 . P3 . C331 . 107.9(2) yes Au4 . P4 . C411 . 105.16(18) yes Au4 . P4 . C421 . 113.97(16) yes C411 . P4 . C421 . 109.9(2) yes Au4 . P4 . C431 . 110.97(17) yes C411 . P4 . C431 . 108.4(2) yes C421 . P4 . C431 . 108.3(2) yes P1 . C111 . C112 . 117.1(4) yes P1 . C111 . C116 . 122.1(4) yes C112 . C111 . C116 . 119.9(5) yes C111 . C112 . Au2 . 119.6(4) yes C111 . C112 . C113 . 117.0(5) yes Au2 . C112 . C113 . 123.1(4) yes F113 . C113 . C112 . 121.0(5) yes F113 . C113 . C114 . 116.3(5) yes C112 . C113 . C114 . 122.7(5) yes F114 . C114 . C113 . 120.5(5) yes F114 . C114 . C115 . 118.6(5) yes C113 . C114 . C115 . 120.9(5) yes C114 . C115 . F115 . 120.4(5) yes C114 . C115 . C116 . 118.3(5) yes F115 . C115 . C116 . 121.3(5) yes C111 . C116 . F116 . 120.6(5) yes C111 . C116 . C115 . 121.2(5) yes F116 . C116 . C115 . 118.1(5) yes P1 . C121 . C122 . 116.9(5) yes P1 . C121 . C126 . 123.8(5) yes C122 . C121 . C126 . 119.2(6) yes C121 . C122 . C123 . 120.0(8) yes C121 . C122 . H1221 . 120.0 no C123 . C122 . H1221 . 120.0 no C122 . C123 . C124 . 120.0(8) yes C122 . C123 . H1231 . 120.0 no C124 . C123 . H1231 . 120.0 no C123 . C124 . C125 . 120.9(7) yes C123 . C124 . H1241 . 119.6 no C125 . C124 . H1241 . 119.6 no C124 . C125 . C126 . 120.5(8) yes C124 . C125 . H1251 . 119.8 no C126 . C125 . H1251 . 119.8 no C125 . C126 . C121 . 119.5(7) yes C125 . C126 . H1261 . 120.2 no C121 . C126 . H1261 . 120.3 no P1 . C131 . C132 . 119.1(4) yes P1 . C131 . C136 . 120.9(4) yes C132 . C131 . C136 . 120.0(5) yes C131 . C132 . C133 . 119.7(6) yes C131 . C132 . H1321 . 120.2 no C133 . C132 . H1321 . 120.1 no C132 . C133 . C134 . 120.2(7) yes C132 . C133 . H1331 . 119.9 no C134 . C133 . H1331 . 119.9 no C133 . C134 . C135 . 119.8(6) yes C133 . C134 . H1341 . 120.1 no C135 . C134 . H1341 . 120.1 no C134 . C135 . C136 . 120.8(6) yes C134 . C135 . H1351 . 119.6 no C136 . C135 . H1351 . 119.6 no C131 . C136 . C135 . 119.5(6) yes C131 . C136 . H1361 . 120.3 no C135 . C136 . H1361 . 120.3 no P2 . C211 . C212 . 115.2(4) yes P2 . C211 . C216 . 125.3(4) yes C212 . C211 . C216 . 119.0(5) yes C211 . C212 . Au1 . 120.3(4) yes C211 . C212 . C213 . 118.6(5) yes Au1 . C212 . C213 . 121.0(4) yes C212 . C213 . F213 . 121.1(5) yes C212 . C213 . C214 . 121.2(6) yes F213 . C213 . C214 . 117.7(5) yes F214 . C214 . C213 . 121.0(6) yes F214 . C214 . C215 . 118.6(6) yes C213 . C214 . C215 . 120.3(5) yes F215 . C215 . C214 . 120.4(6) yes F215 . C215 . C216 . 119.8(6) yes C214 . C215 . C216 . 119.8(5) yes F216 . C216 . C211 . 121.7(5) yes F216 . C216 . C215 . 117.4(5) yes C211 . C216 . C215 . 120.9(6) yes P2 . C221 . C222 . 117.5(4) yes P2 . C221 . C226 . 122.6(4) yes C222 . C221 . C226 . 119.8(5) yes C221 . C222 . C223 . 120.3(5) yes C221 . C222 . H2221 . 119.9 no C223 . C222 . H2221 . 119.9 no C222 . C223 . C224 . 119.7(5) yes C222 . C223 . H2231 . 120.1 no C224 . C223 . H2231 . 120.1 no C223 . C224 . C225 . 120.0(6) yes C223 . C224 . H2241 . 120.0 no C225 . C224 . H2241 . 120.0 no C224 . C225 . C226 . 120.6(6) yes C224 . C225 . H2251 . 119.7 no C226 . C225 . H2251 . 119.7 no C225 . C226 . C221 . 119.6(6) yes C225 . C226 . H2261 . 120.2 no C221 . C226 . H2261 . 120.2 no P2 . C231 . C232 . 118.6(4) yes P2 . C231 . C236 . 122.1(5) yes C232 . C231 . C236 . 119.3(6) yes C231 . C232 . C233 . 120.8(6) yes C231 . C232 . H2321 . 119.6 no C233 . C232 . H2321 . 119.6 no C232 . C233 . C234 . 119.7(7) yes C232 . C233 . H2331 . 120.1 no C234 . C233 . H2331 . 120.1 no C233 . C234 . C235 . 119.2(7) yes C233 . C234 . H2341 . 120.4 no C235 . C234 . H2341 . 120.4 no C234 . C235 . C236 . 121.3(7) yes C234 . C235 . H2351 . 119.4 no C236 . C235 . H2351 . 119.4 no C235 . C236 . C231 . 119.7(7) yes C235 . C236 . H2361 . 120.2 no C231 . C236 . H2361 . 120.2 no P3 . C311 . C312 . 116.3(4) yes P3 . C311 . C316 . 123.2(4) yes C312 . C311 . C316 . 119.9(4) yes C311 . C312 . Au4 . 118.3(3) yes C311 . C312 . C313 . 117.2(4) yes Au4 . C312 . C313 . 123.7(4) yes F313 . C313 . C312 . 121.3(5) yes F313 . C313 . C314 . 115.9(5) yes C312 . C313 . C314 . 122.8(5) yes F314 . C314 . C313 . 121.2(5) yes F314 . C314 . C315 . 119.3(5) yes C313 . C314 . C315 . 119.4(5) yes C314 . C315 . F315 . 119.1(5) yes C314 . C315 . C316 . 119.6(5) yes F315 . C315 . C316 . 121.2(5) yes C311 . C316 . F316 . 121.1(5) yes C311 . C316 . C315 . 120.8(5) yes F316 . C316 . C315 . 118.1(5) yes P3 . C321 . C322 . 117.9(4) yes P3 . C321 . C326 . 122.0(4) yes C322 . C321 . C326 . 120.0(5) yes C321 . C322 . C323 . 120.8(7) yes C321 . C322 . H3221 . 119.6 no C323 . C322 . H3221 . 119.6 no C322 . C323 . C324 . 120.3(7) yes C322 . C323 . H3231 . 119.9 no C324 . C323 . H3231 . 119.9 no C323 . C324 . C325 . 119.1(6) yes C323 . C324 . H3241 . 120.5 no C325 . C324 . H3241 . 120.5 no C324 . C325 . C326 . 121.0(6) yes C324 . C325 . H3251 . 119.5 no C326 . C325 . H3251 . 119.5 no C325 . C326 . C321 . 118.8(6) yes C325 . C326 . H3261 . 120.6 no C321 . C326 . H3261 . 120.6 no P3 . C331 . C332 . 118.1(4) yes P3 . C331 . C336 . 122.1(4) yes C332 . C331 . C336 . 119.7(6) yes C331 . C332 . C333 . 119.7(6) yes C331 . C332 . H3321 . 120.1 no C333 . C332 . H3321 . 120.1 no C332 . C333 . C334 . 120.3(6) yes C332 . C333 . H3331 . 119.8 no C334 . C333 . H3331 . 119.8 no C333 . C334 . C335 . 120.3(6) yes C333 . C334 . H3341 . 119.9 no C335 . C334 . H3341 . 119.9 no C334 . C335 . C336 . 120.0(7) yes C334 . C335 . H3351 . 120.0 no C336 . C335 . H3351 . 120.0 no C331 . C336 . C335 . 119.9(6) yes C331 . C336 . H3361 . 120.1 no C335 . C336 . H3361 . 120.1 no P4 . C411 . C412 . 114.3(4) yes P4 . C411 . C416 . 124.9(4) yes C412 . C411 . C416 . 120.7(5) yes C411 . C412 . Au3 . 119.6(4) yes C411 . C412 . C413 . 117.2(5) yes Au3 . C412 . C413 . 123.0(4) yes F413 . C413 . C412 . 121.5(5) yes F413 . C413 . C414 . 117.0(5) yes C412 . C413 . C414 . 121.5(6) yes F414 . C414 . C413 . 119.9(6) yes F414 . C414 . C415 . 119.0(6) yes C413 . C414 . C415 . 121.0(5) yes F415 . C415 . C414 . 120.3(6) yes F415 . C415 . C416 . 120.7(6) yes C414 . C415 . C416 . 118.9(5) yes C411 . C416 . F416 . 122.1(5) yes C411 . C416 . C415 . 120.4(5) yes F416 . C416 . C415 . 117.5(5) yes P4 . C421 . C422 . 121.4(4) yes P4 . C421 . C426 . 118.3(4) yes C422 . C421 . C426 . 120.1(5) yes C421 . C422 . C423 . 120.2(6) yes C421 . C422 . H4221 . 119.9 no C423 . C422 . H4221 . 119.9 no C422 . C423 . C424 . 119.7(6) yes C422 . C423 . H4231 . 120.2 no C424 . C423 . H4231 . 120.2 no C423 . C424 . C425 . 119.7(6) yes C423 . C424 . H4241 . 120.2 no C425 . C424 . H4241 . 120.2 no C424 . C425 . C426 . 121.4(6) yes C424 . C425 . H4251 . 119.3 no C426 . C425 . H4251 . 119.3 no C421 . C426 . C425 . 118.9(6) yes C421 . C426 . H4261 . 120.6 no C425 . C426 . H4261 . 120.6 no P4 . C431 . C432 . 118.9(4) yes P4 . C431 . C436 . 121.7(4) yes C432 . C431 . C436 . 119.4(5) yes C431 . C432 . C433 . 119.9(5) yes C431 . C432 . H4321 . 120.0 no C433 . C432 . H4321 . 120.0 no C432 . C433 . C434 . 120.7(6) yes C432 . C433 . H4331 . 119.6 no C434 . C433 . H4331 . 119.6 no C433 . C434 . C435 . 119.4(6) yes C433 . C434 . H4341 . 120.3 no C435 . C434 . H4341 . 120.3 no C434 . C435 . C436 . 120.2(6) yes C434 . C435 . H4351 . 119.9 no C436 . C435 . H4351 . 119.9 no C431 . C436 . C435 . 120.2(6) yes C431 . C436 . H4361 . 119.9 no C435 . C436 . H4361 . 119.9 no Cl51 . C501 . Cl52 . 111.8(5) yes Cl51 . C501 . H5011 . 108.9 no Cl52 . C501 . H5011 . 108.9 no Cl51 . C501 . H5012 . 108.9 no Cl52 . C501 . H5012 . 108.9 no H5011 . C501 . H5012 . 109.5 no Cl63 . C601 . Cl61 . 97.0(10) yes Cl61 . C601 . Cl62 . 120.6(13) yes Cl61 . C601 . H6011 . 107.0 no Cl62 . C601 . H6011 . 107.2 no Cl61 . C601 . H6012 . 106.1 no Cl62 . C601 . H6012 . 106.1 no H6011 . C601 . H6012 . 109.5 no Cl63 . C601 . H6013 . 112.9 no Cl61 . C601 . H6013 . 113.2 no Cl63 . C601 . H6014 . 112.0 no Cl61 . C601 . H6014 . 111.8 no H6013 . C601 . H6014 . 109.5 no Cl72 . C701 . Cl71 . 109.1(10) yes Cl72 . C701 . H7011 . 109.5 no Cl71 . C701 . H7011 . 109.6 no Cl72 . C701 . H7012 . 109.6 no Cl71 . C701 . H7012 . 109.6 no H7011 . C701 . H7012 . 109.5 no #------------------------------------------------------------------------------ loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag Br1 C415 3.349(7) . 2_666 no Br1 C414 3.483(7) . 2_666 no Br2 C315 3.453(5) . 2_566 no Br2 C316 3.559(5) . 2_566 no Br2 F315 3.562(3) . 2_566 no Br3 C215 3.566(8) . 2_666 no Br4 C116 3.432(5) . 2_566 no Br4 C115 3.495(6) . 2_566 no Br4 F116 3.528(3) . 2_566 no cl51 F314 3.364(5) . 1_655 no cl51 F313 3.383(4) . 2_666 no cl51 F114 3.418(5) . 3_656 no cl52 F313 3.391(5) . 2_666 no cl52 cl72 3.585(8) . 2_666 no cl61 C415 3.494(9) . 2_666 no cl61 F415 3.510(9) . 2_666 no cl61 C416 3.593(8) . 2_666 no cl62 F213 3.23(2) . 3_656 no cl62 C701 3.47(3) . . no cl63 cl72 2.77(2) . 2_666 no cl63 C701 3.11(3) . . no cl72 F414 3.494(9) . 2_666 no F113 C425 3.419(8) . 4 no F113 C501 3.48(1) . 3_646 no F114 C433 3.282(8) . 2_566 no F114 C432 3.371(6) . 2_566 no F114 C501 3.444(9) . 3_646 no F114 C233 3.563(8) . 4 no F115 F315 3.316(6) . 3_546 no F115 C422 3.424(7) . 2_566 no F115 C226 3.498(7) . 4 no F116 C225 3.228(8) . 4 no F116 C226 3.510(8) . 4 no F213 C435 3.448(8) . 2_666 no F214 C435 3.377(7) . 2_666 no F214 F415 3.507(6) . 4 no F215 C125 3.02(1) . 3_646 no F215 C126 3.288(9) . 3_646 no F215 F415 3.352(8) . 4 no F216 C124 3.05(1) . 4_554 no F216 C123 3.517(9) . 4_554 no F216 C325 3.551(8) . 1_545 no F313 C501 3.127(9) . 2_666 no F313 C135 3.474(7) . 2_566 no F314 C433 3.512(7) . 4_565 no F314 C135 3.590(7) . 2_566 no F315 C422 3.198(7) . 4_565 no F315 C433 3.431(7) . 4_565 no F315 C432 3.536(7) . 4_565 no F315 C423 3.589(8) . 4_565 no F316 C224 3.426(7) . 1_565 no F413 C235 3.306(9) . 2_666 no F413 C701 3.60(3) . . no F414 C701 3.50(3) . 2_666 no F414 C133 3.55(1) . 2_666 no F415 C215 3.224(9) . 4_554 no F415 C214 3.309(8) . 4_554 no F416 C223 3.289(7) . 4_554 no F416 C222 3.340(7) . 4_554 no F416 C324 3.456(9) . 4_564 no C123 C324 3.48(1) . 3_646 no C124 C324 3.50(1) . 3_646 no C222 C425 3.53(1) . 4 no C223 C424 3.38(1) . 4 no C223 C325 3.48(1) . 1_545 no C223 C423 3.49(1) . 4 no C224 C326 3.43(1) . 1_545 no C224 C325 3.579(9) . 1_545 no C225 C423 3.578(9) . 3_545 no #------------------------------------------------------------------------------ loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion _geom_torsion_publ_flag Au1 Au2 P2 C211 . . . . 41.4(2) no Au1 Au2 P2 C221 . . . . 159.5(2) no Au1 Au2 P2 C231 . . . . -77.4(2) no Au1 Au2 C112 C111 . . . . 41.9(3) no Au1 Au2 C112 C113 . . . . -144.8(4) no Au1 P1 C111 C112 . . . . -16.7(3) no Au1 P1 C111 C116 . . . . 152.3(3) no Au1 P1 C121 C122 . . . . -47.4(6) no Au1 P1 C121 C126 . . . . 135.7(6) no Au1 P1 C131 C132 . . . . -67.0(6) no Au1 P1 C131 C136 . . . . 110.7(6) no Au1 C212 C211 P2 . . . . -13.6(6) no Au1 C212 C211 C216 . . . . 173.5(5) no Au1 C212 C213 F213 . . . . 6.1(9) no Au1 C212 C213 C214 . . . . -176.5(5) no Au2 Au1 P1 C111 . . . . 34.5(1) no Au2 Au1 P1 C121 . . . . 148.8(2) no Au2 Au1 P1 C131 . . . . -86.6(2) no Au2 Au1 C212 C211 . . . . 41.3(5) no Au2 Au1 C212 C213 . . . . -142.2(5) no Au2 P2 C211 C212 . . . . -26.2(5) no Au2 P2 C211 C216 . . . . 146.2(5) no Au2 P2 C221 C222 . . . . -55.2(5) no Au2 P2 C221 C226 . . . . 126.6(5) no Au2 P2 C231 C232 . . . . -53.8(5) no Au2 P2 C231 C236 . . . . 124.1(6) no Au2 C112 C111 P1 . . . . -20.3(4) no Au2 C112 C111 C116 . . . . 170.5(3) no Au2 C112 C113 F113 . . . . 9.4(6) no Au2 C112 C113 C114 . . . . -171.5(4) no Au3 Au4 P4 C411 . . . . 44.8(2) no Au3 Au4 P4 C421 . . . . 165.2(2) no Au3 Au4 P4 C431 . . . . -72.3(2) no Au3 Au4 C312 C311 . . . . 45.2(3) no Au3 Au4 C312 C313 . . . . -145.3(4) no Au3 P3 C311 C312 . . . . -15.4(3) no Au3 P3 C311 C316 . . . . 155.8(3) no Au3 P3 C321 C322 . . . . -56.0(6) no Au3 P3 C321 C326 . . . . 123.1(6) no Au3 P3 C331 C332 . . . . -42.2(5) no Au3 P3 C331 C336 . . . . 140.5(4) no Au3 C412 C411 P4 . . . . -12.8(6) no Au3 C412 C411 C416 . . . . 169.8(5) no Au3 C412 C413 F413 . . . . 8.7(9) no Au3 C412 C413 C414 . . . . -171.2(5) no Au4 Au3 P3 C311 . . . . 35.2(1) no Au4 Au3 P3 C321 . . . . 149.6(2) no Au4 Au3 P3 C331 . . . . -87.9(2) no Au4 Au3 C412 C411 . . . . 43.0(5) no Au4 Au3 C412 C413 . . . . -142.2(5) no Au4 P4 C411 C412 . . . . -29.0(5) no Au4 P4 C411 C416 . . . . 148.3(5) no Au4 P4 C421 C422 . . . . 108.7(5) no Au4 P4 C421 C426 . . . . -66.1(5) no Au4 P4 C431 C432 . . . . -44.1(4) no Au4 P4 C431 C436 . . . . 135.9(4) no Au4 C312 C311 P3 . . . . -23.2(4) no Au4 C312 C311 C316 . . . . 165.3(3) no Au4 C312 C313 F313 . . . . 15.8(6) no Au4 C312 C313 C314 . . . . -165.6(3) no Br1 Au1 P1 C111 . . . . -161.1(1) no Br1 Au1 P1 C121 . . . . -46.7(2) no Br1 Au1 P1 C131 . . . . 77.9(2) no Br1 Au1 C212 C211 . . . . -123.2(5) no Br1 Au1 C212 C213 . . . . 53.2(6) no Br2 Au2 P2 C211 . . . . -153.2(2) no Br2 Au2 P2 C221 . . . . -35.1(2) no Br2 Au2 P2 C231 . . . . 88.0(2) no Br2 Au2 C112 C111 . . . . -123.4(3) no Br2 Au2 C112 C113 . . . . 49.9(4) no Br3 Au3 P3 C311 . . . . -154.9(1) no Br3 Au3 P3 C321 . . . . -40.4(2) no Br3 Au3 P3 C331 . . . . 82.0(2) no Br3 Au3 C412 C411 . . . . -126.9(5) no Br3 Au3 C412 C413 . . . . 47.9(5) no Br4 Au4 P4 C411 . . . . -142.4(2) no Br4 Au4 P4 C421 . . . . -22.0(2) no Br4 Au4 P4 C431 . . . . 100.6(2) no Br4 Au4 C312 C311 . . . . -127.3(3) no Br4 Au4 C312 C313 . . . . 42.2(4) no P1 Au1 Au2 P2 . . . . 142.28(5) no P1 Au1 Au2 C112 . . . . -36.4(1) no P1 C111 C112 C113 . . . . 166.0(3) no P1 C111 C116 F116 . . . . 15.7(6) no P1 C111 C116 C115 . . . . -166.4(4) no P1 C121 C122 C123 . . . . -176.3(6) no P1 C121 C126 C125 . . . . 177.1(7) no P1 C131 C132 C133 . . . . 176.0(6) no P1 C131 C136 C135 . . . . -176.2(5) no P2 Au2 Au1 C212 . . . . -39.5(2) no P2 C211 C212 C213 . . . . 169.9(5) no P2 C211 C216 F216 . . . . 10.2(9) no P2 C211 C216 C215 . . . . -168.8(5) no P2 C221 C222 C223 . . . . -176.9(5) no P2 C221 C226 C225 . . . . 178.1(5) no P2 C231 C232 C233 . . . . 178.0(6) no P2 C231 C236 C235 . . . . -177.1(7) no P3 Au3 Au4 P4 . . . . 137.47(5) no P3 Au3 Au4 C312 . . . . -38.0(1) no P3 C311 C312 C313 . . . . 166.6(3) no P3 C311 C316 F316 . . . . 11.5(6) no P3 C311 C316 C315 . . . . -169.1(4) no P3 C321 C322 C323 . . . . -179.2(6) no P3 C321 C326 C325 . . . . 179.3(6) no P3 C331 C332 C333 . . . . -175.6(5) no P3 C331 C336 C335 . . . . 174.5(5) no P4 Au4 Au3 C412 . . . . -42.1(1) no P4 C411 C412 C413 . . . . 172.2(5) no P4 C411 C416 F416 . . . . 6.8(9) no P4 C411 C416 C415 . . . . -173.4(5) no P4 C421 C422 C423 . . . . -174.1(5) no P4 C421 C426 C425 . . . . 175.3(6) no P4 C431 C432 C433 . . . . -178.4(4) no P4 C431 C436 C435 . . . . 179.1(5) no F113 C113 C112 C111 . . . . -177.0(4) no F113 C113 C114 F114 . . . . -0.7(7) no F113 C113 C114 C115 . . . . 179.4(4) no F114 C114 C113 C112 . . . . -179.9(4) no F114 C114 C115 F115 . . . . -1.8(7) no F114 C114 C115 C116 . . . . 178.8(4) no F115 C115 C114 C113 . . . . 178.1(5) no F115 C115 C116 F116 . . . . -1.4(7) no F115 C115 C116 C111 . . . . -179.4(4) no F116 C116 C111 C112 . . . . -175.6(4) no F116 C116 C115 C114 . . . . 178.0(4) no F213 C213 C212 C211 . . . . -177.3(6) no F213 C213 C214 F214 . . . . -2(1) no F213 C213 C214 C215 . . . . -179.8(7) no F214 C214 C213 C212 . . . . -179.5(6) no F214 C214 C215 F215 . . . . 1(1) no F214 C214 C215 C216 . . . . 179.7(7) no F215 C215 C214 C213 . . . . 178.4(7) no F215 C215 C216 F216 . . . . -0(1) no F215 C215 C216 C211 . . . . 178.6(6) no F216 C216 C211 C212 . . . . -177.7(6) no F216 C216 C215 C214 . . . . -179.7(7) no F313 C313 C312 C311 . . . . -174.6(4) no F313 C313 C314 F314 . . . . -2.9(6) no F313 C313 C314 C315 . . . . 178.9(4) no F314 C314 C313 C312 . . . . 178.5(4) no F314 C314 C315 F315 . . . . -0.9(6) no F314 C314 C315 C316 . . . . 178.2(4) no F315 C315 C314 C313 . . . . 177.4(4) no F315 C315 C316 F316 . . . . 1.0(7) no F315 C315 C316 C311 . . . . -178.4(4) no F316 C316 C311 C312 . . . . -177.6(4) no F316 C316 C315 C314 . . . . -178.1(4) no F413 C413 C412 C411 . . . . -176.4(6) no F413 C413 C414 F414 . . . . -1.3(9) no F413 C413 C414 C415 . . . . 179.6(6) no F414 C414 C413 C412 . . . . 178.6(6) no F414 C414 C415 F415 . . . . -0(1) no F414 C414 C415 C416 . . . . 179.7(6) no F415 C415 C414 C413 . . . . 178.7(6) no F415 C415 C416 F416 . . . . -1(1) no F415 C415 C416 C411 . . . . 179.7(6) no F416 C416 C411 C412 . . . . -176.0(6) no F416 C416 C415 C414 . . . . 179.3(6) no C111 P1 C121 C122 . . . . 67.5(6) no C111 P1 C121 C126 . . . . -109.4(7) no C111 P1 C131 C132 . . . . 174.4(5) no C111 P1 C131 C136 . . . . -8.0(7) no C111 C112 C113 C114 . . . . 2.0(7) no C111 C116 C115 C114 . . . . 0.1(7) no C112 Au2 Au1 C212 . . . . 141.8(2) no C112 C111 P1 C121 . . . . -135.3(3) no C112 C111 P1 C131 . . . . 105.6(4) no C112 C111 C116 C115 . . . . 2.3(6) no C112 C113 C114 C115 . . . . 0.3(8) no C113 C112 C111 C116 . . . . -3.3(6) no C113 C114 C115 C116 . . . . -1.4(8) no C116 C111 P1 C121 . . . . 33.7(4) no C116 C111 P1 C131 . . . . -85.4(4) no C121 P1 C131 C132 . . . . 58.4(6) no C121 P1 C131 C136 . . . . -124.0(6) no C121 C122 C123 C124 . . . . -2(1) no C121 C126 C125 C124 . . . . -0(1) no C122 C121 P1 C131 . . . . -173.2(5) no C122 C121 C126 C125 . . . . 0(1) no C122 C123 C124 C125 . . . . 2(2) no C123 C122 C121 C126 . . . . 1(1) no C123 C124 C125 C126 . . . . -1(2) no C126 C121 P1 C131 . . . . 9.8(8) no C131 C132 C133 C134 . . . . 0(1) no C131 C136 C135 C134 . . . . 0(1) no C132 C131 C136 C135 . . . . 1(1) no C132 C133 C134 C135 . . . . 2(1) no C133 C132 C131 C136 . . . . -2(1) no C133 C134 C135 C136 . . . . -2(1) no C211 P2 C221 C222 . . . . 62.4(5) no C211 P2 C221 C226 . . . . -115.7(5) no C211 P2 C231 C232 . . . . -169.8(5) no C211 P2 C231 C236 . . . . 8.1(6) no C211 C212 C213 C214 . . . . 0(1) no C211 C216 C215 C214 . . . . -1(1) no C212 C211 P2 C221 . . . . -150.3(4) no C212 C211 P2 C231 . . . . 91.8(5) no C212 C211 C216 C215 . . . . 3(1) no C212 C213 C214 C215 . . . . 3(1) no C213 C212 C211 C216 . . . . -3.0(9) no C213 C214 C215 C216 . . . . -2(1) no C216 C211 P2 C221 . . . . 22.1(6) no C216 C211 P2 C231 . . . . -95.8(6) no C221 P2 C231 C232 . . . . 73.5(5) no C221 P2 C231 C236 . . . . -108.6(6) no C221 C222 C223 C224 . . . . -2(1) no C221 C226 C225 C224 . . . . -1(1) no C222 C221 P2 C231 . . . . -178.5(5) no C222 C221 C226 C225 . . . . -0(1) no C222 C223 C224 C225 . . . . 1(1) no C223 C222 C221 C226 . . . . 1(1) no C223 C224 C225 C226 . . . . 0(1) no C226 C221 P2 C231 . . . . 3.3(6) no C231 C232 C233 C234 . . . . -1(1) no C231 C236 C235 C234 . . . . -1(2) no C232 C231 C236 C235 . . . . 1(1) no C232 C233 C234 C235 . . . . 0(1) no C233 C232 C231 C236 . . . . 0(1) no C233 C234 C235 C236 . . . . 1(2) no C311 P3 C321 C322 . . . . 59.6(6) no C311 P3 C321 C326 . . . . -121.4(6) no C311 P3 C331 C332 . . . . -163.1(4) no C311 P3 C331 C336 . . . . 19.7(6) no C311 C312 C313 C314 . . . . 4.0(6) no C311 C316 C315 C314 . . . . 2.5(7) no C312 Au4 Au3 C412 . . . . 142.5(2) no C312 C311 P3 C321 . . . . -134.0(3) no C312 C311 P3 C331 . . . . 109.5(4) no C312 C311 C316 C315 . . . . 1.8(7) no C312 C313 C314 C315 . . . . 0.2(7) no C313 C312 C311 C316 . . . . -4.9(6) no C313 C314 C315 C316 . . . . -3.5(6) no C316 C311 P3 C321 . . . . 37.2(4) no C316 C311 P3 C331 . . . . -79.3(4) no C321 P3 C331 C332 . . . . 82.2(5) no C321 P3 C331 C336 . . . . -95.1(5) no C321 C322 C323 C324 . . . . -1(1) no C321 C326 C325 C324 . . . . 1(1) no C322 C321 P3 C331 . . . . 178.2(5) no C322 C321 C326 C325 . . . . -2(1) no C322 C323 C324 C325 . . . . -0(1) no C323 C322 C321 C326 . . . . 2(1) no C323 C324 C325 C326 . . . . 0(1) no C326 C321 P3 C331 . . . . -2.7(7) no C331 C332 C333 C334 . . . . 1.4(9) no C331 C336 C335 C334 . . . . 1(1) no C332 C331 C336 C335 . . . . -2.7(9) no C332 C333 C334 C335 . . . . -4(1) no C333 C332 C331 C336 . . . . 1.7(9) no C333 C334 C335 C336 . . . . 3(1) no C411 P4 C421 C422 . . . . -133.5(5) no C411 P4 C421 C426 . . . . 51.7(6) no C411 P4 C431 C432 . . . . -159.2(4) no C411 P4 C431 C436 . . . . 20.9(5) no C411 C412 C413 C414 . . . . 4(1) no C411 C416 C415 C414 . . . . -0(1) no C412 C411 P4 C421 . . . . -152.1(4) no C412 C411 P4 C431 . . . . 89.8(5) no C412 C411 C416 C415 . . . . 4(1) no C412 C413 C414 C415 . . . . -1(1) no C413 C412 C411 C416 . . . . -5.3(9) no C413 C414 C415 C416 . . . . -1(1) no C416 C411 P4 C421 . . . . 25.2(6) no C416 C411 P4 C431 . . . . -92.9(5) no C421 P4 C431 C432 . . . . 81.6(5) no C421 P4 C431 C436 . . . . -98.3(4) no C421 C422 C423 C424 . . . . -1(1) no C421 C426 C425 C424 . . . . -1(1) no C422 C421 P4 C431 . . . . -15.3(6) no C422 C421 C426 C425 . . . . 0(1) no C422 C423 C424 C425 . . . . 1(1) no C423 C422 C421 C426 . . . . 1(1) no C423 C424 C425 C426 . . . . -0(1) no C426 C421 P4 C431 . . . . 169.9(5) no C431 C432 C433 C434 . . . . -0.8(9) no C431 C436 C435 C434 . . . . -1(1) no C432 C431 C436 C435 . . . . -0.8(8) no C432 C433 C434 C435 . . . . -1(1) no C433 C432 C431 C436 . . . . 1.5(8) no C433 C434 C435 C436 . . . . 2(1) no #------------------------------------------------------------------------------ #===END # Attachment 'ben0607_rerefined.cif.txt' data_ben0607_rerefined _database_code_depnum_ccdc_archive 'CCDC 725988' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 F8 N2 O6 P2, C H2 Cl2 ' _chemical_formula_sum 'C37 H22 Au2 Cl2 F8 N2 O6 P2' _chemical_formula_weight 1269.34 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall -P2yn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 9.3504(3) _cell_length_b 19.5747(6) _cell_length_c 21.6622(6) _cell_angle_alpha 90.00 _cell_angle_beta 98.734(2) _cell_angle_gamma 90.00 _cell_volume 3918.9(2) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 7139 _cell_measurement_theta_max 25.028 _cell_measurement_theta_min 2.546 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.151 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2400 _exptl_absorpt_coefficient_mu 7.784 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.1714 _exptl_absorpt_correction_T_max 0.8000 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9095 _diffrn_reflns_av_R_equivalents 0.0305 _diffrn_reflns_av_sigmaI/netI 0.0578 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 3 _diffrn_reflns_limit_k_min -23 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.82 _diffrn_reflns_theta_max 25.00 _reflns_number_total 6735 _reflns_number_gt 4451 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0220P)^2^+21.5166P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6735 _refine_ls_number_parameters 532 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0847 _refine_ls_R_factor_gt 0.0423 _refine_ls_wR_factor_ref 0.0807 _refine_ls_wR_factor_gt 0.0720 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.020 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl 0.1205(4) 0.09116(16) 0.32633(14) 0.0672(9) Uani 1 1 d . . . C37 C 0.2551(14) 0.1312(5) 0.3814(5) 0.065(3) Uani 1 1 d . . . H37A H 0.3148 0.1616 0.3591 0.078 Uiso 1 1 calc R . . H37B H 0.2078 0.1596 0.4102 0.078 Uiso 1 1 calc R . . Cl2 Cl 0.3661(4) 0.0708(2) 0.42412(17) 0.0923(13) Uani 1 1 d . . . Au1 Au 0.86406(3) 0.85602(2) 0.085079(14) 0.02494(10) Uani 1 1 d . . . Au2 Au 0.63972(3) 0.85796(2) 0.134936(14) 0.02496(10) Uani 1 1 d . . . P1 P 0.7104(3) 0.80387(12) 0.00271(11) 0.0275(5) Uani 1 1 d . . . P2 P 0.7932(3) 0.82188(12) 0.22497(11) 0.0263(5) Uani 1 1 d . . . F1 F 0.4743(6) 0.8378(3) -0.1131(2) 0.0495(16) Uani 1 1 d . . . F2 F 0.2623(7) 0.9308(3) -0.1159(3) 0.0553(16) Uani 1 1 d . . . F3 F 0.2246(6) 0.9985(3) -0.0106(2) 0.0457(15) Uani 1 1 d . . . F4 F 0.4011(6) 0.9752(3) 0.0971(2) 0.0382(13) Uani 1 1 d . . . F5 F 1.0344(6) 0.8618(3) 0.3334(2) 0.0439(14) Uani 1 1 d . . . F6 F 1.2640(6) 0.9429(3) 0.3246(3) 0.0519(16) Uani 1 1 d . . . F7 F 1.2960(6) 1.0017(3) 0.2148(3) 0.0468(15) Uani 1 1 d . . . F8 F 1.1086(6) 0.9736(3) 0.1108(2) 0.0410(14) Uani 1 1 d . . . O1 O 1.0547(7) 0.8583(4) 0.0421(3) 0.0348(15) Uani 1 1 d . . . O2 O 1.0505(9) 0.7482(4) 0.0526(5) 0.082(3) Uani 1 1 d . . . O3 O 1.2222(9) 0.7961(4) 0.0141(4) 0.076(3) Uani 1 1 d . . . O4 O 0.4441(7) 0.8596(4) 0.1770(3) 0.0358(15) Uani 1 1 d . . . O5 O 0.4410(9) 0.7560(4) 0.1452(5) 0.074(3) Uani 1 1 d . . . O6 O 0.2640(8) 0.7982(4) 0.1875(4) 0.059(2) Uani 1 1 d . . . N1 N 1.1095(10) 0.7994(5) 0.0372(4) 0.048(2) Uani 1 1 d . . . N2 N 0.3832(9) 0.8033(5) 0.1698(4) 0.038(2) Uani 1 1 d . . . C1 C 0.5503(9) 0.8569(5) -0.0052(4) 0.0288(19) Uani 1 1 d . . . C2 C 0.4595(10) 0.8698(5) -0.0601(4) 0.033(2) Uani 1 1 d . . . C3 C 0.3484(10) 0.9178(5) -0.0616(4) 0.038(2) Uani 1 1 d . . . C4 C 0.3296(10) 0.9516(5) -0.0089(5) 0.034(2) Uani 1 1 d . . . C5 C 0.4223(10) 0.9386(5) 0.0465(4) 0.031(2) Uani 1 1 d . . . C6 C 0.5267(10) 0.8902(5) 0.0511(4) 0.030(2) Uani 1 1 d . . . C7 C 0.7828(9) 0.8025(5) -0.0701(4) 0.030(2) Uani 1 1 d . . . C8 C 0.7818(10) 0.7422(5) -0.1048(4) 0.034(2) Uani 1 1 d . . . H8 H 0.7434 0.7011 -0.0907 0.041 Uiso 1 1 calc R . . C9 C 0.8387(11) 0.7438(5) -0.1608(5) 0.043(3) Uani 1 1 d . . . H9 H 0.8378 0.7036 -0.1853 0.051 Uiso 1 1 calc R . . C10 C 0.8948(11) 0.8021(6) -0.1803(4) 0.043(3) Uani 1 1 d . . . H10 H 0.9311 0.8025 -0.2189 0.052 Uiso 1 1 calc R . . C11 C 0.9006(11) 0.8611(6) -0.1450(4) 0.045(3) Uani 1 1 d . . . H11 H 0.9433 0.9013 -0.1587 0.054 Uiso 1 1 calc R . . C12 C 0.8446(10) 0.8615(5) -0.0903(4) 0.037(2) Uani 1 1 d . . . H12 H 0.8479 0.9020 -0.0661 0.045 Uiso 1 1 calc R . . C13 C 0.6588(11) 0.7173(5) 0.0187(4) 0.032(2) Uani 1 1 d . . . C14 C 0.5234(12) 0.6919(5) -0.0076(5) 0.051(3) Uani 1 1 d . . . H14 H 0.4555 0.7207 -0.0323 0.061 Uiso 1 1 calc R . . C15 C 0.4896(13) 0.6255(6) 0.0027(6) 0.067(4) Uani 1 1 d . . . H15 H 0.3975 0.6083 -0.0152 0.081 Uiso 1 1 calc R . . C16 C 0.5842(13) 0.5835(6) 0.0377(5) 0.058(3) Uani 1 1 d . . . H16 H 0.5587 0.5373 0.0438 0.070 Uiso 1 1 calc R . . C17 C 0.7148(14) 0.6073(6) 0.0641(6) 0.072(4) Uani 1 1 d . . . H17 H 0.7803 0.5779 0.0894 0.086 Uiso 1 1 calc R . . C18 C 0.7543(13) 0.6750(6) 0.0545(6) 0.061(3) Uani 1 1 d . . . H18 H 0.8467 0.6915 0.0728 0.073 Uiso 1 1 calc R . . C19 C 0.9554(10) 0.8724(4) 0.2243(4) 0.030(2) Uani 1 1 d . . . C20 C 1.0524(11) 0.8889(5) 0.2765(4) 0.034(2) Uani 1 1 d . . . C21 C 1.1680(10) 0.9303(5) 0.2737(5) 0.035(2) Uani 1 1 d . . . C22 C 1.1842(10) 0.9589(5) 0.2171(4) 0.032(2) Uani 1 1 d . . . C23 C 1.0901(10) 0.9434(5) 0.1644(5) 0.033(2) Uani 1 1 d . . . C24 C 0.9766(9) 0.8987(4) 0.1659(4) 0.026(2) Uani 1 1 d . . . C25 C 0.7193(10) 0.8446(5) 0.2943(4) 0.032(2) Uani 1 1 d . . . C26 C 0.7232(11) 0.7995(6) 0.3453(4) 0.047(3) Uani 1 1 d . . . H26 H 0.7639 0.7551 0.3443 0.057 Uiso 1 1 calc R . . C27 C 0.6652(12) 0.8223(7) 0.3975(5) 0.055(3) Uani 1 1 d . . . H27 H 0.6655 0.7924 0.4321 0.065 Uiso 1 1 calc R . . C28 C 0.6079(12) 0.8865(8) 0.4004(5) 0.062(4) Uani 1 1 d . . . H28 H 0.5716 0.9013 0.4368 0.075 Uiso 1 1 calc R . . C29 C 0.6038(12) 0.9294(7) 0.3497(5) 0.060(3) Uani 1 1 d . . . H29 H 0.5606 0.9732 0.3505 0.072 Uiso 1 1 calc R . . C30 C 0.6610(11) 0.9095(5) 0.2983(5) 0.044(3) Uani 1 1 d . . . H30 H 0.6611 0.9406 0.2647 0.053 Uiso 1 1 calc R . . C31 C 0.8433(10) 0.7336(4) 0.2298(4) 0.029(2) Uani 1 1 d . . . C32 C 0.9884(10) 0.7140(5) 0.2405(4) 0.035(2) Uani 1 1 d . . . H32 H 1.0617 0.7480 0.2435 0.042 Uiso 1 1 calc R . . C33 C 1.0270(11) 0.6461(5) 0.2467(5) 0.045(2) Uani 1 1 d . . . H33 H 1.1262 0.6334 0.2532 0.054 Uiso 1 1 calc R . . C34 C 0.9198(12) 0.5961(5) 0.2433(5) 0.052(3) Uani 1 1 d . . . H34 H 0.9458 0.5493 0.2492 0.062 Uiso 1 1 calc R . . C35 C 0.7774(12) 0.6144(6) 0.2315(6) 0.057(3) Uani 1 1 d . . . H35 H 0.7043 0.5804 0.2287 0.069 Uiso 1 1 calc R . . C36 C 0.7389(11) 0.6831(5) 0.2237(5) 0.046(3) Uani 1 1 d . . . H36 H 0.6397 0.6952 0.2139 0.055 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.072(2) 0.0591(19) 0.0646(19) -0.0104(15) -0.0069(17) 0.0122(16) C37 0.084(9) 0.044(7) 0.069(8) -0.020(6) 0.018(7) -0.007(7) Cl2 0.101(3) 0.088(3) 0.077(2) -0.028(2) -0.024(2) 0.037(2) Au1 0.02044(19) 0.0269(2) 0.02765(19) 0.00004(16) 0.00428(15) -0.00174(17) Au2 0.02037(19) 0.0283(2) 0.02619(19) 0.00103(16) 0.00340(14) -0.00067(17) P1 0.0250(13) 0.0303(13) 0.0264(12) -0.0018(10) 0.0014(10) -0.0021(10) P2 0.0222(13) 0.0282(13) 0.0292(13) 0.0029(10) 0.0062(10) 0.0008(10) F1 0.043(4) 0.076(4) 0.028(3) -0.008(3) 0.001(3) 0.001(3) F2 0.048(4) 0.078(4) 0.035(3) 0.010(3) -0.008(3) 0.014(3) F3 0.035(3) 0.050(4) 0.051(3) 0.016(3) 0.003(3) 0.014(3) F4 0.034(3) 0.043(3) 0.038(3) 0.002(3) 0.005(3) 0.007(3) F5 0.043(3) 0.055(4) 0.030(3) 0.002(3) -0.005(2) -0.002(3) F6 0.038(4) 0.057(4) 0.055(4) -0.014(3) -0.013(3) -0.007(3) F7 0.035(3) 0.045(3) 0.061(4) -0.013(3) 0.008(3) -0.015(3) F8 0.039(3) 0.040(3) 0.046(3) 0.001(3) 0.012(3) -0.010(3) O1 0.030(4) 0.034(4) 0.041(4) -0.003(3) 0.011(3) -0.008(3) O2 0.058(6) 0.051(5) 0.149(9) 0.010(5) 0.050(6) 0.011(5) O3 0.043(5) 0.075(6) 0.120(8) -0.037(5) 0.045(5) -0.007(4) O4 0.025(4) 0.046(4) 0.036(4) -0.009(3) 0.006(3) 0.005(4) O5 0.046(5) 0.040(5) 0.143(8) -0.014(5) 0.043(6) -0.007(4) O6 0.035(5) 0.061(5) 0.084(6) 0.018(4) 0.023(4) -0.001(4) N1 0.034(6) 0.048(6) 0.062(6) -0.001(5) 0.013(5) -0.012(5) N2 0.032(5) 0.045(6) 0.042(5) 0.009(4) 0.019(4) 0.015(5) C1 0.021(5) 0.037(5) 0.028(5) 0.000(4) 0.003(4) -0.005(4) C2 0.026(5) 0.049(7) 0.025(5) -0.003(4) 0.001(4) 0.003(5) C3 0.023(5) 0.054(7) 0.034(6) 0.017(5) -0.004(4) -0.005(5) C4 0.027(5) 0.033(6) 0.044(6) 0.006(5) 0.008(5) 0.002(4) C5 0.030(5) 0.036(6) 0.027(5) -0.003(4) 0.011(4) -0.004(4) C6 0.024(5) 0.032(5) 0.034(5) 0.002(4) 0.004(4) -0.005(4) C7 0.019(5) 0.040(6) 0.030(5) 0.000(4) 0.006(4) 0.001(4) C8 0.028(6) 0.035(5) 0.039(6) -0.011(4) 0.002(5) -0.007(4) C9 0.050(7) 0.044(6) 0.038(6) -0.001(5) 0.015(5) 0.001(5) C10 0.039(6) 0.063(7) 0.032(5) -0.003(5) 0.017(5) 0.002(5) C11 0.057(7) 0.045(6) 0.037(5) 0.002(5) 0.017(5) -0.003(6) C12 0.040(6) 0.036(6) 0.037(5) 0.001(5) 0.008(4) 0.000(5) C13 0.039(6) 0.027(5) 0.031(5) 0.001(4) 0.006(4) -0.006(4) C14 0.047(7) 0.035(6) 0.069(8) 0.005(5) 0.000(6) -0.005(5) C15 0.045(8) 0.052(8) 0.098(10) 0.004(7) -0.013(7) -0.024(6) C16 0.062(8) 0.037(7) 0.074(8) 0.011(6) 0.007(7) -0.016(6) C17 0.062(9) 0.043(7) 0.099(10) 0.017(7) -0.024(8) -0.011(6) C18 0.038(7) 0.050(7) 0.088(9) 0.008(7) -0.010(6) -0.004(6) C19 0.024(5) 0.032(6) 0.034(5) 0.001(4) 0.003(4) 0.000(4) C20 0.037(6) 0.030(5) 0.033(5) -0.002(4) -0.002(5) 0.009(5) C21 0.023(5) 0.029(5) 0.049(6) -0.009(5) -0.006(5) -0.001(4) C22 0.027(5) 0.027(5) 0.043(6) -0.011(4) 0.004(4) -0.007(4) C23 0.023(5) 0.027(5) 0.049(6) -0.006(4) 0.003(5) -0.005(4) C24 0.027(5) 0.020(5) 0.033(5) -0.001(4) 0.008(4) 0.004(4) C25 0.025(5) 0.038(6) 0.029(5) 0.001(4) -0.003(4) -0.001(4) C26 0.045(7) 0.066(8) 0.032(6) 0.017(5) 0.007(5) 0.011(6) C27 0.044(7) 0.085(9) 0.034(6) 0.021(6) 0.004(5) -0.016(7) C28 0.046(7) 0.116(11) 0.025(6) -0.004(6) 0.006(5) 0.021(7) C29 0.050(7) 0.088(9) 0.040(6) -0.029(6) 0.001(6) 0.018(7) C30 0.052(7) 0.039(6) 0.044(6) 0.001(5) 0.015(5) 0.003(5) C31 0.031(6) 0.025(5) 0.033(5) 0.000(4) 0.010(4) 0.001(4) C32 0.028(6) 0.033(5) 0.043(6) 0.000(4) -0.001(4) 0.005(4) C33 0.036(6) 0.032(5) 0.065(7) 0.000(5) 0.000(5) 0.006(5) C34 0.050(7) 0.034(6) 0.069(8) -0.004(5) 0.002(6) 0.012(5) C35 0.035(7) 0.041(7) 0.092(9) 0.004(6) -0.003(6) -0.007(5) C36 0.024(6) 0.034(6) 0.078(8) 0.003(5) 0.002(5) 0.003(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cl1 C37 1.779(12) . ? C37 Cl2 1.745(13) . ? C37 H37A 0.9900 . ? C37 H37B 0.9900 . ? Au1 C24 2.077(9) . ? Au1 O1 2.132(6) . ? Au1 P1 2.348(2) . ? Au1 Au2 2.5012(4) . ? Au2 C6 2.056(9) . ? Au2 O4 2.164(6) . ? Au2 P2 2.348(2) . ? P1 C1 1.808(9) . ? P1 C7 1.808(9) . ? P1 C13 1.809(9) . ? P2 C31 1.789(9) . ? P2 C25 1.801(9) . ? P2 C19 1.812(9) . ? F1 C2 1.333(10) . ? F2 C3 1.343(10) . ? F3 C4 1.340(10) . ? F4 C5 1.350(10) . ? F5 C20 1.374(10) . ? F6 C21 1.335(10) . ? F7 C22 1.347(10) . ? F8 C23 1.338(10) . ? O1 N1 1.273(11) . ? O2 N1 1.215(11) . ? O3 N1 1.235(11) . ? O4 N2 1.240(10) . ? O5 N2 1.234(10) . ? O6 N2 1.236(10) . ? C1 C2 1.376(12) . ? C1 C6 1.430(12) . ? C2 C3 1.397(13) . ? C3 C4 1.355(13) . ? C4 C5 1.393(12) . ? C5 C6 1.353(13) . ? C7 C12 1.392(13) . ? C7 C8 1.399(12) . ? C8 C9 1.395(13) . ? C8 H8 0.9500 . ? C9 C10 1.350(14) . ? C9 H9 0.9500 . ? C10 C11 1.382(14) . ? C10 H10 0.9500 . ? C11 C12 1.364(12) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.370(14) . ? C13 C14 1.398(14) . ? C14 C15 1.364(14) . ? C14 H14 0.9500 . ? C15 C16 1.353(15) . ? C15 H15 0.9500 . ? C16 C17 1.350(15) . ? C16 H16 0.9500 . ? C17 C18 1.399(15) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.377(12) . ? C19 C24 1.407(12) . ? C20 C21 1.360(13) . ? C21 C22 1.377(13) . ? C22 C23 1.366(12) . ? C23 C24 1.379(12) . ? C25 C30 1.390(13) . ? C25 C26 1.412(12) . ? C26 C27 1.399(15) . ? C26 H26 0.9500 . ? C27 C28 1.372(16) . ? C27 H27 0.9500 . ? C28 C29 1.378(16) . ? C28 H28 0.9500 . ? C29 C30 1.361(13) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.382(13) . ? C31 C32 1.396(13) . ? C32 C33 1.380(13) . ? C32 H32 0.9500 . ? C33 C34 1.395(14) . ? C33 H33 0.9500 . ? C34 C35 1.366(15) . ? C34 H34 0.9500 . ? C35 C36 1.395(14) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl2 C37 Cl1 111.1(6) . . ? Cl2 C37 H37A 109.4 . . ? Cl1 C37 H37A 109.4 . . ? Cl2 C37 H37B 109.4 . . ? Cl1 C37 H37B 109.4 . . ? H37A C37 H37B 108.0 . . ? C24 Au1 O1 90.5(3) . . ? C24 Au1 P1 171.5(2) . . ? O1 Au1 P1 97.67(18) . . ? C24 Au1 Au2 88.9(2) . . ? O1 Au1 Au2 177.90(19) . . ? P1 Au1 Au2 83.00(6) . . ? C6 Au2 O4 90.8(3) . . ? C6 Au2 P2 173.3(3) . . ? O4 Au2 P2 95.98(17) . . ? C6 Au2 Au1 88.6(2) . . ? O4 Au2 Au1 179.32(16) . . ? P2 Au2 Au1 84.67(6) . . ? C1 P1 C7 109.9(4) . . ? C1 P1 C13 108.4(4) . . ? C7 P1 C13 107.4(4) . . ? C1 P1 Au1 103.0(3) . . ? C7 P1 Au1 113.7(3) . . ? C13 P1 Au1 114.3(3) . . ? C31 P2 C25 108.6(4) . . ? C31 P2 C19 108.4(4) . . ? C25 P2 C19 107.4(4) . . ? C31 P2 Au2 117.4(3) . . ? C25 P2 Au2 110.7(3) . . ? C19 P2 Au2 103.6(3) . . ? N1 O1 Au1 113.0(6) . . ? N2 O4 Au2 109.6(5) . . ? O2 N1 O3 121.2(10) . . ? O2 N1 O1 121.3(9) . . ? O3 N1 O1 117.5(9) . . ? O5 N2 O6 123.3(10) . . ? O5 N2 O4 120.0(8) . . ? O6 N2 O4 116.7(8) . . ? C2 C1 C6 120.0(8) . . ? C2 C1 P1 125.5(7) . . ? C6 C1 P1 114.4(6) . . ? F1 C2 C1 121.8(8) . . ? F1 C2 C3 118.0(8) . . ? C1 C2 C3 120.2(9) . . ? F2 C3 C4 120.5(9) . . ? F2 C3 C2 119.5(9) . . ? C4 C3 C2 120.0(8) . . ? F3 C4 C3 120.1(9) . . ? F3 C4 C5 120.4(9) . . ? C3 C4 C5 119.5(9) . . ? F4 C5 C6 120.3(8) . . ? F4 C5 C4 117.0(8) . . ? C6 C5 C4 122.7(9) . . ? C5 C6 C1 117.3(8) . . ? C5 C6 Au2 123.3(7) . . ? C1 C6 Au2 119.2(7) . . ? C12 C7 C8 119.9(8) . . ? C12 C7 P1 119.4(7) . . ? C8 C7 P1 120.6(7) . . ? C9 C8 C7 118.4(9) . . ? C9 C8 H8 120.8 . . ? C7 C8 H8 120.8 . . ? C10 C9 C8 120.6(9) . . ? C10 C9 H9 119.7 . . ? C8 C9 H9 119.7 . . ? C9 C10 C11 121.1(9) . . ? C9 C10 H10 119.4 . . ? C11 C10 H10 119.4 . . ? C12 C11 C10 119.7(10) . . ? C12 C11 H11 120.1 . . ? C10 C11 H11 120.1 . . ? C11 C12 C7 120.1(10) . . ? C11 C12 H12 119.9 . . ? C7 C12 H12 119.9 . . ? C18 C13 C14 119.2(9) . . ? C18 C13 P1 120.3(8) . . ? C14 C13 P1 120.4(8) . . ? C15 C14 C13 119.4(11) . . ? C15 C14 H14 120.3 . . ? C13 C14 H14 120.3 . . ? C16 C15 C14 121.5(11) . . ? C16 C15 H15 119.3 . . ? C14 C15 H15 119.3 . . ? C17 C16 C15 120.1(11) . . ? C17 C16 H16 120.0 . . ? C15 C16 H16 120.0 . . ? C16 C17 C18 120.4(12) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C13 C18 C17 119.5(11) . . ? C13 C18 H18 120.2 . . ? C17 C18 H18 120.2 . . ? C20 C19 C24 119.2(8) . . ? C20 C19 P2 124.7(7) . . ? C24 C19 P2 116.1(7) . . ? C21 C20 F5 118.5(8) . . ? C21 C20 C19 122.1(9) . . ? F5 C20 C19 119.4(9) . . ? F6 C21 C20 120.9(9) . . ? F6 C21 C22 120.6(9) . . ? C20 C21 C22 118.6(9) . . ? F7 C22 C23 120.8(9) . . ? F7 C22 C21 118.5(8) . . ? C23 C22 C21 120.7(9) . . ? F8 C23 C22 118.4(8) . . ? F8 C23 C24 120.2(8) . . ? C22 C23 C24 121.4(9) . . ? C23 C24 C19 117.9(8) . . ? C23 C24 Au1 121.9(7) . . ? C19 C24 Au1 119.2(6) . . ? C30 C25 C26 119.0(9) . . ? C30 C25 P2 118.8(7) . . ? C26 C25 P2 122.1(7) . . ? C27 C26 C25 117.8(10) . . ? C27 C26 H26 121.1 . . ? C25 C26 H26 121.1 . . ? C28 C27 C26 122.1(10) . . ? C28 C27 H27 119.0 . . ? C26 C27 H27 119.0 . . ? C27 C28 C29 119.0(11) . . ? C27 C28 H28 120.5 . . ? C29 C28 H28 120.5 . . ? C30 C29 C28 120.7(12) . . ? C30 C29 H29 119.6 . . ? C28 C29 H29 119.6 . . ? C29 C30 C25 121.3(10) . . ? C29 C30 H30 119.4 . . ? C25 C30 H30 119.4 . . ? C36 C31 C32 118.3(8) . . ? C36 C31 P2 120.8(7) . . ? C32 C31 P2 120.9(7) . . ? C33 C32 C31 121.0(9) . . ? C33 C32 H32 119.5 . . ? C31 C32 H32 119.5 . . ? C32 C33 C34 119.8(10) . . ? C32 C33 H33 120.1 . . ? C34 C33 H33 120.1 . . ? C35 C34 C33 119.8(10) . . ? C35 C34 H34 120.1 . . ? C33 C34 H34 120.1 . . ? C34 C35 C36 120.2(10) . . ? C34 C35 H35 119.9 . . ? C36 C35 H35 119.9 . . ? C31 C36 C35 120.9(9) . . ? C31 C36 H36 119.6 . . ? C35 C36 H36 119.6 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 138.4(3) . . . . ? P1 Au1 Au2 C6 -44.0(3) . . . . ? C24 Au1 Au2 P2 -41.2(2) . . . . ? P1 Au1 Au2 P2 136.39(8) . . . . ? O1 Au1 P1 C1 -132.4(3) . . . . ? Au2 Au1 P1 C1 45.6(3) . . . . ? O1 Au1 P1 C7 -13.5(4) . . . . ? Au2 Au1 P1 C7 164.5(3) . . . . ? O1 Au1 P1 C13 110.3(4) . . . . ? Au2 Au1 P1 C13 -71.7(4) . . . . ? O4 Au2 P2 C31 101.2(4) . . . . ? Au1 Au2 P2 C31 -78.5(3) . . . . ? O4 Au2 P2 C25 -24.3(4) . . . . ? Au1 Au2 P2 C25 155.9(3) . . . . ? O4 Au2 P2 C19 -139.3(4) . . . . ? Au1 Au2 P2 C19 40.9(3) . . . . ? C24 Au1 O1 N1 107.2(6) . . . . ? P1 Au1 O1 N1 -70.7(6) . . . . ? C6 Au2 O4 N2 89.6(6) . . . . ? P2 Au2 O4 N2 -90.8(6) . . . . ? Au1 O1 N1 O2 4.2(12) . . . . ? Au1 O1 N1 O3 -178.4(7) . . . . ? Au2 O4 N2 O5 4.2(11) . . . . ? Au2 O4 N2 O6 -174.9(6) . . . . ? C7 P1 C1 C2 26.5(10) . . . . ? C13 P1 C1 C2 -90.5(9) . . . . ? Au1 P1 C1 C2 148.0(8) . . . . ? C7 P1 C1 C6 -149.4(7) . . . . ? C13 P1 C1 C6 93.5(7) . . . . ? Au1 P1 C1 C6 -27.9(7) . . . . ? C6 C1 C2 F1 -177.3(8) . . . . ? P1 C1 C2 F1 7.0(14) . . . . ? C6 C1 C2 C3 3.0(14) . . . . ? P1 C1 C2 C3 -172.7(7) . . . . ? F1 C2 C3 F2 -0.9(13) . . . . ? C1 C2 C3 F2 178.7(8) . . . . ? F1 C2 C3 C4 -179.8(8) . . . . ? C1 C2 C3 C4 -0.1(14) . . . . ? F2 C3 C4 F3 0.0(14) . . . . ? C2 C3 C4 F3 178.9(8) . . . . ? F2 C3 C4 C5 -178.4(8) . . . . ? C2 C3 C4 C5 0.4(14) . . . . ? F3 C4 C5 F4 -0.2(13) . . . . ? C3 C4 C5 F4 178.2(8) . . . . ? F3 C4 C5 C6 177.6(8) . . . . ? C3 C4 C5 C6 -4.0(14) . . . . ? F4 C5 C6 C1 -175.6(8) . . . . ? C4 C5 C6 C1 6.7(14) . . . . ? F4 C5 C6 Au2 9.2(12) . . . . ? C4 C5 C6 Au2 -168.5(7) . . . . ? C2 C1 C6 C5 -6.2(13) . . . . ? P1 C1 C6 C5 170.0(7) . . . . ? C2 C1 C6 Au2 169.2(7) . . . . ? P1 C1 C6 Au2 -14.6(9) . . . . ? O4 Au2 C6 C5 40.8(8) . . . . ? Au1 Au2 C6 C5 -139.4(8) . . . . ? O4 Au2 C6 C1 -134.3(7) . . . . ? Au1 Au2 C6 C1 45.5(7) . . . . ? C1 P1 C7 C12 68.8(8) . . . . ? C13 P1 C7 C12 -173.5(7) . . . . ? Au1 P1 C7 C12 -46.0(8) . . . . ? C1 P1 C7 C8 -113.5(8) . . . . ? C13 P1 C7 C8 4.2(9) . . . . ? Au1 P1 C7 C8 131.7(7) . . . . ? C12 C7 C8 C9 -2.5(14) . . . . ? P1 C7 C8 C9 179.9(7) . . . . ? C7 C8 C9 C10 0.8(15) . . . . ? C8 C9 C10 C11 1.4(16) . . . . ? C9 C10 C11 C12 -2.1(16) . . . . ? C10 C11 C12 C7 0.4(15) . . . . ? C8 C7 C12 C11 1.9(14) . . . . ? P1 C7 C12 C11 179.6(8) . . . . ? C1 P1 C13 C18 -148.8(9) . . . . ? C7 P1 C13 C18 92.5(9) . . . . ? Au1 P1 C13 C18 -34.6(10) . . . . ? C1 P1 C13 C14 33.9(9) . . . . ? C7 P1 C13 C14 -84.8(9) . . . . ? Au1 P1 C13 C14 148.1(8) . . . . ? C18 C13 C14 C15 -0.5(17) . . . . ? P1 C13 C14 C15 176.8(9) . . . . ? C13 C14 C15 C16 0(2) . . . . ? C14 C15 C16 C17 1(2) . . . . ? C15 C16 C17 C18 -1(2) . . . . ? C14 C13 C18 C17 0.1(18) . . . . ? P1 C13 C18 C17 -177.2(10) . . . . ? C16 C17 C18 C13 1(2) . . . . ? C31 P2 C19 C20 -80.1(9) . . . . ? C25 P2 C19 C20 37.2(9) . . . . ? Au2 P2 C19 C20 154.5(7) . . . . ? C31 P2 C19 C24 103.3(7) . . . . ? C25 P2 C19 C24 -139.5(7) . . . . ? Au2 P2 C19 C24 -22.2(7) . . . . ? C24 C19 C20 C21 0.4(14) . . . . ? P2 C19 C20 C21 -176.1(7) . . . . ? C24 C19 C20 F5 -178.2(8) . . . . ? P2 C19 C20 F5 5.2(12) . . . . ? F5 C20 C21 F6 1.7(13) . . . . ? C19 C20 C21 F6 -176.9(8) . . . . ? F5 C20 C21 C22 -178.3(8) . . . . ? C19 C20 C21 C22 3.0(14) . . . . ? F6 C21 C22 F7 -2.3(13) . . . . ? C20 C21 C22 F7 177.7(8) . . . . ? F6 C21 C22 C23 176.8(8) . . . . ? C20 C21 C22 C23 -3.2(14) . . . . ? F7 C22 C23 F8 -2.3(13) . . . . ? C21 C22 C23 F8 178.6(8) . . . . ? F7 C22 C23 C24 178.9(8) . . . . ? C21 C22 C23 C24 -0.2(14) . . . . ? F8 C23 C24 C19 -175.2(8) . . . . ? C22 C23 C24 C19 3.6(13) . . . . ? F8 C23 C24 Au1 16.5(12) . . . . ? C22 C23 C24 Au1 -164.7(7) . . . . ? C20 C19 C24 C23 -3.7(12) . . . . ? P2 C19 C24 C23 173.1(7) . . . . ? C20 C19 C24 Au1 164.9(7) . . . . ? P2 C19 C24 Au1 -18.2(9) . . . . ? O1 Au1 C24 C23 31.3(7) . . . . ? Au2 Au1 C24 C23 -146.7(7) . . . . ? O1 Au1 C24 C19 -136.9(7) . . . . ? Au2 Au1 C24 C19 45.2(7) . . . . ? C31 P2 C25 C30 -174.4(8) . . . . ? C19 P2 C25 C30 68.5(9) . . . . ? Au2 P2 C25 C30 -44.0(8) . . . . ? C31 P2 C25 C26 7.9(10) . . . . ? C19 P2 C25 C26 -109.2(8) . . . . ? Au2 P2 C25 C26 138.2(8) . . . . ? C30 C25 C26 C27 1.1(15) . . . . ? P2 C25 C26 C27 178.9(8) . . . . ? C25 C26 C27 C28 -1.0(17) . . . . ? C26 C27 C28 C29 1.7(18) . . . . ? C27 C28 C29 C30 -2.7(18) . . . . ? C28 C29 C30 C25 2.9(18) . . . . ? C26 C25 C30 C29 -2.1(16) . . . . ? P2 C25 C30 C29 -179.9(9) . . . . ? C25 P2 C31 C36 71.3(9) . . . . ? C19 P2 C31 C36 -172.2(8) . . . . ? Au2 P2 C31 C36 -55.3(9) . . . . ? C25 P2 C31 C32 -108.1(8) . . . . ? C19 P2 C31 C32 8.4(9) . . . . ? Au2 P2 C31 C32 125.3(7) . . . . ? C36 C31 C32 C33 -2.0(15) . . . . ? P2 C31 C32 C33 177.4(7) . . . . ? C31 C32 C33 C34 -1.1(15) . . . . ? C32 C33 C34 C35 2.5(17) . . . . ? C33 C34 C35 C36 -0.8(18) . . . . ? C32 C31 C36 C35 3.7(16) . . . . ? P2 C31 C36 C35 -175.7(9) . . . . ? C34 C35 C36 C31 -2.3(18) . . . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 1.670 _refine_diff_density_min -0.960 _refine_diff_density_rms 0.158 # Attachment 'ben0609_rerefined.cif.txt' data_ben0609_rerefined _database_code_depnum_ccdc_archive 'CCDC 725989' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 F8 I2 P2' _chemical_formula_sum 'C36 H20 Au2 F8 I2 P2' _chemical_formula_weight 1314.19 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall -P2yn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 13.5862(2) _cell_length_b 17.8577(3) _cell_length_c 15.0048(2) _cell_angle_alpha 90.00 _cell_angle_beta 92.5220(10) _cell_angle_gamma 90.00 _cell_volume 3636.91(9) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 185897 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 27.485 _exptl_crystal_description prism _exptl_crystal_colour red _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.400 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2408 _exptl_absorpt_coefficient_mu 9.912 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.395 _exptl_absorpt_correction_T_max 0.682 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 65911 _diffrn_reflns_av_R_equivalents 0.0777 _diffrn_reflns_av_sigmaI/netI 0.0275 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.72 _diffrn_reflns_theta_max 25.00 _reflns_number_total 6407 _reflns_number_gt 5694 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0434P)^2^+1.9177P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6407 _refine_ls_number_parameters 451 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0312 _refine_ls_R_factor_gt 0.0249 _refine_ls_wR_factor_ref 0.0659 _refine_ls_wR_factor_gt 0.0631 _refine_ls_goodness_of_fit_ref 1.031 _refine_ls_restrained_S_all 1.031 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.723485(13) 0.073596(9) 0.335010(11) 0.02041(7) Uani 1 1 d . . . Au2 Au 0.563980(13) -0.002392(9) 0.311205(11) 0.01982(7) Uani 1 1 d . . . I1 I 0.88392(2) 0.160054(18) 0.32725(2) 0.03135(9) Uani 1 1 d . . . I2 I 0.40579(3) -0.079001(18) 0.25026(2) 0.03438(10) Uani 1 1 d . . . P1 P 0.79669(9) -0.02674(7) 0.26262(8) 0.0215(2) Uani 1 1 d . . . P2 P 0.48965(9) 0.11364(6) 0.27966(8) 0.0209(3) Uani 1 1 d . . . F1 F 0.8664(2) -0.19106(15) 0.2668(2) 0.0349(7) Uani 1 1 d . . . F2 F 0.7866(2) -0.30356(15) 0.3593(2) 0.0398(7) Uani 1 1 d . . . F3 F 0.6158(2) -0.28206(16) 0.4400(2) 0.0477(8) Uani 1 1 d . . . F4 F 0.5201(2) -0.15239(15) 0.42711(19) 0.0334(7) Uani 1 1 d . . . F5 F 0.7604(2) 0.17330(17) 0.51452(19) 0.0365(7) Uani 1 1 d . . . F6 F 0.6727(2) 0.29865(17) 0.5668(2) 0.0417(8) Uani 1 1 d . . . F7 F 0.5161(2) 0.35587(15) 0.4711(2) 0.0369(7) Uani 1 1 d . . . F8 F 0.4280(2) 0.27429(15) 0.3397(2) 0.0349(7) Uani 1 1 d . . . C1 C 0.7356(3) -0.1093(3) 0.3034(3) 0.0236(10) Uani 1 1 d . . . C2 C 0.7820(3) -0.1794(3) 0.3073(3) 0.0249(10) Uani 1 1 d . . . C3 C 0.7419(4) -0.2371(3) 0.3536(4) 0.0302(11) Uani 1 1 d . . . C4 C 0.6546(4) -0.2262(3) 0.3948(3) 0.0300(11) Uani 1 1 d . . . C5 C 0.6052(4) -0.1586(3) 0.3857(3) 0.0272(11) Uani 1 1 d . . . C6 C 0.6434(3) -0.0994(2) 0.3397(3) 0.0217(10) Uani 1 1 d . . . C7 C 0.7793(3) -0.0238(3) 0.1433(3) 0.0231(10) Uani 1 1 d . . . C8 C 0.8191(4) 0.0367(3) 0.0963(3) 0.0322(12) Uani 1 1 d . . . H8 H 0.8548 0.0750 0.1275 0.039 Uiso 1 1 calc R . . C9 C 0.8058(4) 0.0397(3) 0.0047(3) 0.0395(14) Uani 1 1 d . . . H9 H 0.8336 0.0798 -0.0271 0.047 Uiso 1 1 calc R . . C10 C 0.7524(4) -0.0149(3) -0.0413(3) 0.0384(13) Uani 1 1 d . . . H10 H 0.7436 -0.0123 -0.1044 0.046 Uiso 1 1 calc R . . C11 C 0.7120(4) -0.0734(3) 0.0049(3) 0.0339(12) Uani 1 1 d . . . H11 H 0.6748 -0.1106 -0.0267 0.041 Uiso 1 1 calc R . . C12 C 0.7253(4) -0.0783(3) 0.0969(3) 0.0294(11) Uani 1 1 d . . . H12 H 0.6974 -0.1188 0.1281 0.035 Uiso 1 1 calc R . . C13 C 0.9273(3) -0.0408(2) 0.2901(3) 0.0238(10) Uani 1 1 d . . . C14 C 0.9969(4) -0.0458(3) 0.2269(3) 0.0309(11) Uani 1 1 d . . . H14 H 0.9780 -0.0400 0.1656 0.037 Uiso 1 1 calc R . . C15 C 1.0947(4) -0.0593(3) 0.2520(4) 0.0406(13) Uani 1 1 d . . . H15 H 1.1429 -0.0615 0.2080 0.049 Uiso 1 1 calc R . . C16 C 1.1220(4) -0.0693(3) 0.3408(4) 0.0392(14) Uani 1 1 d . . . H16 H 1.1888 -0.0797 0.3578 0.047 Uiso 1 1 calc R . . C17 C 1.0523(4) -0.0644(3) 0.4057(3) 0.0332(12) Uani 1 1 d . . . H17 H 1.0710 -0.0713 0.4669 0.040 Uiso 1 1 calc R . . C18 C 0.9556(4) -0.0493(3) 0.3801(3) 0.0308(11) Uani 1 1 d . . . H18 H 0.9078 -0.0445 0.4241 0.037 Uiso 1 1 calc R . . C19 C 0.5531(4) 0.1807(2) 0.3530(3) 0.0238(10) Uani 1 1 d . . . C20 C 0.5124(3) 0.2479(3) 0.3797(3) 0.0253(10) Uani 1 1 d . . . C21 C 0.5544(4) 0.2903(3) 0.4475(3) 0.0281(11) Uani 1 1 d . . . C22 C 0.6362(4) 0.2619(3) 0.4942(3) 0.0302(11) Uani 1 1 d . . . C23 C 0.6792(3) 0.1969(3) 0.4664(3) 0.0272(11) Uani 1 1 d . . . C24 C 0.6434(3) 0.1569(3) 0.3936(3) 0.0238(10) Uani 1 1 d . . . C25 C 0.4977(3) 0.1406(3) 0.1645(3) 0.0240(10) Uani 1 1 d . . . C26 C 0.4713(4) 0.2126(3) 0.1343(3) 0.0319(12) Uani 1 1 d . . . H26 H 0.4463 0.2483 0.1745 0.038 Uiso 1 1 calc R . . C27 C 0.4815(4) 0.2313(3) 0.0463(4) 0.0375(13) Uani 1 1 d . . . H27 H 0.4637 0.2800 0.0261 0.045 Uiso 1 1 calc R . . C28 C 0.5176(4) 0.1795(3) -0.0133(3) 0.0360(13) Uani 1 1 d . . . H28 H 0.5247 0.1929 -0.0739 0.043 Uiso 1 1 calc R . . C29 C 0.5430(4) 0.1086(3) 0.0159(3) 0.0312(11) Uani 1 1 d . . . H29 H 0.5668 0.0730 -0.0250 0.037 Uiso 1 1 calc R . . C30 C 0.5341(4) 0.0890(3) 0.1038(3) 0.0273(11) Uani 1 1 d . . . H30 H 0.5527 0.0403 0.1235 0.033 Uiso 1 1 calc R . . C31 C 0.3625(4) 0.1175(2) 0.3114(3) 0.0247(10) Uani 1 1 d . . . C32 C 0.3431(4) 0.0969(3) 0.3981(3) 0.0348(12) Uani 1 1 d . . . H32 H 0.3955 0.0808 0.4376 0.042 Uiso 1 1 calc R . . C33 C 0.2491(4) 0.0997(4) 0.4272(4) 0.0451(14) Uani 1 1 d . . . H33 H 0.2365 0.0846 0.4863 0.054 Uiso 1 1 calc R . . C34 C 0.1726(4) 0.1243(4) 0.3713(4) 0.0500(16) Uani 1 1 d . . . H34 H 0.1075 0.1270 0.3918 0.060 Uiso 1 1 calc R . . C35 C 0.1915(4) 0.1448(4) 0.2852(4) 0.0493(16) Uani 1 1 d . . . H35 H 0.1390 0.1616 0.2462 0.059 Uiso 1 1 calc R . . C36 C 0.2859(4) 0.1414(3) 0.2550(4) 0.0377(13) Uani 1 1 d . . . H36 H 0.2982 0.1555 0.1954 0.045 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01898(11) 0.01977(11) 0.02208(10) -0.00097(7) -0.00354(7) 0.00019(7) Au2 0.01880(11) 0.01788(11) 0.02244(11) 0.00055(6) -0.00293(8) 0.00041(7) I1 0.02547(18) 0.03122(19) 0.03692(19) -0.00301(14) -0.00365(14) -0.00697(13) I2 0.02754(19) 0.03162(19) 0.0431(2) -0.00290(14) -0.00864(15) -0.00651(13) P1 0.0210(6) 0.0208(6) 0.0227(6) 0.0003(5) -0.0010(5) 0.0012(5) P2 0.0205(6) 0.0190(6) 0.0226(6) -0.0006(5) -0.0041(5) 0.0021(5) F1 0.0300(16) 0.0271(15) 0.0485(18) -0.0023(13) 0.0118(14) 0.0054(13) F2 0.0372(17) 0.0193(14) 0.063(2) 0.0066(14) -0.0003(15) 0.0061(13) F3 0.050(2) 0.0300(17) 0.064(2) 0.0197(15) 0.0184(17) 0.0058(15) F4 0.0293(16) 0.0311(15) 0.0407(17) 0.0105(13) 0.0100(13) 0.0022(12) F5 0.0333(17) 0.0456(18) 0.0293(15) -0.0066(13) -0.0136(13) 0.0011(13) F6 0.0503(19) 0.0399(18) 0.0343(16) -0.0159(14) -0.0044(15) -0.0074(15) F7 0.0468(19) 0.0196(14) 0.0446(17) -0.0068(13) 0.0072(15) 0.0010(13) F8 0.0336(16) 0.0271(15) 0.0432(17) -0.0003(13) -0.0073(14) 0.0102(12) C1 0.025(3) 0.018(2) 0.028(2) 0.0028(19) -0.003(2) -0.0036(19) C2 0.025(3) 0.021(2) 0.028(2) -0.0020(19) -0.001(2) 0.0027(19) C3 0.030(3) 0.020(2) 0.041(3) 0.003(2) -0.004(2) 0.007(2) C4 0.034(3) 0.019(2) 0.037(3) 0.008(2) 0.001(2) -0.002(2) C5 0.027(3) 0.028(3) 0.027(3) 0.002(2) 0.001(2) 0.001(2) C6 0.021(2) 0.020(2) 0.023(2) -0.0005(19) -0.0046(19) 0.0009(19) C7 0.022(2) 0.024(2) 0.023(2) 0.002(2) -0.0054(19) 0.0031(19) C8 0.041(3) 0.025(3) 0.030(3) -0.001(2) 0.000(2) -0.003(2) C9 0.061(4) 0.034(3) 0.023(3) 0.008(2) -0.001(3) -0.003(3) C10 0.045(3) 0.047(3) 0.022(3) 0.001(2) -0.007(2) 0.007(3) C11 0.034(3) 0.035(3) 0.032(3) -0.007(2) -0.007(2) -0.001(2) C12 0.031(3) 0.027(3) 0.030(3) -0.002(2) -0.002(2) -0.001(2) C13 0.026(3) 0.016(2) 0.029(2) 0.0004(19) -0.002(2) 0.0008(19) C14 0.024(3) 0.038(3) 0.030(3) 0.001(2) 0.000(2) 0.002(2) C15 0.030(3) 0.050(4) 0.042(3) -0.001(3) 0.007(3) 0.003(3) C16 0.030(3) 0.036(3) 0.051(4) 0.004(3) -0.011(3) 0.003(2) C17 0.034(3) 0.037(3) 0.027(3) 0.001(2) -0.012(2) 0.001(2) C18 0.029(3) 0.031(3) 0.032(3) 0.001(2) -0.003(2) -0.002(2) C19 0.026(3) 0.017(2) 0.028(3) 0.0026(19) -0.003(2) -0.0056(19) C20 0.024(2) 0.025(3) 0.027(2) 0.0025(19) -0.002(2) 0.001(2) C21 0.036(3) 0.018(2) 0.031(3) -0.002(2) 0.010(2) -0.003(2) C22 0.037(3) 0.029(3) 0.024(2) -0.009(2) 0.000(2) -0.009(2) C23 0.023(3) 0.035(3) 0.023(2) -0.001(2) -0.005(2) -0.006(2) C24 0.022(2) 0.021(2) 0.028(2) 0.0016(19) -0.002(2) -0.0032(19) C25 0.019(2) 0.027(3) 0.025(2) 0.001(2) -0.0047(19) -0.0017(19) C26 0.034(3) 0.027(3) 0.034(3) 0.000(2) -0.005(2) 0.003(2) C27 0.050(3) 0.029(3) 0.034(3) 0.010(2) -0.004(3) 0.005(2) C28 0.041(3) 0.041(3) 0.026(3) 0.008(2) -0.004(2) -0.002(2) C29 0.035(3) 0.033(3) 0.025(3) -0.005(2) -0.001(2) 0.002(2) C30 0.026(3) 0.026(3) 0.029(3) 0.001(2) -0.003(2) 0.002(2) C31 0.027(3) 0.017(2) 0.030(3) -0.0023(19) -0.002(2) 0.0016(19) C32 0.022(3) 0.051(3) 0.031(3) 0.002(2) -0.003(2) -0.001(2) C33 0.037(3) 0.065(4) 0.033(3) -0.001(3) 0.004(3) -0.009(3) C34 0.023(3) 0.066(4) 0.061(4) -0.004(3) 0.006(3) -0.001(3) C35 0.028(3) 0.069(4) 0.051(4) 0.005(3) -0.004(3) 0.007(3) C36 0.027(3) 0.048(3) 0.037(3) 0.006(3) -0.005(2) 0.010(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.062(5) . ? Au1 P1 2.3398(12) . ? Au1 Au2 2.5685(2) . ? Au1 I1 2.6778(4) . ? Au2 C6 2.075(4) . ? Au2 P2 2.3441(12) . ? Au2 I2 2.6747(4) . ? P1 C7 1.796(5) . ? P1 C1 1.812(5) . ? P1 C13 1.821(5) . ? P2 C25 1.801(5) . ? P2 C31 1.813(5) . ? P2 C19 1.818(5) . ? F1 C2 1.337(5) . ? F2 C3 1.334(5) . ? F3 C4 1.329(5) . ? F4 C5 1.342(6) . ? F5 C23 1.359(5) . ? F6 C22 1.347(5) . ? F7 C21 1.336(5) . ? F8 C20 1.355(5) . ? C1 C6 1.399(7) . ? C1 C2 1.400(6) . ? C2 C3 1.370(7) . ? C3 C4 1.376(7) . ? C4 C5 1.385(7) . ? C5 C6 1.376(7) . ? C7 C12 1.387(7) . ? C7 C8 1.410(7) . ? C8 C9 1.379(7) . ? C8 H8 0.9500 . ? C9 C10 1.382(8) . ? C9 H9 0.9500 . ? C10 C11 1.379(8) . ? C10 H10 0.9500 . ? C11 C12 1.388(7) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.372(7) . ? C13 C18 1.395(7) . ? C14 C15 1.386(7) . ? C14 H14 0.9500 . ? C15 C16 1.380(8) . ? C15 H15 0.9500 . ? C16 C17 1.391(8) . ? C16 H16 0.9500 . ? C17 C18 1.379(7) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.389(7) . ? C19 C24 1.410(6) . ? C20 C21 1.371(7) . ? C21 C22 1.384(7) . ? C22 C23 1.373(7) . ? C23 C24 1.377(6) . ? C25 C30 1.401(7) . ? C25 C26 1.405(7) . ? C26 C27 1.375(7) . ? C26 H26 0.9500 . ? C27 C28 1.390(8) . ? C27 H27 0.9500 . ? C28 C29 1.379(7) . ? C28 H28 0.9500 . ? C29 C30 1.375(7) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.379(7) . ? C31 C32 1.389(7) . ? C32 C33 1.368(8) . ? C32 H32 0.9500 . ? C33 C34 1.379(8) . ? C33 H33 0.9500 . ? C34 C35 1.378(9) . ? C34 H34 0.9500 . ? C35 C36 1.381(8) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 P1 173.29(13) . . ? C24 Au1 Au2 88.98(13) . . ? P1 Au1 Au2 84.50(3) . . ? C24 Au1 I1 92.79(13) . . ? P1 Au1 I1 93.32(3) . . ? Au2 Au1 I1 169.104(11) . . ? C6 Au2 P2 174.17(13) . . ? C6 Au2 Au1 89.11(12) . . ? P2 Au2 Au1 85.09(3) . . ? C6 Au2 I2 92.64(12) . . ? P2 Au2 I2 92.90(3) . . ? Au1 Au2 I2 167.992(12) . . ? C7 P1 C1 108.6(2) . . ? C7 P1 C13 108.3(2) . . ? C1 P1 C13 105.5(2) . . ? C7 P1 Au1 113.60(15) . . ? C1 P1 Au1 104.86(16) . . ? C13 P1 Au1 115.49(15) . . ? C25 P2 C31 109.9(2) . . ? C25 P2 C19 110.9(2) . . ? C31 P2 C19 104.4(2) . . ? C25 P2 Au2 112.70(16) . . ? C31 P2 Au2 112.82(15) . . ? C19 P2 Au2 105.73(15) . . ? C6 C1 C2 120.4(4) . . ? C6 C1 P1 117.3(3) . . ? C2 C1 P1 121.9(4) . . ? F1 C2 C3 118.7(4) . . ? F1 C2 C1 120.9(4) . . ? C3 C2 C1 120.3(4) . . ? F2 C3 C2 120.8(4) . . ? F2 C3 C4 119.8(4) . . ? C2 C3 C4 119.4(4) . . ? F3 C4 C3 119.5(4) . . ? F3 C4 C5 120.3(5) . . ? C3 C4 C5 120.2(4) . . ? F4 C5 C6 121.4(4) . . ? F4 C5 C4 116.7(4) . . ? C6 C5 C4 121.9(5) . . ? C5 C6 C1 117.5(4) . . ? C5 C6 Au2 122.7(3) . . ? C1 C6 Au2 119.5(3) . . ? C12 C7 C8 119.5(4) . . ? C12 C7 P1 121.5(4) . . ? C8 C7 P1 119.0(4) . . ? C9 C8 C7 119.4(5) . . ? C9 C8 H8 120.3 . . ? C7 C8 H8 120.3 . . ? C8 C9 C10 120.9(5) . . ? C8 C9 H9 119.6 . . ? C10 C9 H9 119.6 . . ? C11 C10 C9 119.7(5) . . ? C11 C10 H10 120.2 . . ? C9 C10 H10 120.2 . . ? C10 C11 C12 120.7(5) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C7 C12 C11 119.8(5) . . ? C7 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C14 C13 C18 119.5(4) . . ? C14 C13 P1 123.2(4) . . ? C18 C13 P1 117.3(4) . . ? C13 C14 C15 120.4(5) . . ? C13 C14 H14 119.8 . . ? C15 C14 H14 119.8 . . ? C16 C15 C14 119.9(5) . . ? C16 C15 H15 120.0 . . ? C14 C15 H15 120.0 . . ? C15 C16 C17 120.3(5) . . ? C15 C16 H16 119.8 . . ? C17 C16 H16 119.8 . . ? C18 C17 C16 119.2(5) . . ? C18 C17 H17 120.4 . . ? C16 C17 H17 120.4 . . ? C17 C18 C13 120.6(5) . . ? C17 C18 H18 119.7 . . ? C13 C18 H18 119.7 . . ? C20 C19 C24 119.0(4) . . ? C20 C19 P2 124.1(4) . . ? C24 C19 P2 116.3(3) . . ? F8 C20 C21 117.0(4) . . ? F8 C20 C19 120.8(4) . . ? C21 C20 C19 122.2(4) . . ? F7 C21 C20 121.8(4) . . ? F7 C21 C22 120.0(4) . . ? C20 C21 C22 118.2(4) . . ? F6 C22 C23 120.7(4) . . ? F6 C22 C21 119.4(4) . . ? C23 C22 C21 119.9(4) . . ? F5 C23 C22 116.6(4) . . ? F5 C23 C24 120.7(4) . . ? C22 C23 C24 122.7(4) . . ? C23 C24 C19 117.2(4) . . ? C23 C24 Au1 122.5(4) . . ? C19 C24 Au1 119.9(3) . . ? C30 C25 C26 119.0(4) . . ? C30 C25 P2 119.1(4) . . ? C26 C25 P2 121.9(4) . . ? C27 C26 C25 119.8(5) . . ? C27 C26 H26 120.1 . . ? C25 C26 H26 120.1 . . ? C26 C27 C28 120.6(5) . . ? C26 C27 H27 119.7 . . ? C28 C27 H27 119.7 . . ? C29 C28 C27 119.8(5) . . ? C29 C28 H28 120.1 . . ? C27 C28 H28 120.1 . . ? C30 C29 C28 120.5(5) . . ? C30 C29 H29 119.8 . . ? C28 C29 H29 119.8 . . ? C29 C30 C25 120.3(5) . . ? C29 C30 H30 119.8 . . ? C25 C30 H30 119.8 . . ? C36 C31 C32 119.2(5) . . ? C36 C31 P2 123.5(4) . . ? C32 C31 P2 117.3(4) . . ? C33 C32 C31 120.5(5) . . ? C33 C32 H32 119.8 . . ? C31 C32 H32 119.8 . . ? C32 C33 C34 120.5(6) . . ? C32 C33 H33 119.8 . . ? C34 C33 H33 119.8 . . ? C35 C34 C33 119.2(5) . . ? C35 C34 H34 120.4 . . ? C33 C34 H34 120.4 . . ? C34 C35 C36 120.7(5) . . ? C34 C35 H35 119.7 . . ? C36 C35 H35 119.7 . . ? C31 C36 C35 120.0(5) . . ? C31 C36 H36 120.0 . . ? C35 C36 H36 120.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -142.53(18) . . . . ? P1 Au1 Au2 C6 39.05(13) . . . . ? I1 Au1 Au2 C6 117.95(14) . . . . ? C24 Au1 Au2 P2 38.12(13) . . . . ? P1 Au1 Au2 P2 -140.31(4) . . . . ? I1 Au1 Au2 P2 -61.40(6) . . . . ? C24 Au1 Au2 I2 118.91(14) . . . . ? P1 Au1 Au2 I2 -59.51(6) . . . . ? I1 Au1 Au2 I2 19.39(9) . . . . ? Au2 Au1 P1 C7 80.05(17) . . . . ? I1 Au1 P1 C7 -89.24(17) . . . . ? Au2 Au1 P1 C1 -38.33(15) . . . . ? I1 Au1 P1 C1 152.38(15) . . . . ? Au2 Au1 P1 C13 -153.96(17) . . . . ? I1 Au1 P1 C13 36.74(17) . . . . ? Au1 Au2 P2 C25 86.16(16) . . . . ? I2 Au2 P2 C25 -81.97(16) . . . . ? Au1 Au2 P2 C31 -148.64(17) . . . . ? I2 Au2 P2 C31 43.22(17) . . . . ? Au1 Au2 P2 C19 -35.19(16) . . . . ? I2 Au2 P2 C19 156.67(16) . . . . ? C7 P1 C1 C6 -100.8(4) . . . . ? C13 P1 C1 C6 143.3(4) . . . . ? Au1 P1 C1 C6 20.9(4) . . . . ? C7 P1 C1 C2 85.6(4) . . . . ? C13 P1 C1 C2 -30.3(4) . . . . ? Au1 P1 C1 C2 -152.6(4) . . . . ? C6 C1 C2 F1 174.7(4) . . . . ? P1 C1 C2 F1 -11.9(6) . . . . ? C6 C1 C2 C3 -5.8(7) . . . . ? P1 C1 C2 C3 167.6(4) . . . . ? F1 C2 C3 F2 0.9(7) . . . . ? C1 C2 C3 F2 -178.6(4) . . . . ? F1 C2 C3 C4 -179.3(5) . . . . ? C1 C2 C3 C4 1.2(7) . . . . ? F2 C3 C4 F3 0.0(8) . . . . ? C2 C3 C4 F3 -179.7(5) . . . . ? F2 C3 C4 C5 -176.9(5) . . . . ? C2 C3 C4 C5 3.3(8) . . . . ? F3 C4 C5 F4 2.4(7) . . . . ? C3 C4 C5 F4 179.3(5) . . . . ? F3 C4 C5 C6 179.7(4) . . . . ? C3 C4 C5 C6 -3.4(8) . . . . ? F4 C5 C6 C1 176.0(4) . . . . ? C4 C5 C6 C1 -1.1(7) . . . . ? F4 C5 C6 Au2 -10.7(6) . . . . ? C4 C5 C6 Au2 172.1(4) . . . . ? C2 C1 C6 C5 5.7(7) . . . . ? P1 C1 C6 C5 -168.0(3) . . . . ? C2 C1 C6 Au2 -167.8(3) . . . . ? P1 C1 C6 Au2 18.5(5) . . . . ? Au1 Au2 C6 C5 143.8(4) . . . . ? I2 Au2 C6 C5 -48.1(4) . . . . ? Au1 Au2 C6 C1 -43.1(3) . . . . ? I2 Au2 C6 C1 125.0(3) . . . . ? C1 P1 C7 C12 0.9(5) . . . . ? C13 P1 C7 C12 115.0(4) . . . . ? Au1 P1 C7 C12 -115.3(4) . . . . ? C1 P1 C7 C8 178.9(4) . . . . ? C13 P1 C7 C8 -67.0(4) . . . . ? Au1 P1 C7 C8 62.7(4) . . . . ? C12 C7 C8 C9 -1.6(7) . . . . ? P1 C7 C8 C9 -179.7(4) . . . . ? C7 C8 C9 C10 1.2(9) . . . . ? C8 C9 C10 C11 -0.1(9) . . . . ? C9 C10 C11 C12 -0.6(8) . . . . ? C8 C7 C12 C11 0.9(7) . . . . ? P1 C7 C12 C11 178.9(4) . . . . ? C10 C11 C12 C7 0.2(8) . . . . ? C7 P1 C13 C14 1.6(5) . . . . ? C1 P1 C13 C14 117.6(4) . . . . ? Au1 P1 C13 C14 -127.1(4) . . . . ? C7 P1 C13 C18 -176.3(4) . . . . ? C1 P1 C13 C18 -60.2(4) . . . . ? Au1 P1 C13 C18 55.1(4) . . . . ? C18 C13 C14 C15 0.1(7) . . . . ? P1 C13 C14 C15 -177.7(4) . . . . ? C13 C14 C15 C16 1.4(8) . . . . ? C14 C15 C16 C17 -1.5(8) . . . . ? C15 C16 C17 C18 0.0(8) . . . . ? C16 C17 C18 C13 1.6(8) . . . . ? C14 C13 C18 C17 -1.6(7) . . . . ? P1 C13 C18 C17 176.3(4) . . . . ? C25 P2 C19 C20 81.6(5) . . . . ? C31 P2 C19 C20 -36.7(5) . . . . ? Au2 P2 C19 C20 -155.9(4) . . . . ? C25 P2 C19 C24 -107.2(4) . . . . ? C31 P2 C19 C24 134.5(4) . . . . ? Au2 P2 C19 C24 15.3(4) . . . . ? C24 C19 C20 F8 177.2(4) . . . . ? P2 C19 C20 F8 -11.8(7) . . . . ? C24 C19 C20 C21 -3.5(7) . . . . ? P2 C19 C20 C21 167.5(4) . . . . ? F8 C20 C21 F7 -2.4(7) . . . . ? C19 C20 C21 F7 178.2(4) . . . . ? F8 C20 C21 C22 175.0(4) . . . . ? C19 C20 C21 C22 -4.4(7) . . . . ? F7 C21 C22 F6 4.2(7) . . . . ? C20 C21 C22 F6 -173.3(4) . . . . ? F7 C21 C22 C23 -175.9(4) . . . . ? C20 C21 C22 C23 6.6(7) . . . . ? F6 C22 C23 F5 -1.4(7) . . . . ? C21 C22 C23 F5 178.8(4) . . . . ? F6 C22 C23 C24 178.9(4) . . . . ? C21 C22 C23 C24 -1.0(8) . . . . ? F5 C23 C24 C19 173.5(4) . . . . ? C22 C23 C24 C19 -6.8(7) . . . . ? F5 C23 C24 Au1 -13.7(6) . . . . ? C22 C23 C24 Au1 166.0(4) . . . . ? C20 C19 C24 C23 8.9(7) . . . . ? P2 C19 C24 C23 -162.8(4) . . . . ? C20 C19 C24 Au1 -164.1(4) . . . . ? P2 C19 C24 Au1 24.2(5) . . . . ? Au2 Au1 C24 C23 141.6(4) . . . . ? I1 Au1 C24 C23 -49.1(4) . . . . ? Au2 Au1 C24 C19 -45.8(4) . . . . ? I1 Au1 C24 C19 123.5(4) . . . . ? C31 P2 C25 C30 -119.0(4) . . . . ? C19 P2 C25 C30 126.2(4) . . . . ? Au2 P2 C25 C30 7.8(4) . . . . ? C31 P2 C25 C26 62.9(4) . . . . ? C19 P2 C25 C26 -52.0(5) . . . . ? Au2 P2 C25 C26 -170.3(3) . . . . ? C30 C25 C26 C27 -0.1(7) . . . . ? P2 C25 C26 C27 178.0(4) . . . . ? C25 C26 C27 C28 0.2(8) . . . . ? C26 C27 C28 C29 0.3(8) . . . . ? C27 C28 C29 C30 -0.8(8) . . . . ? C28 C29 C30 C25 0.9(8) . . . . ? C26 C25 C30 C29 -0.4(7) . . . . ? P2 C25 C30 C29 -178.7(4) . . . . ? C25 P2 C31 C36 -2.9(5) . . . . ? C19 P2 C31 C36 116.1(4) . . . . ? Au2 P2 C31 C36 -129.6(4) . . . . ? C25 P2 C31 C32 178.8(4) . . . . ? C19 P2 C31 C32 -62.1(4) . . . . ? Au2 P2 C31 C32 52.1(4) . . . . ? C36 C31 C32 C33 0.5(8) . . . . ? P2 C31 C32 C33 178.9(4) . . . . ? C31 C32 C33 C34 -1.2(9) . . . . ? C32 C33 C34 C35 1.1(10) . . . . ? C33 C34 C35 C36 -0.3(10) . . . . ? C32 C31 C36 C35 0.2(8) . . . . ? P2 C31 C36 C35 -178.0(5) . . . . ? C34 C35 C36 C31 -0.3(9) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.394 _refine_diff_density_min -1.835 _refine_diff_density_rms 0.149 # Attachment 'neda00201.cif.txt' data_neda00201 _database_code_depnum_ccdc_archive 'CCDC 725990' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C40 H26 Au2 F8 O4 P2, 0,62(H2 O)' _chemical_formula_sum 'C40 H27.24 Au2 F8 O4.62 P2' _chemical_formula_weight 1189.65 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.0844(3) _cell_length_b 11.2569(3) _cell_length_c 18.2943(5) _cell_angle_alpha 92.311(2) _cell_angle_beta 96.760(2) _cell_angle_gamma 114.716(2) _cell_volume 1864.14(10) _cell_formula_units_Z 2 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 126623 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 30.034 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.119 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1128 _exptl_absorpt_coefficient_mu 8.032 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.435 _exptl_absorpt_correction_T_max 0.724 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 49598 _diffrn_reflns_av_R_equivalents 0.0861 _diffrn_reflns_av_sigmaI/netI 0.0633 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.86 _diffrn_reflns_theta_max 28.50 _reflns_number_total 9396 _reflns_number_gt 6623 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; The structure bears an occasionally occupied site of a water molecule (the hydrogen atoms of which have not been located). The s.o.f. of the water oxygen atom (O5a) was refined to 0.62 using a free variable. One of the tetrafluorophenylene groups is twofold disordered (s.o.f ratio 0.62 part a, 0.38 part b) according to the presence vs. absence of the water molecule in the closer proximity. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0359P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9396 _refine_ls_number_parameters 559 _refine_ls_number_restraints 55 _refine_ls_R_factor_all 0.0754 _refine_ls_R_factor_gt 0.0379 _refine_ls_wR_factor_ref 0.0786 _refine_ls_wR_factor_gt 0.0711 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.026 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.70101(2) 0.208867(18) 0.296499(10) 0.02601(6) Uani 1 1 d D . . Au2 Au 0.85429(2) 0.25426(2) 0.160698(11) 0.03170(7) Uani 1 1 d D B . P1 P 0.78531(15) 0.06784(13) 0.35748(7) 0.0267(3) Uani 1 1 d D B . P2 P 0.69526(15) 0.33381(13) 0.11880(7) 0.0281(3) Uani 1 1 d . . . O5A O 1.1815(10) 0.6179(9) 0.2655(6) 0.087(3) Uani 0.62 1 d P A 1 F1A F 1.130(3) 0.174(2) 0.4580(13) 0.039(3) Uani 0.62 1 d PDU B 1 F2A F 1.3014(16) 0.428(2) 0.4892(8) 0.046(3) Uani 0.62 1 d PDU B 1 F3A F 1.2077(13) 0.6104(11) 0.4418(5) 0.060(3) Uani 0.62 1 d PD B 1 F4A F 0.9358(7) 0.5368(7) 0.3608(4) 0.0444(16) Uani 0.62 1 d PD B 1 C1A C 0.9442(15) 0.2225(10) 0.3882(14) 0.0284(12) Uani 0.62 1 d PD B 1 C2A C 1.0795(16) 0.2588(18) 0.4311(11) 0.0349(13) Uani 0.62 1 d PD B 1 C3A C 1.1672(17) 0.3907(18) 0.4488(8) 0.037(2) Uani 0.62 1 d PDU B 1 C4A C 1.1198(16) 0.4815(13) 0.4241(10) 0.044(5) Uani 0.62 1 d PD B 1 C5A C 0.9828(18) 0.4451(12) 0.3812(8) 0.039(4) Uani 0.62 1 d PD B 1 C6A C 0.8944(12) 0.3145(16) 0.3621(11) 0.029(3) Uani 0.62 1 d PDU B 1 F1B F 1.113(4) 0.173(4) 0.466(2) 0.039(3) Uani 0.38 1 d PD B 2 F2B F 1.319(3) 0.442(4) 0.4761(15) 0.046(3) Uani 0.38 1 d PD B 2 F3B F 1.238(2) 0.611(2) 0.4109(9) 0.060(3) Uani 0.38 1 d PD B 2 F4B F 0.9776(13) 0.5353(12) 0.3295(7) 0.0444(16) Uani 0.38 1 d PD B 2 C1B C 0.947(2) 0.2198(16) 0.389(2) 0.0284(12) Uani 0.38 1 d PD B 2 C2B C 1.085(3) 0.264(3) 0.4311(18) 0.0349(13) Uani 0.38 1 d PD B 2 C3B C 1.182(3) 0.395(3) 0.4378(14) 0.037(2) Uani 0.38 1 d PD B 2 C4B C 1.141(3) 0.484(2) 0.4043(19) 0.044(5) Uani 0.38 1 d PD B 2 C5B C 1.003(3) 0.439(2) 0.3612(15) 0.039(4) Uani 0.38 1 d PD B 2 C6B C 0.906(2) 0.309(3) 0.3523(19) 0.029(3) Uani 0.38 1 d PD B 2 O1 O 0.5054(4) 0.0869(3) 0.23381(19) 0.0351(9) Uani 1 1 d . B . O2 O 0.4946(4) -0.0909(3) 0.2879(2) 0.0411(10) Uani 1 1 d . B . O3A O 0.9939(5) 0.1701(4) 0.1901(3) 0.0386(12) Uani 0.823(5) 1 d PD B 3 C39A C 1.1220(7) 0.2445(8) 0.2281(4) 0.0418(19) Uani 0.823(5) 1 d PD B 3 O4A O 1.1726(6) 0.3646(5) 0.2395(3) 0.0513(14) Uani 0.823(5) 1 d PD B 3 C40A C 1.206(3) 0.172(2) 0.2603(13) 0.051(4) Uani 0.823(5) 1 d PD B 3 H40A H 1.2838 0.1789 0.2307 0.077 Uiso 0.823(5) 1 d PR B 3 H40B H 1.1395 0.0789 0.2609 0.077 Uiso 0.823(5) 1 d PR B 3 H40C H 1.2516 0.2105 0.3110 0.077 Uiso 0.823(5) 1 d PR B 3 O3B O 1.0188(18) 0.233(2) 0.2267(10) 0.0386(12) Uani 0.177(5) 1 d PD B 4 C39B C 1.095(4) 0.175(3) 0.2011(15) 0.0418(19) Uani 0.177(5) 1 d PD B 4 O4B O 1.065(3) 0.125(2) 0.1367(13) 0.0513(14) Uani 0.177(5) 1 d PD B 4 C40B C 1.201(13) 0.145(12) 0.253(7) 0.051(4) Uani 0.177(5) 1 d PD B 4 H40D H 1.2869 0.2228 0.2769 0.077 Uiso 0.177(5) 1 d PR B 4 H40E H 1.2332 0.0931 0.2209 0.077 Uiso 0.177(5) 1 d PR B 4 H40F H 1.1494 0.0916 0.2902 0.077 Uiso 0.177(5) 1 d PR B 4 C7 C 0.7094(6) 0.0033(5) 0.4396(3) 0.0284(11) Uani 1 1 d . . . C8 C 0.7345(6) 0.0885(5) 0.5018(3) 0.0323(12) Uani 1 1 d . B . H8 H 0.7920 0.1801 0.5015 0.039 Uiso 1 1 calc R . . C9 C 0.6741(6) 0.0380(6) 0.5652(3) 0.0372(13) Uani 1 1 d . . . H9 H 0.6889 0.0954 0.6079 0.045 Uiso 1 1 calc R B . C10 C 0.5935(6) -0.0950(6) 0.5650(3) 0.0359(13) Uani 1 1 d . B . H10 H 0.5547 -0.1295 0.6083 0.043 Uiso 1 1 calc R . . C11 C 0.5680(6) -0.1798(6) 0.5023(3) 0.0355(13) Uani 1 1 d . . . H11 H 0.5107 -0.2715 0.5026 0.043 Uiso 1 1 calc R B . C12 C 0.6258(6) -0.1305(5) 0.4398(3) 0.0343(12) Uani 1 1 d . B . H12 H 0.6084 -0.1883 0.3968 0.041 Uiso 1 1 calc R . . C13 C 0.8346(6) -0.0513(5) 0.3139(3) 0.0275(11) Uani 1 1 d . . . C14 C 0.9176(6) -0.1021(5) 0.3576(3) 0.0344(13) Uani 1 1 d . B . H14 H 0.9464 -0.0747 0.4091 0.041 Uiso 1 1 calc R . . C15 C 0.9577(6) -0.1935(5) 0.3248(3) 0.0398(14) Uani 1 1 d . . . H15 H 1.0150 -0.2283 0.3538 0.048 Uiso 1 1 calc R B . C16 C 0.9142(6) -0.2339(5) 0.2497(3) 0.0377(13) Uani 1 1 d . B . H16 H 0.9413 -0.2969 0.2279 0.045 Uiso 1 1 calc R . . C17 C 0.8330(6) -0.1843(5) 0.2069(3) 0.0378(13) Uani 1 1 d . . . H17 H 0.8043 -0.2125 0.1555 0.045 Uiso 1 1 calc R B . C18 C 0.7918(6) -0.0915(5) 0.2388(3) 0.0349(12) Uani 1 1 d . B . H18 H 0.7353 -0.0566 0.2092 0.042 Uiso 1 1 calc R . . C19 C 0.4454(6) -0.0375(5) 0.2433(3) 0.0340(12) Uani 1 1 d . . . C20 C 0.3011(7) -0.1162(6) 0.1918(4) 0.0591(19) Uani 1 1 d . B . H20A H 0.2932 -0.2043 0.1782 0.089 Uiso 1 1 calc R . . H20B H 0.2995 -0.0715 0.1470 0.089 Uiso 1 1 calc R . . H20C H 0.2179 -0.1234 0.2169 0.089 Uiso 1 1 calc R . . F5 F 0.5533(3) 0.5225(3) 0.11211(17) 0.0405(8) Uani 1 1 d . B . F6 F 0.4683(4) 0.6264(3) 0.22108(19) 0.0455(8) Uani 1 1 d . . . F7 F 0.4988(4) 0.5584(3) 0.36099(19) 0.0504(9) Uani 1 1 d . B . F8 F 0.6125(4) 0.3863(3) 0.39027(16) 0.0457(8) Uani 1 1 d . . . C21 C 0.6331(5) 0.3985(5) 0.1933(3) 0.0293(11) Uani 1 1 d . B . C22 C 0.5717(6) 0.4864(5) 0.1808(3) 0.0325(12) Uani 1 1 d . . . C23 C 0.5260(6) 0.5406(5) 0.2355(3) 0.0348(13) Uani 1 1 d . B . C24 C 0.5423(6) 0.5072(5) 0.3066(3) 0.0342(12) Uani 1 1 d . . . C25 C 0.6024(6) 0.4192(5) 0.3202(3) 0.0335(12) Uani 1 1 d . B . C26 C 0.6470(5) 0.3618(5) 0.2662(3) 0.0278(11) Uani 1 1 d . B . C27 C 0.7890(6) 0.4698(5) 0.0658(3) 0.0305(12) Uani 1 1 d . B . C28 C 0.7196(7) 0.4897(6) -0.0010(3) 0.0450(15) Uani 1 1 d . . . H28 H 0.6199 0.4320 -0.0194 0.054 Uiso 1 1 calc R B . C29 C 0.7981(7) 0.5944(6) -0.0397(3) 0.0488(16) Uani 1 1 d . B . H29 H 0.7523 0.6063 -0.0855 0.059 Uiso 1 1 calc R . . C30 C 0.9461(7) 0.6840(6) -0.0117(3) 0.0473(16) Uani 1 1 d . . . H30 H 0.9993 0.7573 -0.0370 0.057 Uiso 1 1 calc R B . C31 C 1.0093(7) 0.6599(6) 0.0539(3) 0.0438(15) Uani 1 1 d . B . H31 H 1.1078 0.7185 0.0738 0.053 Uiso 1 1 calc R . . C32 C 0.9341(6) 0.5533(5) 0.0918(3) 0.0338(12) Uani 1 1 d . . . H32 H 0.9826 0.5379 0.1356 0.041 Uiso 1 1 calc R B . C33 C 0.5294(6) 0.2207(5) 0.0578(3) 0.0306(12) Uani 1 1 d . B . C34 C 0.5437(6) 0.1700(6) -0.0085(3) 0.0466(15) Uani 1 1 d . . . H34 H 0.6395 0.1924 -0.0211 0.056 Uiso 1 1 calc R B . C35 C 0.4195(7) 0.0857(6) -0.0582(3) 0.0473(16) Uani 1 1 d . B . H35 H 0.4307 0.0506 -0.1040 0.057 Uiso 1 1 calc R . . C36 C 0.2808(7) 0.0544(6) -0.0397(3) 0.0455(15) Uani 1 1 d . . . H36 H 0.1954 -0.0005 -0.0734 0.055 Uiso 1 1 calc R B . C37 C 0.2665(7) 0.1030(6) 0.0276(3) 0.0444(15) Uani 1 1 d . B . H37 H 0.1709 0.0788 0.0409 0.053 Uiso 1 1 calc R . . C38 C 0.3909(6) 0.1876(5) 0.0770(3) 0.0405(14) Uani 1 1 d . . . H38 H 0.3800 0.2219 0.1232 0.049 Uiso 1 1 calc R B . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02930(12) 0.02369(11) 0.02405(11) 0.00241(8) 0.00049(8) 0.01121(9) Au2 0.03086(12) 0.03612(13) 0.03296(12) 0.00873(9) 0.00518(9) 0.01838(10) P1 0.0308(7) 0.0250(7) 0.0252(7) 0.0030(5) 0.0021(5) 0.0131(6) P2 0.0274(7) 0.0331(7) 0.0250(7) 0.0045(6) 0.0013(5) 0.0145(6) O5A 0.073(6) 0.104(7) 0.121(8) 0.056(6) 0.049(6) 0.061(6) F1A 0.036(5) 0.0400(18) 0.042(5) 0.006(2) -0.004(3) 0.021(3) F2A 0.039(4) 0.043(4) 0.047(5) -0.004(4) -0.013(3) 0.014(3) F3A 0.057(6) 0.028(2) 0.077(8) -0.013(5) -0.025(5) 0.011(3) F4A 0.040(4) 0.0262(19) 0.068(5) -0.001(3) -0.003(3) 0.019(3) C1A 0.030(3) 0.028(3) 0.027(3) 0.004(2) 0.002(2) 0.012(2) C2A 0.043(3) 0.031(3) 0.033(3) 0.001(2) -0.001(3) 0.022(3) C3A 0.034(4) 0.042(3) 0.032(4) -0.004(3) -0.005(3) 0.017(3) C4A 0.040(6) 0.022(3) 0.052(11) -0.009(4) -0.017(6) 0.004(3) C5A 0.049(6) 0.025(3) 0.045(9) -0.004(5) -0.005(6) 0.021(3) C6A 0.031(3) 0.033(3) 0.025(5) -0.003(3) 0.003(3) 0.015(3) F1B 0.036(5) 0.0400(18) 0.042(5) 0.006(2) -0.004(3) 0.021(3) F2B 0.039(4) 0.043(4) 0.047(5) -0.004(4) -0.013(3) 0.014(3) F3B 0.057(6) 0.028(2) 0.077(8) -0.013(5) -0.025(5) 0.011(3) F4B 0.040(4) 0.0262(19) 0.068(5) -0.001(3) -0.003(3) 0.019(3) C1B 0.030(3) 0.028(3) 0.027(3) 0.004(2) 0.002(2) 0.012(2) C2B 0.043(3) 0.031(3) 0.033(3) 0.001(2) -0.001(3) 0.022(3) C3B 0.034(4) 0.042(3) 0.032(4) -0.004(3) -0.005(3) 0.017(3) C4B 0.040(6) 0.022(3) 0.052(11) -0.009(4) -0.017(6) 0.004(3) C5B 0.049(6) 0.025(3) 0.045(9) -0.004(5) -0.005(6) 0.021(3) C6B 0.031(3) 0.033(3) 0.025(5) -0.003(3) 0.003(3) 0.015(3) O1 0.036(2) 0.028(2) 0.036(2) -0.0032(16) -0.0034(16) 0.0112(17) O2 0.049(2) 0.0263(19) 0.042(2) 0.0047(17) 0.0065(19) 0.0099(19) O3A 0.030(3) 0.037(3) 0.055(3) 0.008(2) 0.006(2) 0.020(2) C39A 0.023(4) 0.049(5) 0.055(5) 0.025(4) 0.011(3) 0.014(4) O4A 0.042(3) 0.043(3) 0.064(4) 0.008(3) -0.001(3) 0.016(3) C40A 0.041(4) 0.068(12) 0.054(7) 0.023(7) 0.008(4) 0.030(7) O3B 0.030(3) 0.037(3) 0.055(3) 0.008(2) 0.006(2) 0.020(2) C39B 0.023(4) 0.049(5) 0.055(5) 0.025(4) 0.011(3) 0.014(4) O4B 0.042(3) 0.043(3) 0.064(4) 0.008(3) -0.001(3) 0.016(3) C40B 0.041(4) 0.068(12) 0.054(7) 0.023(7) 0.008(4) 0.030(7) C7 0.034(3) 0.030(3) 0.025(3) 0.005(2) 0.005(2) 0.016(2) C8 0.031(3) 0.035(3) 0.031(3) 0.000(2) 0.002(2) 0.015(3) C9 0.034(3) 0.046(3) 0.034(3) -0.004(3) 0.002(2) 0.020(3) C10 0.034(3) 0.049(4) 0.027(3) 0.013(3) 0.006(2) 0.019(3) C11 0.028(3) 0.042(3) 0.040(3) 0.013(3) 0.010(2) 0.016(3) C12 0.033(3) 0.034(3) 0.035(3) 0.003(2) 0.000(2) 0.015(3) C13 0.031(3) 0.022(3) 0.028(3) 0.007(2) 0.007(2) 0.009(2) C14 0.041(3) 0.031(3) 0.031(3) 0.002(2) 0.000(2) 0.017(3) C15 0.041(3) 0.025(3) 0.052(4) 0.007(3) 0.006(3) 0.014(3) C16 0.039(3) 0.027(3) 0.048(3) 0.002(2) 0.017(3) 0.012(3) C17 0.041(3) 0.032(3) 0.034(3) -0.003(2) 0.010(3) 0.009(3) C18 0.036(3) 0.035(3) 0.030(3) 0.002(2) 0.008(2) 0.012(3) C19 0.030(3) 0.034(3) 0.034(3) -0.004(2) 0.004(2) 0.011(3) C20 0.039(4) 0.044(4) 0.078(5) -0.009(3) -0.005(3) 0.007(3) F5 0.0453(19) 0.0474(19) 0.0383(18) 0.0112(15) -0.0012(14) 0.0303(17) F6 0.045(2) 0.0370(18) 0.067(2) 0.0093(16) 0.0111(17) 0.0281(16) F7 0.071(2) 0.0403(19) 0.051(2) 0.0016(16) 0.0202(18) 0.0318(19) F8 0.073(2) 0.0418(19) 0.0297(17) 0.0035(14) 0.0129(16) 0.0305(18) C21 0.024(3) 0.030(3) 0.030(3) -0.001(2) 0.003(2) 0.008(2) C22 0.026(3) 0.033(3) 0.034(3) 0.004(2) -0.006(2) 0.011(2) C23 0.030(3) 0.026(3) 0.048(3) 0.004(2) 0.003(2) 0.012(2) C24 0.032(3) 0.029(3) 0.041(3) -0.004(2) 0.010(2) 0.012(3) C25 0.040(3) 0.030(3) 0.030(3) 0.005(2) 0.005(2) 0.014(3) C26 0.022(3) 0.029(3) 0.032(3) 0.002(2) 0.003(2) 0.011(2) C27 0.028(3) 0.038(3) 0.030(3) 0.005(2) 0.004(2) 0.019(3) C28 0.037(3) 0.055(4) 0.049(4) 0.025(3) 0.007(3) 0.023(3) C29 0.045(4) 0.064(4) 0.046(4) 0.027(3) 0.012(3) 0.028(3) C30 0.063(4) 0.044(4) 0.044(4) 0.005(3) 0.013(3) 0.030(3) C31 0.038(3) 0.040(3) 0.042(3) -0.007(3) 0.007(3) 0.006(3) C32 0.037(3) 0.034(3) 0.028(3) -0.003(2) 0.006(2) 0.013(3) C33 0.027(3) 0.036(3) 0.023(3) 0.006(2) -0.003(2) 0.009(2) C34 0.028(3) 0.054(4) 0.051(4) -0.006(3) 0.000(3) 0.013(3) C35 0.045(4) 0.062(4) 0.030(3) -0.002(3) -0.004(3) 0.021(3) C36 0.048(4) 0.041(3) 0.036(3) -0.003(3) -0.014(3) 0.015(3) C37 0.032(3) 0.042(3) 0.048(4) 0.002(3) -0.004(3) 0.008(3) C38 0.041(3) 0.033(3) 0.041(3) -0.002(3) 0.004(3) 0.010(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6A 2.013(5) . ? Au1 C6B 2.013(6) . ? Au1 O1 2.041(3) . ? Au1 C26 2.088(5) . ? Au1 P1 2.3527(13) . ? Au1 Au2 3.0279(3) . ? Au2 O3A 2.037(4) . ? Au2 O3B 2.037(4) . ? Au2 P2 2.2200(13) . ? P1 C13 1.802(5) . ? P1 C7 1.807(5) . ? P1 C1A 1.814(5) . ? P1 C1B 1.814(5) . ? P2 C21 1.813(5) . ? P2 C27 1.817(5) . ? P2 C33 1.825(5) . ? F1A C2A 1.343(7) . ? F2A C3A 1.348(6) . ? F3A C4A 1.347(7) . ? F4A C5A 1.352(7) . ? C1A C2A 1.378(7) . ? C1A C6A 1.404(8) . ? C2A C3A 1.374(8) . ? C3A C4A 1.368(9) . ? C4A C5A 1.392(8) . ? C5A C6A 1.366(8) . ? F1B C2B 1.343(7) . ? F2B C3B 1.348(6) . ? F3B C4B 1.347(7) . ? F4B C5B 1.352(7) . ? C1B C2B 1.378(7) . ? C1B C6B 1.404(8) . ? C2B C3B 1.374(8) . ? C3B C4B 1.368(9) . ? C4B C5B 1.392(8) . ? C5B C6B 1.366(8) . ? O1 C19 1.301(6) . ? O2 C19 1.211(7) . ? O3A C39A 1.300(8) . ? C39A O4A 1.228(8) . ? C39A C40A 1.499(10) . ? C40A H40A 0.9800 . ? C40A H40B 0.9800 . ? C40A H40C 0.9800 . ? O3B C39B 1.304(18) . ? C39B O4B 1.232(19) . ? C39B C40B 1.499(10) . ? C40B H40D 0.9800 . ? C40B H40E 0.9800 . ? C40B H40F 0.9800 . ? C7 C8 1.385(7) . ? C7 C12 1.386(7) . ? C8 C9 1.403(8) . ? C8 H8 0.9500 . ? C9 C10 1.372(8) . ? C9 H9 0.9500 . ? C10 C11 1.388(8) . ? C10 H10 0.9500 . ? C11 C12 1.376(7) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.388(7) . ? C13 C14 1.395(7) . ? C14 C15 1.393(8) . ? C14 H14 0.9500 . ? C15 C16 1.387(8) . ? C15 H15 0.9500 . ? C16 C17 1.366(8) . ? C16 H16 0.9500 . ? C17 C18 1.405(7) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.524(8) . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? F5 C22 1.352(6) . ? F6 C23 1.340(6) . ? F7 C24 1.335(6) . ? F8 C25 1.353(6) . ? C21 C22 1.383(7) . ? C21 C26 1.421(7) . ? C22 C23 1.371(8) . ? C23 C24 1.379(8) . ? C24 C25 1.377(8) . ? C25 C26 1.375(7) . ? C27 C32 1.379(7) . ? C27 C28 1.408(7) . ? C28 C29 1.392(8) . ? C28 H28 0.9500 . ? C29 C30 1.424(9) . ? C29 H29 0.9500 . ? C30 C31 1.382(8) . ? C30 H30 0.9500 . ? C31 C32 1.387(8) . ? C31 H31 0.9500 . ? C32 H32 0.9500 . ? C33 C34 1.368(8) . ? C33 C38 1.381(8) . ? C34 C35 1.401(8) . ? C34 H34 0.9500 . ? C35 C36 1.381(9) . ? C35 H35 0.9500 . ? C36 C37 1.375(8) . ? C36 H36 0.9500 . ? C37 C38 1.400(8) . ? C37 H37 0.9500 . ? C38 H38 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6A Au1 C6B 7.0(18) . . ? C6A Au1 O1 174.8(6) . . ? C6B Au1 O1 170.8(11) . . ? C6A Au1 C26 99.1(6) . . ? C6B Au1 C26 101.4(9) . . ? O1 Au1 C26 85.95(17) . . ? C6A Au1 P1 69.9(6) . . ? C6B Au1 P1 68.7(9) . . ? O1 Au1 P1 104.92(11) . . ? C26 Au1 P1 166.39(14) . . ? C6A Au1 Au2 90.9(7) . . ? C6B Au1 Au2 84.5(12) . . ? O1 Au1 Au2 90.69(10) . . ? C26 Au1 Au2 85.08(14) . . ? P1 Au1 Au2 102.66(3) . . ? O3A Au2 O3B 25.2(6) . . ? O3A Au2 P2 174.64(15) . . ? O3B Au2 P2 160.2(6) . . ? O3A Au2 Au1 98.14(14) . . ? O3B Au2 Au1 85.0(6) . . ? P2 Au2 Au1 85.07(4) . . ? C13 P1 C7 107.6(2) . . ? C13 P1 C1A 112.4(8) . . ? C7 P1 C1A 106.4(9) . . ? C13 P1 C1B 111.2(12) . . ? C7 P1 C1B 105.9(14) . . ? C13 P1 Au1 126.01(17) . . ? C7 P1 Au1 118.17(17) . . ? C1A P1 Au1 81.4(6) . . ? C1B P1 Au1 83.0(10) . . ? C21 P2 C27 107.0(2) . . ? C21 P2 C33 106.5(2) . . ? C27 P2 C33 106.1(2) . . ? C21 P2 Au2 112.04(17) . . ? C27 P2 Au2 108.13(17) . . ? C33 P2 Au2 116.53(18) . . ? C2A C1A C6A 122.6(9) . . ? C2A C1A P1 135.1(15) . . ? C6A C1A P1 102.1(10) . . ? F1A C2A C3A 117.7(18) . . ? F1A C2A C1A 124.5(19) . . ? C3A C2A C1A 117.8(13) . . ? F2A C3A C4A 121.0(19) . . ? F2A C3A C2A 118.7(17) . . ? C4A C3A C2A 120.2(14) . . ? F3A C4A C3A 119.3(15) . . ? F3A C4A C5A 118.5(15) . . ? C3A C4A C5A 122.1(11) . . ? F4A C5A C6A 120.5(16) . . ? F4A C5A C4A 120.8(14) . . ? C6A C5A C4A 118.7(9) . . ? C5A C6A C1A 118.5(7) . . ? C5A C6A Au1 135.7(15) . . ? C1A C6A Au1 105.6(10) . . ? C2B C1B C6B 119.4(14) . . ? C2B C1B P1 140(2) . . ? C6B C1B P1 100.0(17) . . ? F1B C2B C3B 124(3) . . ? F1B C2B C1B 115(3) . . ? C3B C2B C1B 121(2) . . ? F2B C3B C4B 117(3) . . ? F2B C3B C2B 123(3) . . ? C4B C3B C2B 120(2) . . ? F3B C4B C3B 119(3) . . ? F3B C4B C5B 122(3) . . ? C3B C4B C5B 119.2(18) . . ? F4B C5B C6B 125(3) . . ? F4B C5B C4B 113(2) . . ? C6B C5B C4B 121.6(13) . . ? C5B C6B C1B 118.6(11) . . ? C5B C6B Au1 133(2) . . ? C1B C6B Au1 108.2(16) . . ? C19 O1 Au1 119.7(3) . . ? C39A O3A Au2 117.7(5) . . ? O4A C39A O3A 124.7(6) . . ? O4A C39A C40A 120.6(10) . . ? O3A C39A C40A 114.6(10) . . ? C39A C40A H40A 109.8 . . ? C39A C40A H40B 109.9 . . ? H40A C40A H40B 109.5 . . ? C39A C40A H40C 108.8 . . ? H40A C40A H40C 109.5 . . ? H40B C40A H40C 109.5 . . ? C39B O3B Au2 121.6(16) . . ? O4B C39B O3B 121(3) . . ? O4B C39B C40B 117(6) . . ? O3B C39B C40B 120(6) . . ? H40D C40B H40E 109.5 . . ? H40D C40B H40F 109.5 . . ? H40E C40B H40F 109.5 . . ? C8 C7 C12 120.5(5) . . ? C8 C7 P1 119.6(4) . . ? C12 C7 P1 119.9(4) . . ? C7 C8 C9 119.4(5) . . ? C7 C8 H8 120.3 . . ? C9 C8 H8 120.3 . . ? C10 C9 C8 119.5(5) . . ? C10 C9 H9 120.3 . . ? C8 C9 H9 120.3 . . ? C9 C10 C11 120.9(5) . . ? C9 C10 H10 119.6 . . ? C11 C10 H10 119.6 . . ? C12 C11 C10 119.8(5) . . ? C12 C11 H11 120.1 . . ? C10 C11 H11 120.1 . . ? C11 C12 C7 119.9(5) . . ? C11 C12 H12 120.0 . . ? C7 C12 H12 120.0 . . ? C18 C13 C14 120.7(5) . . ? C18 C13 P1 121.1(4) . . ? C14 C13 P1 118.2(4) . . ? C15 C14 C13 119.0(5) . . ? C15 C14 H14 120.5 . . ? C13 C14 H14 120.5 . . ? C16 C15 C14 120.1(5) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C17 C16 C15 120.9(5) . . ? C17 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? C16 C17 C18 120.0(5) . . ? C16 C17 H17 120.0 . . ? C18 C17 H17 120.0 . . ? C13 C18 C17 119.3(5) . . ? C13 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? O2 C19 O1 125.7(5) . . ? O2 C19 C20 120.6(5) . . ? O1 C19 C20 113.7(5) . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C22 C21 C26 118.0(5) . . ? C22 C21 P2 120.7(4) . . ? C26 C21 P2 121.3(4) . . ? F5 C22 C23 116.6(5) . . ? F5 C22 C21 120.3(5) . . ? C23 C22 C21 123.1(5) . . ? F6 C23 C22 121.1(5) . . ? F6 C23 C24 119.9(5) . . ? C22 C23 C24 119.0(5) . . ? F7 C24 C25 120.8(5) . . ? F7 C24 C23 120.3(5) . . ? C25 C24 C23 118.8(5) . . ? F8 C25 C26 119.6(5) . . ? F8 C25 C24 116.9(5) . . ? C26 C25 C24 123.4(5) . . ? C25 C26 C21 117.7(5) . . ? C25 C26 Au1 116.1(4) . . ? C21 C26 Au1 125.7(4) . . ? C32 C27 C28 119.8(5) . . ? C32 C27 P2 117.9(4) . . ? C28 C27 P2 122.3(4) . . ? C29 C28 C27 119.5(6) . . ? C29 C28 H28 120.2 . . ? C27 C28 H28 120.2 . . ? C28 C29 C30 120.9(6) . . ? C28 C29 H29 119.5 . . ? C30 C29 H29 119.5 . . ? C31 C30 C29 117.2(6) . . ? C31 C30 H30 121.4 . . ? C29 C30 H30 121.4 . . ? C30 C31 C32 122.5(6) . . ? C30 C31 H31 118.8 . . ? C32 C31 H31 118.8 . . ? C27 C32 C31 120.0(5) . . ? C27 C32 H32 120.0 . . ? C31 C32 H32 120.0 . . ? C34 C33 C38 120.0(5) . . ? C34 C33 P2 119.0(4) . . ? C38 C33 P2 121.0(4) . . ? C33 C34 C35 121.1(6) . . ? C33 C34 H34 119.4 . . ? C35 C34 H34 119.4 . . ? C36 C35 C34 119.0(6) . . ? C36 C35 H35 120.5 . . ? C34 C35 H35 120.5 . . ? C37 C36 C35 119.8(5) . . ? C37 C36 H36 120.1 . . ? C35 C36 H36 120.1 . . ? C36 C37 C38 121.0(6) . . ? C36 C37 H37 119.5 . . ? C38 C37 H37 119.5 . . ? C33 C38 C37 119.0(5) . . ? C33 C38 H38 120.5 . . ? C37 C38 H38 120.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6A Au1 Au2 O3A 59.8(6) . . . . ? C6B Au1 Au2 O3A 56.9(10) . . . . ? O1 Au1 Au2 O3A -115.30(17) . . . . ? C26 Au1 Au2 O3A 158.82(19) . . . . ? P1 Au1 Au2 O3A -9.84(14) . . . . ? C6A Au1 Au2 O3B 38.3(9) . . . . ? C6B Au1 Au2 O3B 35.4(11) . . . . ? O1 Au1 Au2 O3B -136.8(7) . . . . ? C26 Au1 Au2 O3B 137.3(7) . . . . ? P1 Au1 Au2 O3B -31.3(7) . . . . ? C6A Au1 Au2 P2 -124.6(6) . . . . ? C6B Au1 Au2 P2 -127.5(9) . . . . ? O1 Au1 Au2 P2 60.38(11) . . . . ? C26 Au1 Au2 P2 -25.50(14) . . . . ? P1 Au1 Au2 P2 165.84(5) . . . . ? C6A Au1 P1 C13 -117.0(7) . . . . ? C6B Au1 P1 C13 -109.7(13) . . . . ? O1 Au1 P1 C13 63.4(2) . . . . ? C26 Au1 P1 C13 -154.4(6) . . . . ? Au2 Au1 P1 C13 -30.7(2) . . . . ? C6A Au1 P1 C7 98.5(7) . . . . ? C6B Au1 P1 C7 105.9(13) . . . . ? O1 Au1 P1 C7 -81.0(2) . . . . ? C26 Au1 P1 C7 61.2(6) . . . . ? Au2 Au1 P1 C7 -175.21(19) . . . . ? C6A Au1 P1 C1A -5.5(9) . . . . ? C6B Au1 P1 C1A 1.9(18) . . . . ? O1 Au1 P1 C1A 174.9(9) . . . . ? C26 Au1 P1 C1A -42.9(11) . . . . ? Au2 Au1 P1 C1A 80.8(9) . . . . ? C6A Au1 P1 C1B -5.9(18) . . . . ? C6B Au1 P1 C1B 1.5(15) . . . . ? O1 Au1 P1 C1B 174.6(15) . . . . ? C26 Au1 P1 C1B -43.2(16) . . . . ? Au2 Au1 P1 C1B 80.4(15) . . . . ? O3B Au2 P2 C21 -33(2) . . . . ? Au1 Au2 P2 C21 26.65(18) . . . . ? O3B Au2 P2 C27 84(2) . . . . ? Au1 Au2 P2 C27 144.37(18) . . . . ? O3B Au2 P2 C33 -156(2) . . . . ? Au1 Au2 P2 C33 -96.29(19) . . . . ? C13 P1 C1A C2A -52.2(18) . . . . ? C7 P1 C1A C2A 65.4(17) . . . . ? C1B P1 C1A C2A -10(80) . . . . ? Au1 P1 C1A C2A -177.7(17) . . . . ? C13 P1 C1A C6A 133.1(12) . . . . ? C7 P1 C1A C6A -109.3(13) . . . . ? C1B P1 C1A C6A 176(100) . . . . ? Au1 P1 C1A C6A 7.6(12) . . . . ? C6A C1A C2A F1A 179(2) . . . . ? P1 C1A C2A F1A 5(2) . . . . ? C6A C1A C2A C3A 0.6(14) . . . . ? P1 C1A C2A C3A -173(2) . . . . ? F1A C2A C3A F2A 2.9(17) . . . . ? C1A C2A C3A F2A -178.5(12) . . . . ? F1A C2A C3A C4A -178.8(17) . . . . ? C1A C2A C3A C4A -0.2(12) . . . . ? F2A C3A C4A F3A -1(2) . . . . ? C2A C3A C4A F3A -179.6(13) . . . . ? F2A C3A C4A C5A 178.8(15) . . . . ? C2A C3A C4A C5A 1(2) . . . . ? F3A C4A C5A F4A -3(2) . . . . ? C3A C4A C5A F4A 176.5(14) . . . . ? F3A C4A C5A C6A 178.9(16) . . . . ? C3A C4A C5A C6A -1(3) . . . . ? F4A C5A C6A C1A -176.2(15) . . . . ? C4A C5A C6A C1A 2(3) . . . . ? F4A C5A C6A Au1 8(3) . . . . ? C4A C5A C6A Au1 -173.7(17) . . . . ? C2A C1A C6A C5A -1(2) . . . . ? P1 C1A C6A C5A 174.2(18) . . . . ? C2A C1A C6A Au1 175.3(12) . . . . ? P1 C1A C6A Au1 -9.1(15) . . . . ? C6B Au1 C6A C5A 104(13) . . . . ? C26 Au1 C6A C5A -5(2) . . . . ? P1 Au1 C6A C5A -177(2) . . . . ? Au2 Au1 C6A C5A 80(2) . . . . ? C6B Au1 C6A C1A -71(12) . . . . ? C26 Au1 C6A C1A 179.0(12) . . . . ? P1 Au1 C6A C1A 7.3(12) . . . . ? Au2 Au1 C6A C1A -95.8(13) . . . . ? C13 P1 C1B C2B -52(3) . . . . ? C7 P1 C1B C2B 65(3) . . . . ? C1A P1 C1B C2B 170(84) . . . . ? Au1 P1 C1B C2B -178(3) . . . . ? C13 P1 C1B C6B 124.0(19) . . . . ? C7 P1 C1B C6B -119(2) . . . . ? C1A P1 C1B C6B -14(80) . . . . ? Au1 P1 C1B C6B -2(2) . . . . ? C6B C1B C2B F1B 178(3) . . . . ? P1 C1B C2B F1B -6(4) . . . . ? C6B C1B C2B C3B 1(2) . . . . ? P1 C1B C2B C3B 176(4) . . . . ? F1B C2B C3B F2B 5(3) . . . . ? C1B C2B C3B F2B -178(2) . . . . ? F1B C2B C3B C4B -176(3) . . . . ? C1B C2B C3B C4B 2(2) . . . . ? F2B C3B C4B F3B 0(4) . . . . ? C2B C3B C4B F3B -179(2) . . . . ? F2B C3B C4B C5B 177(3) . . . . ? C2B C3B C4B C5B -3(4) . . . . ? F3B C4B C5B F4B -1(5) . . . . ? C3B C4B C5B F4B -178(3) . . . . ? F3B C4B C5B C6B 178(3) . . . . ? C3B C4B C5B C6B 1(5) . . . . ? F4B C5B C6B C1B -180(3) . . . . ? C4B C5B C6B C1B 2(5) . . . . ? F4B C5B C6B Au1 -2(6) . . . . ? C4B C5B C6B Au1 179(3) . . . . ? C2B C1B C6B C5B -2(4) . . . . ? P1 C1B C6B C5B -179(3) . . . . ? C2B C1B C6B Au1 179.3(19) . . . . ? P1 C1B C6B Au1 2(2) . . . . ? C6A Au1 C6B C5B -81(12) . . . . ? C26 Au1 C6B C5B -10(4) . . . . ? P1 Au1 C6B C5B 180(4) . . . . ? Au2 Au1 C6B C5B 74(4) . . . . ? C6A Au1 C6B C1B 97(12) . . . . ? C26 Au1 C6B C1B 168(2) . . . . ? P1 Au1 C6B C1B -2(2) . . . . ? Au2 Au1 C6B C1B -108(2) . . . . ? C26 Au1 O1 C19 -161.2(4) . . . . ? P1 Au1 O1 C19 10.4(4) . . . . ? Au2 Au1 O1 C19 113.7(4) . . . . ? O3B Au2 O3A C39A -29.9(16) . . . . ? Au1 Au2 O3A C39A -89.0(5) . . . . ? Au2 O3A C39A O4A -9.8(10) . . . . ? Au2 O3A C39A C40A 168.6(14) . . . . ? O3A Au2 O3B C39B 22(2) . . . . ? P2 Au2 O3B C39B -156(2) . . . . ? Au1 Au2 O3B C39B 144(3) . . . . ? Au2 O3B C39B O4B -4(5) . . . . ? Au2 O3B C39B C40B -172(6) . . . . ? C13 P1 C7 C8 145.3(4) . . . . ? C1A P1 C7 C8 24.7(8) . . . . ? C1B P1 C7 C8 26.4(12) . . . . ? Au1 P1 C7 C8 -64.2(5) . . . . ? C13 P1 C7 C12 -35.1(5) . . . . ? C1A P1 C7 C12 -155.8(8) . . . . ? C1B P1 C7 C12 -154.1(11) . . . . ? Au1 P1 C7 C12 115.4(4) . . . . ? C12 C7 C8 C9 -0.2(8) . . . . ? P1 C7 C8 C9 179.4(4) . . . . ? C7 C8 C9 C10 1.2(8) . . . . ? C8 C9 C10 C11 -1.6(8) . . . . ? C9 C10 C11 C12 1.0(8) . . . . ? C10 C11 C12 C7 0.1(8) . . . . ? C8 C7 C12 C11 -0.5(8) . . . . ? P1 C7 C12 C11 180.0(4) . . . . ? C7 P1 C13 C18 131.3(4) . . . . ? C1A P1 C13 C18 -112.0(9) . . . . ? C1B P1 C13 C18 -113.2(14) . . . . ? Au1 P1 C13 C18 -16.2(5) . . . . ? C7 P1 C13 C14 -48.9(5) . . . . ? C1A P1 C13 C14 67.9(9) . . . . ? C1B P1 C13 C14 66.7(14) . . . . ? Au1 P1 C13 C14 163.6(3) . . . . ? C18 C13 C14 C15 0.3(8) . . . . ? P1 C13 C14 C15 -179.5(4) . . . . ? C13 C14 C15 C16 -0.6(8) . . . . ? C14 C15 C16 C17 0.6(8) . . . . ? C15 C16 C17 C18 -0.3(8) . . . . ? C14 C13 C18 C17 0.0(8) . . . . ? P1 C13 C18 C17 179.8(4) . . . . ? C16 C17 C18 C13 0.0(8) . . . . ? Au1 O1 C19 O2 0.8(8) . . . . ? Au1 O1 C19 C20 -179.1(4) . . . . ? C27 P2 C21 C22 41.8(5) . . . . ? C33 P2 C21 C22 -71.3(5) . . . . ? Au2 P2 C21 C22 160.2(4) . . . . ? C27 P2 C21 C26 -137.6(4) . . . . ? C33 P2 C21 C26 109.2(4) . . . . ? Au2 P2 C21 C26 -19.3(5) . . . . ? C26 C21 C22 F5 -178.7(4) . . . . ? P2 C21 C22 F5 1.9(7) . . . . ? C26 C21 C22 C23 1.0(8) . . . . ? P2 C21 C22 C23 -178.5(4) . . . . ? F5 C22 C23 F6 -1.0(7) . . . . ? C21 C22 C23 F6 179.3(5) . . . . ? F5 C22 C23 C24 -180.0(5) . . . . ? C21 C22 C23 C24 0.3(8) . . . . ? F6 C23 C24 F7 1.0(8) . . . . ? C22 C23 C24 F7 -180.0(5) . . . . ? F6 C23 C24 C25 -179.7(5) . . . . ? C22 C23 C24 C25 -0.7(8) . . . . ? F7 C24 C25 F8 1.1(8) . . . . ? C23 C24 C25 F8 -178.2(5) . . . . ? F7 C24 C25 C26 179.0(5) . . . . ? C23 C24 C25 C26 -0.3(8) . . . . ? F8 C25 C26 C21 179.5(5) . . . . ? C24 C25 C26 C21 1.6(8) . . . . ? F8 C25 C26 Au1 7.8(6) . . . . ? C24 C25 C26 Au1 -170.0(4) . . . . ? C22 C21 C26 C25 -1.9(7) . . . . ? P2 C21 C26 C25 177.5(4) . . . . ? C22 C21 C26 Au1 168.8(4) . . . . ? P2 C21 C26 Au1 -11.7(6) . . . . ? C6A Au1 C26 C25 -72.9(8) . . . . ? C6B Au1 C26 C25 -79.6(13) . . . . ? O1 Au1 C26 C25 105.9(4) . . . . ? P1 Au1 C26 C25 -37.6(9) . . . . ? Au2 Au1 C26 C25 -163.0(4) . . . . ? C6A Au1 C26 C21 116.3(8) . . . . ? C6B Au1 C26 C21 109.5(13) . . . . ? O1 Au1 C26 C21 -64.9(4) . . . . ? P1 Au1 C26 C21 151.5(4) . . . . ? Au2 Au1 C26 C21 26.1(4) . . . . ? C21 P2 C27 C32 82.0(5) . . . . ? C33 P2 C27 C32 -164.6(4) . . . . ? Au2 P2 C27 C32 -38.9(5) . . . . ? C21 P2 C27 C28 -99.7(5) . . . . ? C33 P2 C27 C28 13.7(5) . . . . ? Au2 P2 C27 C28 139.4(4) . . . . ? C32 C27 C28 C29 -0.6(9) . . . . ? P2 C27 C28 C29 -178.9(5) . . . . ? C27 C28 C29 C30 -1.9(10) . . . . ? C28 C29 C30 C31 2.0(9) . . . . ? C29 C30 C31 C32 0.2(9) . . . . ? C28 C27 C32 C31 2.8(8) . . . . ? P2 C27 C32 C31 -178.8(4) . . . . ? C30 C31 C32 C27 -2.7(9) . . . . ? C21 P2 C33 C34 171.7(5) . . . . ? C27 P2 C33 C34 57.9(5) . . . . ? Au2 P2 C33 C34 -62.5(5) . . . . ? C21 P2 C33 C38 -7.3(5) . . . . ? C27 P2 C33 C38 -121.1(5) . . . . ? Au2 P2 C33 C38 118.5(4) . . . . ? C38 C33 C34 C35 0.8(9) . . . . ? P2 C33 C34 C35 -178.2(5) . . . . ? C33 C34 C35 C36 0.4(10) . . . . ? C34 C35 C36 C37 -1.8(9) . . . . ? C35 C36 C37 C38 2.1(9) . . . . ? C34 C33 C38 C37 -0.5(9) . . . . ? P2 C33 C38 C37 178.4(4) . . . . ? C36 C37 C38 C33 -1.0(9) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 28.50 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 2.017 _refine_diff_density_min -1.579 _refine_diff_density_rms 0.173 # Attachment 'neda00302.cif.txt' data_neda00302 _database_code_depnum_ccdc_archive 'CCDC 725991' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 F8 P2' _chemical_formula_sum 'C36 H20 Au2 F8 P2' _chemical_formula_weight 1060.39 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.7539(2) _cell_length_b 12.7320(2) _cell_length_c 12.8969(2) _cell_angle_alpha 90.4600(10) _cell_angle_beta 113.9920(10) _cell_angle_gamma 98.3480(10) _cell_volume 1591.77(5) _cell_formula_units_Z 2 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 40911 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description polyhedron _exptl_crystal_colour colorless _exptl_crystal_size_max 0.11 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.212 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 992 _exptl_absorpt_coefficient_mu 9.381 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.421 _exptl_absorpt_correction_T_max 0.574 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 53442 _diffrn_reflns_av_R_equivalents 0.0644 _diffrn_reflns_av_sigmaI/netI 0.0334 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.78 _diffrn_reflns_theta_max 28.00 _reflns_number_total 7679 _reflns_number_gt 5225 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0247P)^2^+1.0031P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7679 _refine_ls_number_parameters 433 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0470 _refine_ls_R_factor_gt 0.0240 _refine_ls_wR_factor_ref 0.0591 _refine_ls_wR_factor_gt 0.0537 _refine_ls_goodness_of_fit_ref 1.019 _refine_ls_restrained_S_all 1.019 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.854860(15) 0.475202(11) 0.448109(12) 0.01750(5) Uani 1 1 d . . . Au2 Au 0.145001(15) 0.026134(11) 0.050227(12) 0.01611(5) Uani 1 1 d . . . P1 P 0.87473(11) 0.32355(8) 0.54244(9) 0.0179(2) Uani 1 1 d . . . P2 P 0.11528(11) 0.17610(8) 0.12977(9) 0.0174(2) Uani 1 1 d . . . F1 F 0.9770(3) 0.14656(18) 0.6937(2) 0.0306(6) Uani 1 1 d . . . F2 F 1.2309(3) 0.13723(19) 0.8497(2) 0.0309(6) Uani 1 1 d . . . F3 F 1.4450(3) 0.2868(2) 0.8656(2) 0.0383(7) Uani 1 1 d . . . F4 F 1.4056(2) 0.4486(2) 0.7307(2) 0.0341(6) Uani 1 1 d . . . F5 F 0.0064(2) 0.34312(17) 0.2232(2) 0.0272(6) Uani 1 1 d . . . F6 F -0.2529(3) 0.34597(18) 0.2004(2) 0.0298(6) Uani 1 1 d . . . F7 F -0.4609(2) 0.19399(18) 0.06585(19) 0.0260(5) Uani 1 1 d . . . F8 F -0.4130(2) 0.04226(18) -0.0531(2) 0.0263(5) Uani 1 1 d . . . C1 C 1.0533(4) 0.3111(3) 0.6336(3) 0.0187(8) Uani 1 1 d . . . C2 C 1.0795(4) 0.2261(3) 0.7017(3) 0.0212(9) Uani 1 1 d . . . C3 C 1.2083(5) 0.2179(3) 0.7801(3) 0.0240(9) Uani 1 1 d . . . C4 C 1.3181(4) 0.2944(3) 0.7887(4) 0.0260(10) Uani 1 1 d . . . C5 C 1.2927(4) 0.3769(3) 0.7183(3) 0.0221(9) Uani 1 1 d . . . C6 C 1.1647(4) 0.3902(3) 0.6409(3) 0.0181(8) Uani 1 1 d . . . C7 C 0.7907(4) 0.3188(3) 0.6397(3) 0.0195(8) Uani 1 1 d . . . C8 C 0.7325(4) 0.2250(3) 0.6695(4) 0.0246(9) Uani 1 1 d . . . H8 H 0.7238 0.1584 0.6313 0.030 Uiso 1 1 calc R . . C9 C 0.6872(4) 0.2306(4) 0.7564(4) 0.0292(10) Uani 1 1 d . . . H9 H 0.6487 0.1672 0.7780 0.035 Uiso 1 1 calc R . . C10 C 0.6980(5) 0.3274(4) 0.8113(4) 0.0312(11) Uani 1 1 d . . . H10 H 0.6692 0.3301 0.8717 0.037 Uiso 1 1 calc R . . C11 C 0.7507(5) 0.4200(4) 0.7782(4) 0.0292(10) Uani 1 1 d . . . H11 H 0.7547 0.4867 0.8141 0.035 Uiso 1 1 calc R . . C12 C 0.7978(4) 0.4167(3) 0.6932(3) 0.0242(9) Uani 1 1 d . . . H12 H 0.8348 0.4807 0.6714 0.029 Uiso 1 1 calc R . . C13 C 0.8003(4) 0.2033(3) 0.4464(3) 0.0190(9) Uani 1 1 d . . . C14 C 0.8853(5) 0.1458(3) 0.4176(3) 0.0241(9) Uani 1 1 d . . . H14 H 0.9828 0.1641 0.4544 0.029 Uiso 1 1 calc R . . C15 C 0.8245(5) 0.0620(3) 0.3347(3) 0.0250(9) Uani 1 1 d . . . H15 H 0.8810 0.0228 0.3144 0.030 Uiso 1 1 calc R . . C16 C 0.6829(5) 0.0346(3) 0.2812(3) 0.0271(10) Uani 1 1 d . . . H16 H 0.6430 -0.0238 0.2255 0.032 Uiso 1 1 calc R . . C17 C 0.5989(5) 0.0917(3) 0.3081(3) 0.0247(9) Uani 1 1 d . . . H17 H 0.5014 0.0729 0.2708 0.030 Uiso 1 1 calc R . . C18 C 0.6578(4) 0.1770(3) 0.3904(3) 0.0213(9) Uani 1 1 d . . . H18 H 0.6004 0.2172 0.4082 0.026 Uiso 1 1 calc R . . C19 C -0.0645(4) 0.1827(3) 0.1028(3) 0.0167(8) Uani 1 1 d . . . C20 C -0.0948(4) 0.2641(3) 0.1561(3) 0.0201(9) Uani 1 1 d . . . C21 C -0.2267(5) 0.2680(3) 0.1437(3) 0.0219(9) Uani 1 1 d . . . C22 C -0.3326(4) 0.1916(3) 0.0752(3) 0.0205(9) Uani 1 1 d . . . C23 C -0.3031(4) 0.1125(3) 0.0179(3) 0.0194(8) Uani 1 1 d . . . C24 C -0.1722(4) 0.1040(3) 0.0299(3) 0.0176(8) Uani 1 1 d . . . C25 C 0.1765(4) 0.2933(3) 0.0737(3) 0.0166(8) Uani 1 1 d . . . C26 C 0.3183(4) 0.3195(3) 0.1034(4) 0.0239(9) Uani 1 1 d . . . H26 H 0.3809 0.2803 0.1567 0.029 Uiso 1 1 calc R . . C27 C 0.3666(4) 0.4029(3) 0.0547(4) 0.0248(9) Uani 1 1 d . . . H27 H 0.4630 0.4216 0.0760 0.030 Uiso 1 1 calc R . . C28 C 0.2774(5) 0.4592(3) -0.0241(4) 0.0271(10) Uani 1 1 d . . . H28 H 0.3121 0.5166 -0.0567 0.033 Uiso 1 1 calc R . . C29 C 0.1368(5) 0.4323(3) -0.0560(4) 0.0280(10) Uani 1 1 d . . . H29 H 0.0750 0.4704 -0.1115 0.034 Uiso 1 1 calc R . . C30 C 0.0856(5) 0.3494(3) -0.0070(3) 0.0244(9) Uani 1 1 d . . . H30 H -0.0109 0.3313 -0.0285 0.029 Uiso 1 1 calc R . . C31 C 0.2100(4) 0.1889(3) 0.2838(3) 0.0205(9) Uani 1 1 d . . . C32 C 0.2049(5) 0.0949(3) 0.3387(4) 0.0289(10) Uani 1 1 d . . . H32 H 0.1565 0.0298 0.2950 0.035 Uiso 1 1 calc R . . C33 C 0.2692(5) 0.0961(4) 0.4551(4) 0.0360(11) Uani 1 1 d . . . H33 H 0.2647 0.0320 0.4916 0.043 Uiso 1 1 calc R . . C34 C 0.3406(5) 0.1902(4) 0.5195(4) 0.0348(11) Uani 1 1 d . . . H34 H 0.3846 0.1909 0.6001 0.042 Uiso 1 1 calc R . . C35 C 0.3477(5) 0.2826(4) 0.4665(4) 0.0374(12) Uani 1 1 d . . . H35 H 0.3973 0.3470 0.5108 0.045 Uiso 1 1 calc R . . C36 C 0.2828(5) 0.2828(3) 0.3482(4) 0.0277(10) Uani 1 1 d . . . H36 H 0.2886 0.3470 0.3122 0.033 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01967(9) 0.01536(8) 0.01665(9) 0.00096(6) 0.00725(7) 0.00103(6) Au2 0.01832(9) 0.01405(8) 0.01536(9) -0.00102(6) 0.00675(7) 0.00142(6) P1 0.0207(6) 0.0149(5) 0.0177(5) 0.0008(4) 0.0081(5) 0.0014(4) P2 0.0196(5) 0.0141(5) 0.0173(5) -0.0005(4) 0.0068(4) 0.0019(4) F1 0.0347(15) 0.0192(12) 0.0374(16) 0.0081(11) 0.0154(13) 0.0014(11) F2 0.0402(16) 0.0295(14) 0.0276(14) 0.0148(11) 0.0159(12) 0.0133(12) F3 0.0244(15) 0.0527(17) 0.0326(15) 0.0201(13) 0.0055(12) 0.0091(13) F4 0.0207(13) 0.0387(15) 0.0346(15) 0.0131(12) 0.0043(12) -0.0002(12) F5 0.0277(14) 0.0187(12) 0.0297(14) -0.0095(10) 0.0072(11) 0.0015(10) F6 0.0409(16) 0.0243(13) 0.0294(14) -0.0019(11) 0.0174(13) 0.0126(12) F7 0.0238(13) 0.0340(14) 0.0248(13) 0.0063(11) 0.0124(11) 0.0118(11) F8 0.0211(13) 0.0292(13) 0.0257(13) -0.0046(11) 0.0081(11) 0.0004(10) C1 0.024(2) 0.0172(19) 0.018(2) 0.0003(16) 0.0101(18) 0.0062(16) C2 0.025(2) 0.018(2) 0.022(2) 0.0031(16) 0.0113(19) 0.0031(17) C3 0.038(3) 0.023(2) 0.019(2) 0.0046(17) 0.018(2) 0.0092(19) C4 0.024(2) 0.032(2) 0.023(2) 0.0053(19) 0.009(2) 0.0099(19) C5 0.021(2) 0.025(2) 0.020(2) 0.0011(17) 0.0099(18) -0.0003(18) C6 0.024(2) 0.0149(18) 0.015(2) -0.0026(15) 0.0082(18) 0.0032(16) C7 0.017(2) 0.025(2) 0.015(2) 0.0034(16) 0.0051(17) 0.0012(17) C8 0.025(2) 0.023(2) 0.024(2) 0.0025(18) 0.010(2) -0.0001(18) C9 0.023(2) 0.033(2) 0.029(3) 0.009(2) 0.010(2) -0.0028(19) C10 0.026(2) 0.050(3) 0.021(2) 0.001(2) 0.014(2) 0.004(2) C11 0.031(3) 0.032(2) 0.027(2) -0.0020(19) 0.013(2) 0.010(2) C12 0.027(2) 0.029(2) 0.019(2) 0.0012(18) 0.0093(19) 0.0073(19) C13 0.026(2) 0.0151(19) 0.0109(19) 0.0005(15) 0.0040(17) 0.0000(17) C14 0.028(2) 0.020(2) 0.020(2) -0.0001(17) 0.0076(19) -0.0011(18) C15 0.033(3) 0.020(2) 0.025(2) 0.0032(18) 0.015(2) 0.0059(19) C16 0.039(3) 0.021(2) 0.017(2) 0.0015(17) 0.007(2) 0.0043(19) C17 0.027(2) 0.023(2) 0.017(2) 0.0009(17) 0.0030(19) -0.0003(18) C18 0.025(2) 0.019(2) 0.020(2) 0.0031(17) 0.0092(19) 0.0053(17) C19 0.018(2) 0.0169(19) 0.0142(19) 0.0028(15) 0.0058(17) 0.0024(16) C20 0.026(2) 0.0141(19) 0.020(2) -0.0016(16) 0.0108(19) -0.0009(16) C21 0.037(3) 0.021(2) 0.013(2) 0.0043(16) 0.0132(19) 0.0130(19) C22 0.021(2) 0.023(2) 0.022(2) 0.0071(17) 0.0116(19) 0.0073(17) C23 0.023(2) 0.020(2) 0.014(2) 0.0011(16) 0.0065(17) 0.0012(17) C24 0.024(2) 0.0191(19) 0.0133(19) 0.0048(15) 0.0103(17) 0.0069(17) C25 0.023(2) 0.0120(18) 0.015(2) -0.0042(15) 0.0078(17) 0.0010(16) C26 0.024(2) 0.022(2) 0.025(2) -0.0010(18) 0.0093(19) 0.0060(18) C27 0.022(2) 0.026(2) 0.031(3) 0.0003(19) 0.016(2) 0.0001(18) C28 0.039(3) 0.020(2) 0.027(2) -0.0002(18) 0.019(2) -0.0009(19) C29 0.033(3) 0.025(2) 0.025(2) 0.0092(18) 0.009(2) 0.0074(19) C30 0.025(2) 0.025(2) 0.022(2) 0.0050(17) 0.0095(19) 0.0011(18) C31 0.025(2) 0.025(2) 0.0111(19) -0.0020(16) 0.0071(18) 0.0030(18) C32 0.037(3) 0.025(2) 0.023(2) 0.0032(18) 0.010(2) 0.004(2) C33 0.049(3) 0.039(3) 0.022(2) 0.012(2) 0.015(2) 0.012(2) C34 0.039(3) 0.047(3) 0.015(2) 0.002(2) 0.005(2) 0.014(2) C35 0.036(3) 0.041(3) 0.029(3) -0.014(2) 0.008(2) 0.004(2) C36 0.033(3) 0.025(2) 0.022(2) -0.0015(18) 0.009(2) 0.0034(19) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.058(4) 2_766 ? Au1 P1 2.2803(10) . ? Au1 Au1 2.8198(3) 2_766 ? Au2 C24 2.063(4) 2 ? Au2 P2 2.2831(10) . ? Au2 Au2 2.8187(3) 2 ? P1 C7 1.817(4) . ? P1 C13 1.823(4) . ? P1 C1 1.831(4) . ? P2 C25 1.817(4) . ? P2 C31 1.820(4) . ? P2 C19 1.835(4) . ? F1 C2 1.354(4) . ? F2 C3 1.353(4) . ? F3 C4 1.340(5) . ? F4 C5 1.361(4) . ? F5 C20 1.359(4) . ? F6 C21 1.355(4) . ? F7 C22 1.340(4) . ? F8 C23 1.354(4) . ? C1 C2 1.386(5) . ? C1 C6 1.420(5) . ? C2 C3 1.362(6) . ? C3 C4 1.383(6) . ? C4 C5 1.378(6) . ? C5 C6 1.369(6) . ? C6 Au1 2.058(4) 2_766 ? C7 C12 1.397(6) . ? C7 C8 1.397(5) . ? C8 C9 1.396(6) . ? C8 H8 0.9500 . ? C9 C10 1.382(6) . ? C9 H9 0.9500 . ? C10 C11 1.381(6) . ? C10 H10 0.9500 . ? C11 C12 1.384(5) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.389(6) . ? C13 C14 1.405(6) . ? C14 C15 1.386(5) . ? C14 H14 0.9500 . ? C15 C16 1.380(6) . ? C15 H15 0.9500 . ? C16 C17 1.381(6) . ? C16 H16 0.9500 . ? C17 C18 1.393(5) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.386(5) . ? C19 C24 1.411(5) . ? C20 C21 1.370(6) . ? C21 C22 1.368(6) . ? C22 C23 1.391(5) . ? C23 C24 1.373(5) . ? C24 Au2 2.063(4) 2 ? C25 C30 1.391(6) . ? C25 C26 1.400(6) . ? C26 C27 1.381(6) . ? C26 H26 0.9500 . ? C27 C28 1.374(6) . ? C27 H27 0.9500 . ? C28 C29 1.383(6) . ? C28 H28 0.9500 . ? C29 C30 1.394(5) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.384(6) . ? C31 C32 1.402(6) . ? C32 C33 1.373(6) . ? C32 H32 0.9500 . ? C33 C34 1.383(6) . ? C33 H33 0.9500 . ? C34 C35 1.373(7) . ? C34 H34 0.9500 . ? C35 C36 1.396(6) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 P1 178.54(10) 2_766 . ? C6 Au1 Au1 93.07(11) 2_766 2_766 ? P1 Au1 Au1 87.45(3) . 2_766 ? C24 Au2 P2 176.46(10) 2 . ? C24 Au2 Au2 93.66(11) 2 2 ? P2 Au2 Au2 86.54(3) . 2 ? C7 P1 C13 107.16(18) . . ? C7 P1 C1 103.93(18) . . ? C13 P1 C1 107.06(18) . . ? C7 P1 Au1 112.05(14) . . ? C13 P1 Au1 112.63(13) . . ? C1 P1 Au1 113.42(13) . . ? C25 P2 C31 107.85(18) . . ? C25 P2 C19 106.65(18) . . ? C31 P2 C19 105.80(18) . . ? C25 P2 Au2 109.94(12) . . ? C31 P2 Au2 111.91(14) . . ? C19 P2 Au2 114.34(13) . . ? C2 C1 C6 119.4(4) . . ? C2 C1 P1 119.4(3) . . ? C6 C1 P1 121.1(3) . . ? F1 C2 C3 116.4(3) . . ? F1 C2 C1 121.3(4) . . ? C3 C2 C1 122.4(4) . . ? F2 C3 C2 121.6(4) . . ? F2 C3 C4 119.4(4) . . ? C2 C3 C4 119.0(4) . . ? F3 C4 C5 122.1(4) . . ? F3 C4 C3 119.3(4) . . ? C5 C4 C3 118.6(4) . . ? F4 C5 C6 120.1(4) . . ? F4 C5 C4 115.4(4) . . ? C6 C5 C4 124.5(4) . . ? C5 C6 C1 116.0(4) . . ? C5 C6 Au1 118.9(3) . 2_766 ? C1 C6 Au1 125.0(3) . 2_766 ? C12 C7 C8 120.1(4) . . ? C12 C7 P1 115.4(3) . . ? C8 C7 P1 124.3(3) . . ? C9 C8 C7 118.9(4) . . ? C9 C8 H8 120.5 . . ? C7 C8 H8 120.5 . . ? C10 C9 C8 120.8(4) . . ? C10 C9 H9 119.6 . . ? C8 C9 H9 119.6 . . ? C11 C10 C9 119.8(4) . . ? C11 C10 H10 120.1 . . ? C9 C10 H10 120.1 . . ? C10 C11 C12 120.6(4) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C11 C12 C7 119.7(4) . . ? C11 C12 H12 120.1 . . ? C7 C12 H12 120.1 . . ? C18 C13 C14 119.9(4) . . ? C18 C13 P1 119.2(3) . . ? C14 C13 P1 120.3(3) . . ? C15 C14 C13 118.9(4) . . ? C15 C14 H14 120.5 . . ? C13 C14 H14 120.5 . . ? C16 C15 C14 120.9(4) . . ? C16 C15 H15 119.6 . . ? C14 C15 H15 119.6 . . ? C15 C16 C17 120.4(4) . . ? C15 C16 H16 119.8 . . ? C17 C16 H16 119.8 . . ? C16 C17 C18 119.6(4) . . ? C16 C17 H17 120.2 . . ? C18 C17 H17 120.2 . . ? C13 C18 C17 120.2(4) . . ? C13 C18 H18 119.9 . . ? C17 C18 H18 119.9 . . ? C20 C19 C24 119.7(4) . . ? C20 C19 P2 119.9(3) . . ? C24 C19 P2 120.4(3) . . ? F5 C20 C21 117.5(3) . . ? F5 C20 C19 120.8(4) . . ? C21 C20 C19 121.7(4) . . ? F6 C21 C22 119.7(4) . . ? F6 C21 C20 120.6(4) . . ? C22 C21 C20 119.8(4) . . ? F7 C22 C21 119.6(4) . . ? F7 C22 C23 121.8(4) . . ? C21 C22 C23 118.6(4) . . ? F8 C23 C24 120.6(3) . . ? F8 C23 C22 115.8(3) . . ? C24 C23 C22 123.6(4) . . ? C23 C24 C19 116.7(3) . . ? C23 C24 Au2 118.4(3) . 2 ? C19 C24 Au2 124.8(3) . 2 ? C30 C25 C26 119.6(4) . . ? C30 C25 P2 121.7(3) . . ? C26 C25 P2 118.3(3) . . ? C27 C26 C25 119.6(4) . . ? C27 C26 H26 120.2 . . ? C25 C26 H26 120.2 . . ? C28 C27 C26 121.0(4) . . ? C28 C27 H27 119.5 . . ? C26 C27 H27 119.5 . . ? C27 C28 C29 119.9(4) . . ? C27 C28 H28 120.1 . . ? C29 C28 H28 120.1 . . ? C28 C29 C30 120.2(4) . . ? C28 C29 H29 119.9 . . ? C30 C29 H29 119.9 . . ? C25 C30 C29 119.7(4) . . ? C25 C30 H30 120.2 . . ? C29 C30 H30 120.2 . . ? C36 C31 C32 119.2(4) . . ? C36 C31 P2 125.2(3) . . ? C32 C31 P2 115.6(3) . . ? C33 C32 C31 120.5(4) . . ? C33 C32 H32 119.8 . . ? C31 C32 H32 119.8 . . ? C32 C33 C34 120.3(4) . . ? C32 C33 H33 119.9 . . ? C34 C33 H33 119.9 . . ? C35 C34 C33 119.7(4) . . ? C35 C34 H34 120.1 . . ? C33 C34 H34 120.1 . . ? C34 C35 C36 120.8(4) . . ? C34 C35 H35 119.6 . . ? C36 C35 H35 119.6 . . ? C31 C36 C35 119.6(4) . . ? C31 C36 H36 120.2 . . ? C35 C36 H36 120.2 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag Au1 Au1 P1 C7 118.49(14) 2_766 . . . ? Au1 Au1 P1 C13 -120.60(15) 2_766 . . . ? Au1 Au1 P1 C1 1.20(13) 2_766 . . . ? Au2 Au2 P2 C25 -115.02(14) 2 . . . ? Au2 Au2 P2 C31 125.14(14) 2 . . . ? Au2 Au2 P2 C19 4.88(13) 2 . . . ? C7 P1 C1 C2 53.7(3) . . . . ? C13 P1 C1 C2 -59.5(3) . . . . ? Au1 P1 C1 C2 175.7(3) . . . . ? C7 P1 C1 C6 -122.4(3) . . . . ? C13 P1 C1 C6 124.4(3) . . . . ? Au1 P1 C1 C6 -0.5(3) . . . . ? C6 C1 C2 F1 -177.0(3) . . . . ? P1 C1 C2 F1 6.8(5) . . . . ? C6 C1 C2 C3 3.2(6) . . . . ? P1 C1 C2 C3 -173.0(3) . . . . ? F1 C2 C3 F2 -3.1(6) . . . . ? C1 C2 C3 F2 176.7(4) . . . . ? F1 C2 C3 C4 177.3(3) . . . . ? C1 C2 C3 C4 -3.0(6) . . . . ? F2 C3 C4 F3 0.4(6) . . . . ? C2 C3 C4 F3 -180.0(4) . . . . ? F2 C3 C4 C5 -179.1(4) . . . . ? C2 C3 C4 C5 0.6(6) . . . . ? F3 C4 C5 F4 1.2(6) . . . . ? C3 C4 C5 F4 -179.4(4) . . . . ? F3 C4 C5 C6 -177.9(4) . . . . ? C3 C4 C5 C6 1.5(6) . . . . ? F4 C5 C6 C1 179.7(3) . . . . ? C4 C5 C6 C1 -1.2(6) . . . . ? F4 C5 C6 Au1 -3.9(5) . . . 2_766 ? C4 C5 C6 Au1 175.2(3) . . . 2_766 ? C2 C1 C6 C5 -1.1(5) . . . . ? P1 C1 C6 C5 175.1(3) . . . . ? C2 C1 C6 Au1 -177.3(3) . . . 2_766 ? P1 C1 C6 Au1 -1.1(5) . . . 2_766 ? C13 P1 C7 C12 -159.2(3) . . . . ? C1 P1 C7 C12 87.6(3) . . . . ? Au1 P1 C7 C12 -35.2(3) . . . . ? C13 P1 C7 C8 26.4(4) . . . . ? C1 P1 C7 C8 -86.7(4) . . . . ? Au1 P1 C7 C8 150.4(3) . . . . ? C12 C7 C8 C9 -2.6(6) . . . . ? P1 C7 C8 C9 171.5(3) . . . . ? C7 C8 C9 C10 0.8(6) . . . . ? C8 C9 C10 C11 1.7(7) . . . . ? C9 C10 C11 C12 -2.4(7) . . . . ? C10 C11 C12 C7 0.7(7) . . . . ? C8 C7 C12 C11 1.9(6) . . . . ? P1 C7 C12 C11 -172.7(3) . . . . ? C7 P1 C13 C18 51.0(4) . . . . ? C1 P1 C13 C18 162.0(3) . . . . ? Au1 P1 C13 C18 -72.7(3) . . . . ? C7 P1 C13 C14 -137.4(3) . . . . ? C1 P1 C13 C14 -26.4(4) . . . . ? Au1 P1 C13 C14 98.9(3) . . . . ? C18 C13 C14 C15 -1.2(6) . . . . ? P1 C13 C14 C15 -172.8(3) . . . . ? C13 C14 C15 C16 -0.3(6) . . . . ? C14 C15 C16 C17 1.1(6) . . . . ? C15 C16 C17 C18 -0.4(6) . . . . ? C14 C13 C18 C17 1.9(6) . . . . ? P1 C13 C18 C17 173.5(3) . . . . ? C16 C17 C18 C13 -1.1(6) . . . . ? C25 P2 C19 C20 -65.0(3) . . . . ? C31 P2 C19 C20 49.7(4) . . . . ? Au2 P2 C19 C20 173.3(3) . . . . ? C25 P2 C19 C24 116.4(3) . . . . ? C31 P2 C19 C24 -129.0(3) . . . . ? Au2 P2 C19 C24 -5.3(3) . . . . ? C24 C19 C20 F5 -177.4(3) . . . . ? P2 C19 C20 F5 3.9(5) . . . . ? C24 C19 C20 C21 2.8(6) . . . . ? P2 C19 C20 C21 -175.9(3) . . . . ? F5 C20 C21 F6 -2.5(6) . . . . ? C19 C20 C21 F6 177.3(3) . . . . ? F5 C20 C21 C22 178.6(3) . . . . ? C19 C20 C21 C22 -1.6(6) . . . . ? F6 C21 C22 F7 -0.8(6) . . . . ? C20 C21 C22 F7 178.1(3) . . . . ? F6 C21 C22 C23 -180.0(3) . . . . ? C20 C21 C22 C23 -1.1(6) . . . . ? F7 C22 C23 F8 4.0(5) . . . . ? C21 C22 C23 F8 -176.8(3) . . . . ? F7 C22 C23 C24 -176.4(4) . . . . ? C21 C22 C23 C24 2.8(6) . . . . ? F8 C23 C24 C19 178.0(3) . . . . ? C22 C23 C24 C19 -1.6(6) . . . . ? F8 C23 C24 Au2 -5.9(5) . . . 2 ? C22 C23 C24 Au2 174.5(3) . . . 2 ? C20 C19 C24 C23 -1.2(5) . . . . ? P2 C19 C24 C23 177.4(3) . . . . ? C20 C19 C24 Au2 -177.0(3) . . . 2 ? P2 C19 C24 Au2 1.6(5) . . . 2 ? C31 P2 C25 C30 -133.5(3) . . . . ? C19 P2 C25 C30 -20.2(4) . . . . ? Au2 P2 C25 C30 104.3(3) . . . . ? C31 P2 C25 C26 53.9(3) . . . . ? C19 P2 C25 C26 167.2(3) . . . . ? Au2 P2 C25 C26 -68.3(3) . . . . ? C30 C25 C26 C27 1.9(6) . . . . ? P2 C25 C26 C27 174.7(3) . . . . ? C25 C26 C27 C28 -1.3(6) . . . . ? C26 C27 C28 C29 -0.3(6) . . . . ? C27 C28 C29 C30 1.1(6) . . . . ? C26 C25 C30 C29 -1.1(6) . . . . ? P2 C25 C30 C29 -173.6(3) . . . . ? C28 C29 C30 C25 -0.4(6) . . . . ? C25 P2 C31 C36 17.7(4) . . . . ? C19 P2 C31 C36 -96.1(4) . . . . ? Au2 P2 C31 C36 138.8(3) . . . . ? C25 P2 C31 C32 -163.2(3) . . . . ? C19 P2 C31 C32 83.0(4) . . . . ? Au2 P2 C31 C32 -42.1(4) . . . . ? C36 C31 C32 C33 1.1(7) . . . . ? P2 C31 C32 C33 -178.0(4) . . . . ? C31 C32 C33 C34 -0.4(7) . . . . ? C32 C33 C34 C35 -0.4(7) . . . . ? C33 C34 C35 C36 0.4(7) . . . . ? C32 C31 C36 C35 -1.1(7) . . . . ? P2 C31 C36 C35 178.0(3) . . . . ? C34 C35 C36 C31 0.3(7) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.028 _refine_diff_density_min -1.030 _refine_diff_density_rms 0.141 # Attachment 'neda00401.cif.txt' data_neda00401 _database_code_depnum_ccdc_archive 'CCDC 725992' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 F8 N2 O6 P2' _chemical_formula_sum 'C36 H20 Au2 F8 N2 O6 P2' _chemical_formula_weight 1184.41 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 10.1875(3) _cell_length_b 34.2523(12) _cell_length_c 10.5338(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.854(2) _cell_angle_gamma 90.00 _cell_volume 3675.3(2) _cell_formula_units_Z 4 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 198099 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 27.485 _exptl_crystal_description piece _exptl_crystal_colour colorless _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.19 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.141 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2232 _exptl_absorpt_coefficient_mu 8.151 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.194 _exptl_absorpt_correction_T_max 0.440 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 29664 _diffrn_reflns_av_R_equivalents 0.0790 _diffrn_reflns_av_sigmaI/netI 0.0539 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -44 _diffrn_reflns_limit_k_max 44 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.68 _diffrn_reflns_theta_max 27.36 _reflns_number_total 8226 _reflns_number_gt 6597 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0664P)^2^+17.3143P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8226 _refine_ls_number_parameters 505 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0716 _refine_ls_R_factor_gt 0.0530 _refine_ls_wR_factor_ref 0.1368 _refine_ls_wR_factor_gt 0.1288 _refine_ls_goodness_of_fit_ref 1.106 _refine_ls_restrained_S_all 1.106 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0.002 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.60581(3) 0.148761(8) 0.55684(3) 0.03407(11) Uani 1 1 d . . . Au2 Au 0.48263(3) 0.074417(9) 0.45113(3) 0.03543(11) Uani 1 1 d . . . P1 P 0.7162(2) 0.17323(6) 0.3764(2) 0.0323(4) Uani 1 1 d . . . P2 P 0.4465(2) 0.06301(6) 0.6545(2) 0.0329(4) Uani 1 1 d . . . F1 F 0.5614(6) 0.21896(16) 0.1292(5) 0.0536(14) Uani 1 1 d . . . F2 F 0.2968(7) 0.2330(2) 0.1400(7) 0.080(2) Uani 1 1 d . . . F3 F 0.1559(6) 0.2059(2) 0.3319(8) 0.075(2) Uani 1 1 d . . . F4 F 0.2663(5) 0.16677(17) 0.5248(7) 0.0629(17) Uani 1 1 d . . . F5 F 0.2567(5) 0.07765(14) 0.8793(5) 0.0448(13) Uani 1 1 d . . . F6 F 0.1864(6) 0.14649(16) 0.9767(6) 0.0586(16) Uani 1 1 d . . . F7 F 0.3086(10) 0.21294(17) 0.9029(8) 0.104(3) Uani 1 1 d . . . F8 F 0.4998(8) 0.21046(15) 0.7296(7) 0.083(3) Uani 1 1 d . . . N1 N 0.8471(9) 0.1105(3) 0.6479(8) 0.054(2) Uani 1 1 d . . . N2 N 0.4171(7) 0.0981(2) 0.2034(7) 0.0361(16) Uani 1 1 d . . . O1 O 0.7451(7) 0.1297(2) 0.6901(6) 0.0514(16) Uani 1 1 d . . . O2 O 0.8521(9) 0.1007(3) 0.5384(7) 0.072(2) Uani 1 1 d . . . O3 O 0.9325(9) 0.1032(3) 0.7281(8) 0.083(3) Uani 1 1 d . . . O4 O 0.5165(6) 0.08411(18) 0.2585(6) 0.0420(14) Uani 1 1 d . . . O5 O 0.3146(6) 0.1061(2) 0.2598(7) 0.0503(16) Uani 1 1 d . . . O6 O 0.4294(7) 0.1066(2) 0.0858(7) 0.0591(19) Uani 1 1 d . . . C1 C 0.5522(8) 0.1870(2) 0.3300(9) 0.0371(19) Uani 1 1 d . . . C2 C 0.4911(10) 0.2061(3) 0.2284(9) 0.046(2) Uani 1 1 d . . . C3 C 0.3564(10) 0.2128(3) 0.2317(11) 0.053(3) Uani 1 1 d . . . C4 C 0.2878(10) 0.1992(3) 0.3315(13) 0.059(3) Uani 1 1 d . . . C5 C 0.3443(9) 0.1798(3) 0.4304(11) 0.049(2) Uani 1 1 d . . . C6 C 0.4795(8) 0.1736(2) 0.4334(9) 0.040(2) Uani 1 1 d . . . C7 C 0.8097(8) 0.2161(2) 0.4198(9) 0.039(2) Uani 1 1 d . . . C8 C 0.7934(13) 0.2507(3) 0.3552(11) 0.062(3) Uani 1 1 d . . . H8 H 0.7351 0.2522 0.2867 0.075 Uiso 1 1 calc R . . C9 C 0.8660(15) 0.2838(3) 0.3938(14) 0.077(4) Uani 1 1 d . . . H9 H 0.8568 0.3071 0.3492 0.093 Uiso 1 1 calc R . . C10 C 0.9491(11) 0.2820(3) 0.4959(13) 0.064(3) Uani 1 1 d . . . H10 H 0.9968 0.3039 0.5209 0.077 Uiso 1 1 calc R . . C11 C 0.9626(12) 0.2472(4) 0.5628(13) 0.071(3) Uani 1 1 d . . . H11 H 1.0180 0.2459 0.6337 0.085 Uiso 1 1 calc R . . C12 C 0.8943(11) 0.2147(3) 0.5241(12) 0.061(3) Uani 1 1 d . . . H12 H 0.9048 0.1914 0.5685 0.073 Uiso 1 1 calc R . . C13 C 0.7978(8) 0.1468(2) 0.2521(8) 0.0336(18) Uani 1 1 d . . . C14 C 0.7324(9) 0.1381(2) 0.1395(8) 0.0358(18) Uani 1 1 d . . . H14 H 0.6452 0.1454 0.1276 0.043 Uiso 1 1 calc R . . C15 C 0.7988(10) 0.1181(3) 0.0431(10) 0.045(2) Uani 1 1 d . . . H15 H 0.7550 0.1121 -0.0325 0.055 Uiso 1 1 calc R . . C16 C 0.9265(10) 0.1073(3) 0.0594(9) 0.046(2) Uani 1 1 d . . . H16 H 0.9695 0.0941 -0.0049 0.055 Uiso 1 1 calc R . . C17 C 0.9929(9) 0.1161(3) 0.1729(10) 0.047(2) Uani 1 1 d . . . H17 H 1.0796 0.1083 0.1846 0.056 Uiso 1 1 calc R . . C18 C 0.9295(8) 0.1366(2) 0.2688(9) 0.040(2) Uani 1 1 d . . . H18 H 0.9746 0.1434 0.3430 0.048 Uiso 1 1 calc R . . C19 C 0.4068(8) 0.1082(2) 0.7362(9) 0.0371(19) Uani 1 1 d . . . C20 C 0.3157(8) 0.1098(2) 0.8329(9) 0.039(2) Uani 1 1 d . . . C21 C 0.2802(10) 0.1452(3) 0.8875(10) 0.047(2) Uani 1 1 d . . . C22 C 0.3402(13) 0.1779(3) 0.8494(12) 0.069(4) Uani 1 1 d . . . C23 C 0.4382(12) 0.1767(3) 0.7615(11) 0.056(3) Uani 1 1 d . . . C24 C 0.4711(9) 0.1422(2) 0.7024(9) 0.043(2) Uani 1 1 d . . . C25 C 0.3076(8) 0.0308(2) 0.6683(8) 0.0350(18) Uani 1 1 d . . . C26 C 0.1846(9) 0.0435(2) 0.6274(10) 0.043(2) Uani 1 1 d . . . H26 H 0.1738 0.0689 0.5980 0.051 Uiso 1 1 calc R . . C27 C 0.0768(9) 0.0182(3) 0.6303(11) 0.055(3) Uani 1 1 d . . . H27 H -0.0065 0.0270 0.6072 0.066 Uiso 1 1 calc R . . C28 C 0.0959(10) -0.0202(3) 0.6678(12) 0.057(3) Uani 1 1 d . . . H28 H 0.0258 -0.0376 0.6651 0.068 Uiso 1 1 calc R . . C29 C 0.2173(8) -0.0328(2) 0.7092(9) 0.0378(19) Uani 1 1 d . . . H29 H 0.2284 -0.0584 0.7366 0.045 Uiso 1 1 calc R . . C30 C 0.3231(8) -0.0074(2) 0.7100(8) 0.0338(17) Uani 1 1 d . . . H30 H 0.4049 -0.0160 0.7387 0.041 Uiso 1 1 calc R . . C31 C 0.5796(7) 0.0386(2) 0.7387(9) 0.0355(18) Uani 1 1 d . . . C32 C 0.5907(9) 0.0395(3) 0.8690(10) 0.045(2) Uani 1 1 d . . . H32 H 0.5354 0.0557 0.9147 0.054 Uiso 1 1 calc R . . C33 C 0.6808(11) 0.0173(4) 0.9327(11) 0.059(3) Uani 1 1 d . . . H33 H 0.6898 0.0191 1.0205 0.071 Uiso 1 1 calc R . . C34 C 0.7604(10) -0.0086(3) 0.8624(11) 0.058(3) Uani 1 1 d . . . H34 H 0.8200 -0.0247 0.9047 0.070 Uiso 1 1 calc R . . C35 C 0.7505(9) -0.0100(3) 0.7326(11) 0.053(3) Uani 1 1 d . . . H35 H 0.8029 -0.0271 0.6869 0.064 Uiso 1 1 calc R . . C36 C 0.6604(8) 0.0144(2) 0.6692(9) 0.0378(19) Uani 1 1 d . . . H36 H 0.6550 0.0144 0.5809 0.045 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.04104(18) 0.02385(16) 0.03772(19) -0.00133(12) 0.01446(13) -0.00404(12) Au2 0.04329(19) 0.02506(17) 0.0382(2) -0.00082(12) 0.01076(14) -0.00367(12) P1 0.0384(11) 0.0243(10) 0.0344(11) 0.0009(8) 0.0090(9) -0.0026(8) P2 0.0372(11) 0.0253(10) 0.0364(12) -0.0001(9) 0.0099(9) -0.0019(8) F1 0.070(4) 0.048(3) 0.043(3) 0.008(3) 0.011(3) 0.017(3) F2 0.083(5) 0.091(5) 0.064(4) -0.001(4) -0.017(4) 0.042(4) F3 0.040(3) 0.071(4) 0.113(6) -0.009(4) -0.003(3) 0.012(3) F4 0.035(3) 0.050(3) 0.105(5) 0.000(3) 0.028(3) -0.006(2) F5 0.054(3) 0.033(3) 0.049(3) 0.004(2) 0.023(2) -0.007(2) F6 0.075(4) 0.046(3) 0.056(4) 0.006(3) 0.039(3) 0.010(3) F7 0.185(8) 0.030(3) 0.100(6) -0.007(3) 0.104(6) 0.008(4) F8 0.134(6) 0.022(3) 0.095(5) -0.012(3) 0.077(5) -0.014(3) N1 0.070(6) 0.048(5) 0.043(5) 0.011(4) 0.004(4) 0.016(4) N2 0.037(4) 0.031(4) 0.041(4) -0.010(3) 0.002(3) -0.006(3) O1 0.061(4) 0.052(4) 0.042(4) -0.002(3) 0.007(3) 0.007(3) O2 0.094(6) 0.083(6) 0.039(4) 0.002(4) 0.011(4) 0.045(5) O3 0.090(6) 0.104(7) 0.056(5) -0.004(5) -0.011(5) 0.044(6) O4 0.054(4) 0.036(3) 0.037(3) 0.002(3) 0.005(3) 0.000(3) O5 0.046(4) 0.049(4) 0.055(4) -0.005(3) 0.006(3) 0.003(3) O6 0.067(5) 0.068(5) 0.042(4) 0.008(4) -0.003(3) -0.003(4) C1 0.043(4) 0.023(4) 0.046(5) -0.009(4) 0.007(4) -0.002(3) C2 0.062(6) 0.035(5) 0.042(5) -0.004(4) 0.001(4) 0.001(4) C3 0.053(6) 0.042(5) 0.065(7) -0.006(5) -0.006(5) 0.005(4) C4 0.041(5) 0.047(6) 0.090(9) -0.017(6) -0.002(5) 0.010(4) C5 0.044(5) 0.029(4) 0.074(7) 0.004(5) 0.014(5) -0.004(4) C6 0.038(4) 0.027(4) 0.055(6) -0.006(4) 0.009(4) 0.003(3) C7 0.039(4) 0.029(4) 0.050(5) -0.007(4) 0.015(4) -0.005(3) C8 0.100(9) 0.039(5) 0.047(6) 0.004(5) -0.003(6) -0.022(6) C9 0.115(11) 0.038(6) 0.080(9) 0.001(6) 0.024(8) -0.024(6) C10 0.067(7) 0.043(6) 0.084(9) -0.027(6) 0.028(6) -0.026(5) C11 0.068(7) 0.069(8) 0.075(9) -0.008(7) -0.005(6) -0.019(6) C12 0.057(6) 0.043(6) 0.082(8) -0.004(5) -0.011(6) -0.018(5) C13 0.039(4) 0.027(4) 0.036(5) 0.002(3) 0.017(3) -0.003(3) C14 0.045(5) 0.029(4) 0.034(5) 0.001(3) 0.010(4) -0.005(3) C15 0.058(6) 0.031(4) 0.048(6) -0.009(4) 0.016(4) -0.006(4) C16 0.058(6) 0.040(5) 0.040(5) -0.002(4) 0.021(4) 0.000(4) C17 0.046(5) 0.040(5) 0.056(6) 0.009(4) 0.020(4) 0.003(4) C18 0.040(4) 0.033(4) 0.047(5) 0.007(4) 0.011(4) -0.006(4) C19 0.045(5) 0.025(4) 0.041(5) 0.002(4) 0.008(4) 0.002(3) C20 0.043(4) 0.031(4) 0.042(5) 0.008(4) 0.018(4) 0.001(3) C21 0.057(6) 0.036(5) 0.047(6) 0.007(4) 0.029(5) 0.005(4) C22 0.107(9) 0.029(5) 0.072(8) -0.002(5) 0.055(7) 0.007(5) C23 0.086(7) 0.019(4) 0.063(7) -0.004(4) 0.036(6) -0.002(4) C24 0.052(5) 0.030(4) 0.048(6) -0.006(4) 0.030(4) -0.003(4) C25 0.042(4) 0.028(4) 0.035(5) 0.005(3) 0.008(3) -0.005(3) C26 0.041(4) 0.027(4) 0.060(6) 0.008(4) 0.002(4) 0.008(4) C27 0.037(5) 0.046(6) 0.081(8) 0.007(5) -0.004(5) -0.003(4) C28 0.054(6) 0.032(5) 0.084(8) 0.012(5) 0.006(5) -0.006(4) C29 0.037(4) 0.029(4) 0.048(5) 0.008(4) 0.003(4) 0.000(3) C30 0.034(4) 0.034(4) 0.034(4) 0.002(3) 0.002(3) 0.000(3) C31 0.029(4) 0.032(4) 0.046(5) -0.001(4) 0.008(3) -0.007(3) C32 0.048(5) 0.041(5) 0.047(6) -0.002(4) 0.007(4) -0.004(4) C33 0.056(6) 0.072(7) 0.049(6) 0.002(5) 0.001(5) 0.004(5) C34 0.050(6) 0.062(7) 0.062(7) 0.019(6) -0.007(5) 0.004(5) C35 0.039(5) 0.055(6) 0.066(7) -0.002(5) 0.007(5) -0.001(4) C36 0.037(4) 0.027(4) 0.050(5) 0.005(4) 0.010(4) -0.004(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.005(9) . ? Au1 C24 2.084(8) . ? Au1 O1 2.086(7) . ? Au1 P1 2.375(2) . ? Au1 Au2 3.0426(4) . ? Au2 O4 2.090(6) . ? Au2 P2 2.214(2) . ? P1 C1 1.797(9) . ? P1 C7 1.805(9) . ? P1 C13 1.806(8) . ? P2 C25 1.801(8) . ? P2 C31 1.814(9) . ? P2 C19 1.820(8) . ? F1 C2 1.350(11) . ? F2 C3 1.329(12) . ? F3 C4 1.363(11) . ? F4 C5 1.357(11) . ? F5 C20 1.349(9) . ? F6 C21 1.351(10) . ? F7 C22 1.365(11) . ? F8 C23 1.359(10) . ? N1 O2 1.203(11) . ? N1 O3 1.229(11) . ? N1 O1 1.312(10) . ? N2 O5 1.240(9) . ? N2 O4 1.255(9) . ? N2 O6 1.280(10) . ? C1 C2 1.393(13) . ? C1 C6 1.404(12) . ? C2 C3 1.392(14) . ? C3 C4 1.353(16) . ? C4 C5 1.358(16) . ? C5 C6 1.393(13) . ? C7 C8 1.376(14) . ? C7 C12 1.387(15) . ? C8 C9 1.411(16) . ? C8 H8 0.9300 . ? C9 C10 1.361(19) . ? C9 H9 0.9300 . ? C10 C11 1.390(18) . ? C10 H10 0.9300 . ? C11 C12 1.370(15) . ? C11 H11 0.9300 . ? C12 H12 0.9300 . ? C13 C14 1.385(13) . ? C13 C18 1.394(12) . ? C14 C15 1.407(12) . ? C14 H14 0.9300 . ? C15 C16 1.360(14) . ? C15 H15 0.9300 . ? C16 C17 1.398(14) . ? C16 H16 0.9300 . ? C17 C18 1.397(13) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? C19 C24 1.387(11) . ? C19 C20 1.389(12) . ? C20 C21 1.393(12) . ? C21 C22 1.341(13) . ? C22 C23 1.373(14) . ? C23 C24 1.379(12) . ? C25 C26 1.389(12) . ? C25 C30 1.389(11) . ? C26 C27 1.400(13) . ? C26 H26 0.9300 . ? C27 C28 1.385(14) . ? C27 H27 0.9300 . ? C28 C29 1.375(13) . ? C28 H28 0.9300 . ? C29 C30 1.385(11) . ? C29 H29 0.9300 . ? C30 H30 0.9300 . ? C31 C32 1.376(13) . ? C31 C36 1.384(12) . ? C32 C33 1.361(14) . ? C32 H32 0.9300 . ? C33 C34 1.418(16) . ? C33 H33 0.9300 . ? C34 C35 1.370(15) . ? C34 H34 0.9300 . ? C35 C36 1.405(14) . ? C35 H35 0.9300 . ? C36 H36 0.9300 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 C24 95.7(4) . . ? C6 Au1 O1 173.2(3) . . ? C24 Au1 O1 85.4(4) . . ? C6 Au1 P1 68.8(3) . . ? C24 Au1 P1 162.0(3) . . ? O1 Au1 P1 108.9(2) . . ? C6 Au1 Au2 81.9(2) . . ? C24 Au1 Au2 84.7(3) . . ? O1 Au1 Au2 104.9(2) . . ? P1 Au1 Au2 101.54(5) . . ? O4 Au2 P2 178.97(18) . . ? O4 Au2 Au1 98.58(17) . . ? P2 Au2 Au1 82.37(6) . . ? C1 P1 C7 109.9(4) . . ? C1 P1 C13 111.8(4) . . ? C7 P1 C13 110.2(4) . . ? C1 P1 Au1 82.0(3) . . ? C7 P1 Au1 109.8(3) . . ? C13 P1 Au1 129.2(3) . . ? C25 P2 C31 105.1(4) . . ? C25 P2 C19 107.6(4) . . ? C31 P2 C19 109.3(4) . . ? C25 P2 Au2 109.2(3) . . ? C31 P2 Au2 114.9(3) . . ? C19 P2 Au2 110.4(3) . . ? O2 N1 O3 124.3(9) . . ? O2 N1 O1 120.6(8) . . ? O3 N1 O1 115.1(9) . . ? O5 N2 O4 122.8(8) . . ? O5 N2 O6 120.6(8) . . ? O4 N2 O6 116.4(7) . . ? N1 O1 Au1 117.6(6) . . ? N2 O4 Au2 111.5(5) . . ? C2 C1 C6 121.0(8) . . ? C2 C1 P1 137.3(7) . . ? C6 C1 P1 101.6(6) . . ? F1 C2 C3 120.1(9) . . ? F1 C2 C1 120.8(9) . . ? C3 C2 C1 119.1(10) . . ? F2 C3 C4 120.5(10) . . ? F2 C3 C2 120.5(11) . . ? C4 C3 C2 119.0(10) . . ? C3 C4 C5 123.1(9) . . ? C3 C4 F3 117.7(11) . . ? C5 C4 F3 119.2(11) . . ? C4 C5 F4 118.5(9) . . ? C4 C5 C6 120.0(9) . . ? F4 C5 C6 121.5(10) . . ? C5 C6 C1 117.7(9) . . ? C5 C6 Au1 134.7(8) . . ? C1 C6 Au1 107.5(6) . . ? C8 C7 C12 119.3(9) . . ? C8 C7 P1 121.1(8) . . ? C12 C7 P1 119.5(7) . . ? C7 C8 C9 119.5(11) . . ? C7 C8 H8 120.3 . . ? C9 C8 H8 120.3 . . ? C10 C9 C8 120.5(11) . . ? C10 C9 H9 119.7 . . ? C8 C9 H9 119.7 . . ? C9 C10 C11 119.7(10) . . ? C9 C10 H10 120.1 . . ? C11 C10 H10 120.1 . . ? C12 C11 C10 119.9(12) . . ? C12 C11 H11 120.0 . . ? C10 C11 H11 120.0 . . ? C11 C12 C7 121.0(11) . . ? C11 C12 H12 119.5 . . ? C7 C12 H12 119.5 . . ? C14 C13 C18 120.3(8) . . ? C14 C13 P1 120.6(6) . . ? C18 C13 P1 119.1(7) . . ? C13 C14 C15 119.5(9) . . ? C13 C14 H14 120.2 . . ? C15 C14 H14 120.2 . . ? C16 C15 C14 120.7(10) . . ? C16 C15 H15 119.7 . . ? C14 C15 H15 119.6 . . ? C15 C16 C17 119.9(9) . . ? C15 C16 H16 120.0 . . ? C17 C16 H16 120.0 . . ? C18 C17 C16 120.3(9) . . ? C18 C17 H17 119.8 . . ? C16 C17 H17 119.8 . . ? C13 C18 C17 119.2(9) . . ? C13 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? C24 C19 C20 118.6(8) . . ? C24 C19 P2 119.0(6) . . ? C20 C19 P2 122.4(6) . . ? F5 C20 C19 122.7(8) . . ? F5 C20 C21 116.2(7) . . ? C19 C20 C21 121.1(8) . . ? C22 C21 F6 120.7(8) . . ? C22 C21 C20 118.9(8) . . ? F6 C21 C20 120.4(8) . . ? C21 C22 F7 119.9(9) . . ? C21 C22 C23 121.0(9) . . ? F7 C22 C23 118.9(9) . . ? F8 C23 C22 118.9(8) . . ? F8 C23 C24 120.0(8) . . ? C22 C23 C24 121.0(9) . . ? C23 C24 C19 119.0(8) . . ? C23 C24 Au1 114.0(6) . . ? C19 C24 Au1 126.7(6) . . ? C26 C25 C30 119.3(8) . . ? C26 C25 P2 119.4(6) . . ? C30 C25 P2 121.1(6) . . ? C25 C26 C27 120.3(8) . . ? C25 C26 H26 119.9 . . ? C27 C26 H26 119.9 . . ? C28 C27 C26 119.2(9) . . ? C28 C27 H27 120.4 . . ? C26 C27 H27 120.4 . . ? C29 C28 C27 120.6(9) . . ? C29 C28 H28 119.7 . . ? C27 C28 H28 119.7 . . ? C28 C29 C30 120.1(8) . . ? C28 C29 H29 119.9 . . ? C30 C29 H29 120.0 . . ? C29 C30 C25 120.4(8) . . ? C29 C30 H30 119.8 . . ? C25 C30 H30 119.8 . . ? C32 C31 C36 120.1(9) . . ? C32 C31 P2 121.8(7) . . ? C36 C31 P2 117.6(7) . . ? C33 C32 C31 121.5(9) . . ? C33 C32 H32 119.2 . . ? C31 C32 H32 119.2 . . ? C32 C33 C34 118.6(10) . . ? C32 C33 H33 120.7 . . ? C34 C33 H33 120.7 . . ? C35 C34 C33 120.7(10) . . ? C35 C34 H34 119.7 . . ? C33 C34 H34 119.7 . . ? C34 C35 C36 119.4(10) . . ? C34 C35 H35 120.3 . . ? C36 C35 H35 120.3 . . ? C31 C36 C35 119.6(9) . . ? C31 C36 H36 120.2 . . ? C35 C36 H36 120.2 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 Au1 Au2 O4 54.9(3) . . . . ? C24 Au1 Au2 O4 151.5(3) . . . . ? O1 Au1 Au2 O4 -124.7(3) . . . . ? P1 Au1 Au2 O4 -11.40(19) . . . . ? C6 Au1 Au2 P2 -125.5(3) . . . . ? C24 Au1 Au2 P2 -28.9(3) . . . . ? O1 Au1 Au2 P2 54.9(2) . . . . ? P1 Au1 Au2 P2 168.21(8) . . . . ? C6 Au1 P1 C1 -0.1(4) . . . . ? C24 Au1 P1 C1 -32.3(10) . . . . ? O1 Au1 P1 C1 -173.3(3) . . . . ? Au2 Au1 P1 C1 76.4(3) . . . . ? C6 Au1 P1 C7 108.2(4) . . . . ? C24 Au1 P1 C7 76.0(10) . . . . ? O1 Au1 P1 C7 -65.0(4) . . . . ? Au2 Au1 P1 C7 -175.3(3) . . . . ? C6 Au1 P1 C13 -111.8(5) . . . . ? C24 Au1 P1 C13 -144.0(10) . . . . ? O1 Au1 P1 C13 75.0(4) . . . . ? Au2 Au1 P1 C13 -35.3(4) . . . . ? Au1 Au2 P2 C25 154.7(3) . . . . ? Au1 Au2 P2 C31 -87.6(3) . . . . ? Au1 Au2 P2 C19 36.6(3) . . . . ? O2 N1 O1 Au1 -7.8(13) . . . . ? O3 N1 O1 Au1 173.1(8) . . . . ? C24 Au1 O1 N1 150.0(7) . . . . ? P1 Au1 O1 N1 -41.3(7) . . . . ? Au2 Au1 O1 N1 66.8(7) . . . . ? O5 N2 O4 Au2 2.2(9) . . . . ? O6 N2 O4 Au2 177.4(6) . . . . ? Au1 Au2 O4 N2 -97.5(5) . . . . ? C7 P1 C1 C2 70.9(10) . . . . ? C13 P1 C1 C2 -51.7(10) . . . . ? Au1 P1 C1 C2 179.1(10) . . . . ? C7 P1 C1 C6 -108.0(6) . . . . ? C13 P1 C1 C6 129.3(6) . . . . ? Au1 P1 C1 C6 0.2(5) . . . . ? C6 C1 C2 F1 -179.9(8) . . . . ? P1 C1 C2 F1 1.3(15) . . . . ? C6 C1 C2 C3 1.8(13) . . . . ? P1 C1 C2 C3 -177.0(8) . . . . ? F1 C2 C3 F2 -2.6(15) . . . . ? C1 C2 C3 F2 175.7(9) . . . . ? F1 C2 C3 C4 179.3(9) . . . . ? C1 C2 C3 C4 -2.4(15) . . . . ? F2 C3 C4 C5 -177.2(10) . . . . ? C2 C3 C4 C5 0.9(16) . . . . ? F2 C3 C4 F3 2.3(15) . . . . ? C2 C3 C4 F3 -179.6(9) . . . . ? C3 C4 C5 F4 -178.8(9) . . . . ? F3 C4 C5 F4 1.7(15) . . . . ? C3 C4 C5 C6 1.2(16) . . . . ? F3 C4 C5 C6 -178.3(9) . . . . ? C4 C5 C6 C1 -1.8(14) . . . . ? F4 C5 C6 C1 178.2(8) . . . . ? C4 C5 C6 Au1 177.8(8) . . . . ? F4 C5 C6 Au1 -2.2(15) . . . . ? C2 C1 C6 C5 0.3(13) . . . . ? P1 C1 C6 C5 179.4(7) . . . . ? C2 C1 C6 Au1 -179.4(7) . . . . ? P1 C1 C6 Au1 -0.2(6) . . . . ? C24 Au1 C6 C5 -8.9(10) . . . . ? P1 Au1 C6 C5 -179.4(10) . . . . ? Au2 Au1 C6 C5 74.9(9) . . . . ? C24 Au1 C6 C1 170.7(6) . . . . ? P1 Au1 C6 C1 0.2(5) . . . . ? Au2 Au1 C6 C1 -105.6(6) . . . . ? C1 P1 C7 C8 -37.2(10) . . . . ? C13 P1 C7 C8 86.4(9) . . . . ? Au1 P1 C7 C8 -125.7(8) . . . . ? C1 P1 C7 C12 139.4(8) . . . . ? C13 P1 C7 C12 -97.1(8) . . . . ? Au1 P1 C7 C12 50.9(8) . . . . ? C12 C7 C8 C9 1.9(17) . . . . ? P1 C7 C8 C9 178.5(9) . . . . ? C7 C8 C9 C10 -1.6(19) . . . . ? C8 C9 C10 C11 -0.1(19) . . . . ? C9 C10 C11 C12 1.3(19) . . . . ? C10 C11 C12 C7 -1.0(19) . . . . ? C8 C7 C12 C11 -0.7(17) . . . . ? P1 C7 C12 C11 -177.3(9) . . . . ? C1 P1 C13 C14 -2.4(8) . . . . ? C7 P1 C13 C14 -124.9(7) . . . . ? Au1 P1 C13 C14 95.2(7) . . . . ? C1 P1 C13 C18 174.9(6) . . . . ? C7 P1 C13 C18 52.5(8) . . . . ? Au1 P1 C13 C18 -87.4(7) . . . . ? C18 C13 C14 C15 1.5(12) . . . . ? P1 C13 C14 C15 178.8(6) . . . . ? C13 C14 C15 C16 -0.2(13) . . . . ? C14 C15 C16 C17 0.0(14) . . . . ? C15 C16 C17 C18 -1.2(14) . . . . ? C14 C13 C18 C17 -2.7(12) . . . . ? P1 C13 C18 C17 179.9(6) . . . . ? C16 C17 C18 C13 2.6(13) . . . . ? C25 P2 C19 C24 -156.4(8) . . . . ? C31 P2 C19 C24 90.0(8) . . . . ? Au2 P2 C19 C24 -37.3(9) . . . . ? C25 P2 C19 C20 24.8(9) . . . . ? C31 P2 C19 C20 -88.9(8) . . . . ? Au2 P2 C19 C20 143.8(7) . . . . ? C24 C19 C20 F5 -174.3(9) . . . . ? P2 C19 C20 F5 4.6(13) . . . . ? C24 C19 C20 C21 5.8(15) . . . . ? P2 C19 C20 C21 -175.3(8) . . . . ? F5 C20 C21 C22 176.9(11) . . . . ? C19 C20 C21 C22 -3.2(17) . . . . ? F5 C20 C21 F6 -3.5(15) . . . . ? C19 C20 C21 F6 176.5(9) . . . . ? F6 C21 C22 F7 1(2) . . . . ? C20 C21 C22 F7 -179.0(12) . . . . ? F6 C21 C22 C23 178.1(12) . . . . ? C20 C21 C22 C23 -2(2) . . . . ? C21 C22 C23 F8 -177.3(13) . . . . ? F7 C22 C23 F8 -1(2) . . . . ? C21 C22 C23 C24 5(2) . . . . ? F7 C22 C23 C24 -178.2(12) . . . . ? F8 C23 C24 C19 -179.8(11) . . . . ? C22 C23 C24 C19 -2.3(19) . . . . ? F8 C23 C24 Au1 -4.8(15) . . . . ? C22 C23 C24 Au1 172.7(11) . . . . ? C20 C19 C24 C23 -3.0(15) . . . . ? P2 C19 C24 C23 178.0(9) . . . . ? C20 C19 C24 Au1 -177.3(7) . . . . ? P2 C19 C24 Au1 3.7(13) . . . . ? C6 Au1 C24 C23 -72.8(9) . . . . ? O1 Au1 C24 C23 100.4(9) . . . . ? P1 Au1 C24 C23 -42.9(16) . . . . ? Au2 Au1 C24 C23 -154.1(9) . . . . ? C6 Au1 C24 C19 101.7(10) . . . . ? O1 Au1 C24 C19 -85.0(9) . . . . ? P1 Au1 C24 C19 131.6(7) . . . . ? Au2 Au1 C24 C19 20.4(9) . . . . ? C31 P2 C25 C26 171.7(7) . . . . ? C19 P2 C25 C26 55.3(8) . . . . ? Au2 P2 C25 C26 -64.5(8) . . . . ? C31 P2 C25 C30 -13.2(8) . . . . ? C19 P2 C25 C30 -129.7(7) . . . . ? Au2 P2 C25 C30 110.5(7) . . . . ? C30 C25 C26 C27 1.1(14) . . . . ? P2 C25 C26 C27 176.2(8) . . . . ? C25 C26 C27 C28 -3.4(17) . . . . ? C26 C27 C28 C29 3.9(18) . . . . ? C27 C28 C29 C30 -1.9(17) . . . . ? C28 C29 C30 C25 -0.5(14) . . . . ? C26 C25 C30 C29 0.9(13) . . . . ? P2 C25 C30 C29 -174.1(7) . . . . ? C25 P2 C31 C32 -79.4(8) . . . . ? C19 P2 C31 C32 35.8(8) . . . . ? Au2 P2 C31 C32 160.5(6) . . . . ? C25 P2 C31 C36 92.0(7) . . . . ? C19 P2 C31 C36 -152.7(6) . . . . ? Au2 P2 C31 C36 -28.0(7) . . . . ? C36 C31 C32 C33 0.5(14) . . . . ? P2 C31 C32 C33 171.7(8) . . . . ? C31 C32 C33 C34 -2.8(16) . . . . ? C32 C33 C34 C35 2.5(17) . . . . ? C33 C34 C35 C36 0.1(16) . . . . ? C32 C31 C36 C35 2.2(12) . . . . ? P2 C31 C36 C35 -169.4(7) . . . . ? C34 C35 C36 C31 -2.4(14) . . . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.36 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 3.913 _refine_diff_density_min -2.628 _refine_diff_density_rms 0.223 # Attachment 'neda00402.cif.txt' data_neda00402 _database_code_depnum_ccdc_archive 'CCDC 725993' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C72 H40 Au4 F16 P4, 0.86(C H2 Cl2)' _chemical_formula_sum 'C75.44 H46.88 Au4 Cl6.88 F16 P4' _chemical_formula_weight 2412.93 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P42/n _symmetry_space_group_name_Hall '-P 4bc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-y, x+1/2, z+1/2' 'y+1/2, -x, z+1/2' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'y, -x-1/2, -z-1/2' '-y-1/2, x, -z-1/2' _cell_length_a 15.9440(3) _cell_length_b 15.9440(3) _cell_length_c 14.7921(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3760.32(11) _cell_formula_units_Z 2 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 28531 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description polyhedron _exptl_crystal_colour colorless _exptl_crystal_size_max 0.17 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.131 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2273 _exptl_absorpt_coefficient_mu 8.192 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.374 _exptl_absorpt_correction_T_max 0.484 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 41538 _diffrn_reflns_av_R_equivalents 0.0415 _diffrn_reflns_av_sigmaI/netI 0.0347 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.90 _diffrn_reflns_theta_max 35.00 _reflns_number_total 8284 _reflns_number_gt 6147 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; The structure bears twofold disordered dichloromethane molecules in the asym. unit (less than 1 molecule, the s.o.f. were refined to 0.36 and 0.50.) One of the phenyl groups is slightly disordered (rotational twofold disorder in 0.50:0.50 ratio). CHECKCIF/PLATON reports a single bonded metal atom, however, the coordination number of the Au atoms is 2 (with distances Au-C 2.056A and Au-P 2.288A). Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0346P)^2^+3.9891P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8284 _refine_ls_number_parameters 283 _refine_ls_number_restraints 25 _refine_ls_R_factor_all 0.0527 _refine_ls_R_factor_gt 0.0318 _refine_ls_wR_factor_ref 0.0774 _refine_ls_wR_factor_gt 0.0722 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.031 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.278802(6) 0.378055(6) 0.215592(6) 0.01890(4) Uani 1 1 d . A . P1 P 0.23491(5) 0.45117(5) 0.34001(5) 0.02152(14) Uani 1 1 d D . . F1 F 0.26177(16) 0.47407(15) 0.55141(13) 0.0479(6) Uani 1 1 d . A . F2 F 0.20992(16) 0.36970(17) 0.68071(13) 0.0525(6) Uani 1 1 d . . . F3 F 0.12760(14) 0.22585(17) 0.63800(13) 0.0456(5) Uani 1 1 d . A . F4 F 0.09754(12) 0.18624(13) 0.46511(12) 0.0329(4) Uani 1 1 d . . . C1 C 0.20478(17) 0.38526(19) 0.43515(17) 0.0223(5) Uani 1 1 d . A . C2 C 0.2208(2) 0.4039(2) 0.5253(2) 0.0301(7) Uani 1 1 d . . . C3 C 0.1948(2) 0.3510(3) 0.5937(2) 0.0346(8) Uani 1 1 d . A . C4 C 0.1527(2) 0.2784(2) 0.5722(2) 0.0317(7) Uani 1 1 d . . . C5 C 0.13741(18) 0.2600(2) 0.4826(2) 0.0259(6) Uani 1 1 d . A . C6 C 0.16169(17) 0.31118(18) 0.41195(17) 0.0207(5) Uani 1 1 d . . . C7 C 0.30810(19) 0.5315(2) 0.3784(2) 0.0278(6) Uani 1 1 d . A . C8 C 0.2808(2) 0.6100(2) 0.4060(3) 0.0456(10) Uani 1 1 d . . . H8 H 0.2228 0.6235 0.4038 0.055 Uiso 1 1 calc R A . C9 C 0.3382(3) 0.6688(3) 0.4368(4) 0.0553(12) Uani 1 1 d . A . H9 H 0.3190 0.7220 0.4571 0.066 Uiso 1 1 calc R . . C10 C 0.4223(2) 0.6509(3) 0.4382(3) 0.0540(12) Uani 1 1 d . . . H10 H 0.4614 0.6920 0.4580 0.065 Uiso 1 1 calc R A . C11 C 0.4500(2) 0.5727(3) 0.4105(4) 0.0557(12) Uani 1 1 d . A . H11 H 0.5082 0.5598 0.4118 0.067 Uiso 1 1 calc R . . C12 C 0.3929(2) 0.5131(2) 0.3808(3) 0.0403(8) Uani 1 1 d . . . H12 H 0.4120 0.4594 0.3619 0.048 Uiso 1 1 calc R A . C13A C 0.1431(8) 0.5128(16) 0.3107(10) 0.0240(13) Uani 0.50 1 d PD A 1 C14A C 0.1448(6) 0.5507(9) 0.2253(9) 0.0288(15) Uani 0.50 1 d PD A 1 H14A H 0.1921 0.5448 0.1869 0.035 Uiso 0.50 1 calc PR A 1 C15A C 0.0755(6) 0.5970(10) 0.1983(11) 0.0364(14) Uani 0.50 1 d PD A 1 H15A H 0.0760 0.6245 0.1413 0.044 Uiso 0.50 1 calc PR A 1 C16A C 0.0056(7) 0.6037(6) 0.2537(5) 0.0364(14) Uani 0.50 1 d PD A 1 H16A H -0.0400 0.6386 0.2368 0.044 Uiso 0.50 1 calc PR A 1 C17A C 0.0030(5) 0.5590(5) 0.3342(6) 0.0364(14) Uani 0.50 1 d PD A 1 H17A H -0.0463 0.5614 0.3702 0.044 Uiso 0.50 1 calc PR A 1 C18A C 0.0703(5) 0.5111(5) 0.3634(5) 0.0288(15) Uani 0.50 1 d PD A 1 H18A H 0.0671 0.4784 0.4170 0.035 Uiso 0.50 1 calc PR A 1 C13B C 0.1385(9) 0.5063(16) 0.3115(8) 0.0240(13) Uani 0.50 1 d PD A 2 C14B C 0.1291(6) 0.5458(10) 0.2277(9) 0.0326(17) Uani 0.50 1 d PD A 2 H14B H 0.1699 0.5351 0.1823 0.039 Uiso 0.50 1 calc PR A 2 C15B C 0.0636(6) 0.5998(10) 0.2071(11) 0.0370(14) Uani 0.50 1 d PD A 2 H15B H 0.0599 0.6252 0.1491 0.044 Uiso 0.50 1 calc PR A 2 C16B C 0.0035(7) 0.6160(6) 0.2727(5) 0.0370(14) Uani 0.50 1 d PD A 2 H16B H -0.0436 0.6502 0.2586 0.044 Uiso 0.50 1 calc PR A 2 C17B C 0.0121(5) 0.5824(5) 0.3587(6) 0.0370(14) Uani 0.50 1 d PD A 2 H17B H -0.0286 0.5935 0.4040 0.044 Uiso 0.50 1 calc PR A 2 C18B C 0.0811(5) 0.5323(5) 0.3774(6) 0.0326(17) Uani 0.50 1 d PD A 2 H18B H 0.0898 0.5147 0.4380 0.039 Uiso 0.50 1 calc PR A 2 Cl1 Cl 0.3292(2) 0.9300(3) 0.6984(3) 0.0775(11) Uani 0.36 1 d PD B 3 C19 C 0.4128(6) 0.8710(8) 0.6669(5) 0.058(3) Uani 0.36 1 d PD B 3 H19A H 0.4639 0.8959 0.6937 0.069 Uiso 0.36 1 calc PR B 3 H19B H 0.4061 0.8142 0.6930 0.069 Uiso 0.36 1 calc PR B 3 Cl2 Cl 0.4276(3) 0.8614(3) 0.5540(3) 0.0611(11) Uani 0.36 1 d PD B 3 Cl3 Cl 0.26876(18) 0.77706(18) 0.6816(2) 0.0799(8) Uani 0.50 1 d PD . 4 C20 C 0.3313(4) 0.8629(5) 0.6758(6) 0.074(3) Uani 0.50 1 d PD C 4 H20A H 0.2957 0.9129 0.6658 0.089 Uiso 0.50 1 calc PR C 4 H20B H 0.3599 0.8701 0.7347 0.089 Uiso 0.50 1 calc PR C 4 Cl4 Cl 0.4049(3) 0.8589(3) 0.5932(3) 0.0842(13) Uani 0.50 1 d PD C 4 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02131(6) 0.01788(5) 0.01752(5) -0.00114(3) 0.00068(3) -0.00010(4) P1 0.0193(3) 0.0227(3) 0.0225(3) -0.0054(3) -0.0014(3) 0.0022(3) F1 0.0607(15) 0.0547(14) 0.0284(10) -0.0188(9) -0.0065(9) -0.0126(11) F2 0.0571(15) 0.0853(19) 0.0151(8) -0.0092(10) -0.0030(9) 0.0004(13) F3 0.0448(13) 0.0711(16) 0.0208(9) 0.0136(10) 0.0074(8) 0.0004(11) F4 0.0290(10) 0.0403(11) 0.0293(9) 0.0085(8) 0.0051(7) -0.0045(8) C1 0.0190(12) 0.0310(15) 0.0170(11) -0.0049(10) -0.0020(9) 0.0049(10) C2 0.0276(15) 0.0383(17) 0.0245(13) -0.0110(12) -0.0034(11) 0.0033(13) C3 0.0298(16) 0.057(2) 0.0169(12) -0.0058(13) -0.0005(11) 0.0068(15) C4 0.0235(14) 0.055(2) 0.0170(12) 0.0062(12) 0.0043(10) 0.0074(14) C5 0.0180(12) 0.0373(17) 0.0223(12) 0.0011(11) 0.0020(10) 0.0040(11) C6 0.0164(11) 0.0284(13) 0.0174(11) 0.0001(10) 0.0010(9) 0.0044(10) C7 0.0201(13) 0.0283(15) 0.0350(15) -0.0102(12) -0.0043(11) 0.0013(11) C8 0.0235(16) 0.0346(19) 0.079(3) -0.0234(19) -0.0099(17) 0.0027(14) C9 0.035(2) 0.036(2) 0.094(4) -0.029(2) -0.014(2) 0.0021(16) C10 0.0302(19) 0.044(2) 0.088(3) -0.026(2) -0.016(2) -0.0039(16) C11 0.0229(17) 0.051(2) 0.094(3) -0.027(2) -0.015(2) 0.0049(16) C12 0.0231(15) 0.0380(19) 0.060(2) -0.0177(17) -0.0096(15) 0.0064(14) C13A 0.0195(17) 0.019(3) 0.0335(14) -0.0034(13) -0.0033(12) -0.002(2) C14A 0.020(3) 0.024(3) 0.042(3) 0.005(2) 0.000(2) 0.004(3) C15A 0.028(2) 0.034(3) 0.047(3) 0.000(2) 0.002(2) 0.010(2) C16A 0.028(2) 0.034(3) 0.047(3) 0.000(2) 0.002(2) 0.010(2) C17A 0.028(2) 0.034(3) 0.047(3) 0.000(2) 0.002(2) 0.010(2) C18A 0.020(3) 0.024(3) 0.042(3) 0.005(2) 0.000(2) 0.004(3) C13B 0.0195(17) 0.019(3) 0.0335(14) -0.0034(13) -0.0033(12) -0.002(2) C14B 0.024(3) 0.033(3) 0.041(3) -0.004(2) 0.000(2) 0.000(3) C15B 0.032(3) 0.032(2) 0.047(3) -0.001(2) -0.003(2) 0.013(2) C16B 0.032(3) 0.032(2) 0.047(3) -0.001(2) -0.003(2) 0.013(2) C17B 0.032(3) 0.032(2) 0.047(3) -0.001(2) -0.003(2) 0.013(2) C18B 0.024(3) 0.033(3) 0.041(3) -0.004(2) 0.000(2) 0.000(3) Cl1 0.053(2) 0.090(3) 0.090(3) -0.001(2) -0.0066(19) 0.022(2) C19 0.051(8) 0.046(7) 0.076(10) -0.016(7) -0.017(7) 0.013(6) Cl2 0.062(3) 0.060(2) 0.061(2) -0.015(2) -0.0111(19) -0.012(2) Cl3 0.0539(17) 0.068(2) 0.118(2) 0.0049(16) 0.0033(15) 0.0066(12) C20 0.106(10) 0.042(5) 0.074(7) -0.011(5) -0.033(7) 0.030(6) Cl4 0.075(3) 0.076(2) 0.101(3) 0.023(3) -0.004(2) -0.0205(19) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.056(3) 7_566 ? Au1 P1 2.2882(7) . ? Au1 Au1 3.12972(16) 8_656 ? Au1 Au1 3.12972(16) 7_566 ? P1 C13A 1.815(6) . ? P1 C13B 1.820(6) . ? P1 C1 1.821(3) . ? P1 C7 1.823(3) . ? F1 C2 1.353(4) . ? F2 C3 1.343(3) . ? F3 C4 1.345(4) . ? F4 C5 1.361(4) . ? C1 C2 1.390(4) . ? C1 C6 1.409(4) . ? C2 C3 1.380(5) . ? C3 C4 1.376(5) . ? C4 C5 1.379(4) . ? C5 C6 1.381(4) . ? C6 Au1 2.056(3) 8_656 ? C7 C12 1.383(4) . ? C7 C8 1.387(5) . ? C8 C9 1.387(5) . ? C8 H8 0.9500 . ? C9 C10 1.372(6) . ? C9 H9 0.9500 . ? C10 C11 1.385(6) . ? C10 H10 0.9500 . ? C11 C12 1.388(5) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13A C18A 1.399(4) . ? C13A C14A 1.399(4) . ? C14A C15A 1.387(4) . ? C14A H14A 0.9500 . ? C15A C16A 1.388(4) . ? C15A H15A 0.9500 . ? C16A C17A 1.388(4) . ? C16A H16A 0.9500 . ? C17A C18A 1.387(4) . ? C17A H17A 0.9500 . ? C18A H18A 0.9500 . ? C13B C18B 1.400(4) . ? C13B C14B 1.400(4) . ? C14B C15B 1.388(4) . ? C14B H14B 0.9500 . ? C15B C16B 1.388(4) . ? C15B H15B 0.9500 . ? C16B C17B 1.388(4) . ? C16B H16B 0.9500 . ? C17B C18B 1.387(4) . ? C17B H17B 0.9500 . ? C18B H18B 0.9500 . ? Cl1 C19 1.695(5) . ? C19 Cl2 1.695(5) . ? C19 H19A 0.9900 . ? C19 H19B 0.9900 . ? Cl3 Cl3 1.050(5) 2_565 ? Cl3 C20 1.695(5) . ? C20 Cl4 1.695(5) . ? C20 H20A 0.9900 . ? C20 H20B 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 P1 166.37(8) 7_566 . ? C6 Au1 Au1 110.07(7) 7_566 8_656 ? P1 Au1 Au1 75.62(2) . 8_656 ? C6 Au1 Au1 85.71(8) 7_566 7_566 ? P1 Au1 Au1 107.468(19) . 7_566 ? Au1 Au1 Au1 83.927(2) 8_656 7_566 ? C13A P1 C1 106.5(4) . . ? C13B P1 C1 103.6(5) . . ? C13A P1 C7 102.1(9) . . ? C13B P1 C7 105.9(10) . . ? C1 P1 C7 109.47(14) . . ? C13A P1 Au1 109.3(7) . . ? C13B P1 Au1 108.6(6) . . ? C1 P1 Au1 114.09(9) . . ? C7 P1 Au1 114.36(11) . . ? C2 C1 C6 120.1(3) . . ? C2 C1 P1 124.8(2) . . ? C6 C1 P1 115.11(19) . . ? F1 C2 C3 116.1(3) . . ? F1 C2 C1 122.6(3) . . ? C3 C2 C1 121.2(3) . . ? F2 C3 C4 119.8(3) . . ? F2 C3 C2 120.9(3) . . ? C4 C3 C2 119.3(3) . . ? F3 C4 C3 120.1(3) . . ? F3 C4 C5 120.7(3) . . ? C3 C4 C5 119.2(3) . . ? F4 C5 C4 116.7(3) . . ? F4 C5 C6 119.9(3) . . ? C4 C5 C6 123.4(3) . . ? C5 C6 C1 116.6(3) . . ? C5 C6 Au1 117.3(2) . 8_656 ? C1 C6 Au1 125.7(2) . 8_656 ? C12 C7 C8 119.4(3) . . ? C12 C7 P1 119.0(2) . . ? C8 C7 P1 121.7(2) . . ? C7 C8 C9 120.0(3) . . ? C7 C8 H8 120.0 . . ? C9 C8 H8 120.0 . . ? C10 C9 C8 120.6(4) . . ? C10 C9 H9 119.7 . . ? C8 C9 H9 119.7 . . ? C9 C10 C11 119.6(4) . . ? C9 C10 H10 120.2 . . ? C11 C10 H10 120.2 . . ? C10 C11 C12 120.1(3) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C7 C12 C11 120.3(3) . . ? C7 C12 H12 119.9 . . ? C11 C12 H12 119.9 . . ? C18A C13A C14A 121.8(7) . . ? C18A C13A P1 121.6(6) . . ? C14A C13A P1 115.7(5) . . ? C15A C14A C13A 118.4(9) . . ? C15A C14A H14A 120.8 . . ? C13A C14A H14A 120.8 . . ? C14A C15A C16A 120.6(11) . . ? C14A C15A H15A 119.7 . . ? C16A C15A H15A 119.7 . . ? C15A C16A C17A 119.5(9) . . ? C15A C16A H16A 120.3 . . ? C17A C16A H16A 120.3 . . ? C18A C17A C16A 121.8(7) . . ? C18A C17A H17A 119.1 . . ? C16A C17A H17A 119.1 . . ? C17A C18A C13A 117.2(7) . . ? C17A C18A H18A 121.4 . . ? C13A C18A H18A 121.4 . . ? C18B C13B C14B 114.5(9) . . ? C18B C13B P1 122.3(7) . . ? C14B C13B P1 120.8(6) . . ? C15B C14B C13B 123.6(10) . . ? C15B C14B H14B 118.2 . . ? C13B C14B H14B 118.2 . . ? C14B C15B C16B 118.9(10) . . ? C14B C15B H15B 120.6 . . ? C16B C15B H15B 120.6 . . ? C17B C16B C15B 120.0(9) . . ? C17B C16B H16B 120.0 . . ? C15B C16B H16B 120.0 . . ? C18B C17B C16B 118.9(8) . . ? C18B C17B H17B 120.5 . . ? C16B C17B H17B 120.5 . . ? C17B C18B C13B 123.4(7) . . ? C17B C18B H18B 118.3 . . ? C13B C18B H18B 118.3 . . ? Cl2 C19 Cl1 115.5(6) . . ? Cl2 C19 H19A 108.4 . . ? Cl1 C19 H19A 108.4 . . ? Cl2 C19 H19B 108.4 . . ? Cl1 C19 H19B 108.4 . . ? H19A C19 H19B 107.5 . . ? Cl3 Cl3 C20 176.8(4) 2_565 . ? Cl4 C20 Cl3 114.5(5) . . ? Cl4 C20 H20A 108.6 . . ? Cl3 C20 H20A 108.6 . . ? Cl4 C20 H20B 108.6 . . ? Cl3 C20 H20B 108.6 . . ? H20A C20 H20B 107.6 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 Au1 P1 C13A 39.8(8) 7_566 . . . ? Au1 Au1 P1 C13A -76.7(8) 8_656 . . . ? Au1 Au1 P1 C13A -155.4(8) 7_566 . . . ? C6 Au1 P1 C13B 44.0(9) 7_566 . . . ? Au1 Au1 P1 C13B -72.5(8) 8_656 . . . ? Au1 Au1 P1 C13B -151.2(8) 7_566 . . . ? C6 Au1 P1 C1 158.9(3) 7_566 . . . ? Au1 Au1 P1 C1 42.44(10) 8_656 . . . ? Au1 Au1 P1 C1 -36.31(10) 7_566 . . . ? C6 Au1 P1 C7 -74.0(4) 7_566 . . . ? Au1 Au1 P1 C7 169.55(12) 8_656 . . . ? Au1 Au1 P1 C7 90.81(12) 7_566 . . . ? C13A P1 C1 C2 -97.3(10) . . . . ? C13B P1 C1 C2 -100.1(9) . . . . ? C7 P1 C1 C2 12.5(3) . . . . ? Au1 P1 C1 C2 142.1(2) . . . . ? C13A P1 C1 C6 82.2(10) . . . . ? C13B P1 C1 C6 79.4(9) . . . . ? C7 P1 C1 C6 -168.1(2) . . . . ? Au1 P1 C1 C6 -38.5(2) . . . . ? C6 C1 C2 F1 -179.9(3) . . . . ? P1 C1 C2 F1 -0.5(5) . . . . ? C6 C1 C2 C3 -0.3(5) . . . . ? P1 C1 C2 C3 179.1(3) . . . . ? F1 C2 C3 F2 0.2(5) . . . . ? C1 C2 C3 F2 -179.5(3) . . . . ? F1 C2 C3 C4 180.0(3) . . . . ? C1 C2 C3 C4 0.3(5) . . . . ? F2 C3 C4 F3 -0.8(5) . . . . ? C2 C3 C4 F3 179.4(3) . . . . ? F2 C3 C4 C5 179.9(3) . . . . ? C2 C3 C4 C5 0.1(5) . . . . ? F3 C4 C5 F4 -1.1(4) . . . . ? C3 C4 C5 F4 178.3(3) . . . . ? F3 C4 C5 C6 -179.9(3) . . . . ? C3 C4 C5 C6 -0.5(5) . . . . ? F4 C5 C6 C1 -178.2(2) . . . . ? C4 C5 C6 C1 0.5(4) . . . . ? F4 C5 C6 Au1 7.7(4) . . . 8_656 ? C4 C5 C6 Au1 -173.6(2) . . . 8_656 ? C2 C1 C6 C5 -0.1(4) . . . . ? P1 C1 C6 C5 -179.6(2) . . . . ? C2 C1 C6 Au1 173.5(2) . . . 8_656 ? P1 C1 C6 Au1 -6.0(3) . . . 8_656 ? C13A P1 C7 C12 -160.5(4) . . . . ? C13B P1 C7 C12 -162.1(4) . . . . ? C1 P1 C7 C12 86.8(3) . . . . ? Au1 P1 C7 C12 -42.6(3) . . . . ? C13A P1 C7 C8 20.1(5) . . . . ? C13B P1 C7 C8 18.5(5) . . . . ? C1 P1 C7 C8 -92.6(3) . . . . ? Au1 P1 C7 C8 138.0(3) . . . . ? C12 C7 C8 C9 -0.9(7) . . . . ? P1 C7 C8 C9 178.5(4) . . . . ? C7 C8 C9 C10 1.7(8) . . . . ? C8 C9 C10 C11 -1.5(8) . . . . ? C9 C10 C11 C12 0.6(8) . . . . ? C8 C7 C12 C11 0.0(6) . . . . ? P1 C7 C12 C11 -179.4(4) . . . . ? C10 C11 C12 C7 0.1(7) . . . . ? C13B P1 C13A C18A 50(13) . . . . ? C1 P1 C13A C18A 7(2) . . . . ? C7 P1 C13A C18A -108(2) . . . . ? Au1 P1 C13A C18A 130.2(19) . . . . ? C13B P1 C13A C14A -120(16) . . . . ? C1 P1 C13A C14A -163.4(18) . . . . ? C7 P1 C13A C14A 82(2) . . . . ? Au1 P1 C13A C14A -40(2) . . . . ? C18A C13A C14A C15A 9(3) . . . . ? P1 C13A C14A C15A 178.6(16) . . . . ? C13A C14A C15A C16A -2(3) . . . . ? C14A C15A C16A C17A -4(2) . . . . ? C15A C16A C17A C18A 3.5(16) . . . . ? C16A C17A C18A C13A 3.2(19) . . . . ? C14A C13A C18A C17A -9(3) . . . . ? P1 C13A C18A C17A -178.7(13) . . . . ? C13A P1 C13B C18B -102(16) . . . . ? C1 P1 C13B C18B 36(2) . . . . ? C7 P1 C13B C18B -79(2) . . . . ? Au1 P1 C13B C18B 157.5(18) . . . . ? C13A P1 C13B C14B 60(13) . . . . ? C1 P1 C13B C14B -163(2) . . . . ? C7 P1 C13B C14B 82(2) . . . . ? Au1 P1 C13B C14B -41(2) . . . . ? C18B C13B C14B C15B -6(3) . . . . ? P1 C13B C14B C15B -169.3(16) . . . . ? C13B C14B C15B C16B 0(3) . . . . ? C14B C15B C16B C17B 4(2) . . . . ? C15B C16B C17B C18B -0.4(15) . . . . ? C16B C17B C18B C13B -6.9(19) . . . . ? C14B C13B C18B C17B 10(3) . . . . ? P1 C13B C18B C17B 172.6(13) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.689 _refine_diff_density_min -1.669 _refine_diff_density_rms 0.147 # Attachment 'neda00502_final.cif.txt' data_neda00502_final _database_code_depnum_ccdc_archive 'CCDC 725994' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C38 H26 Au2 F8 P2' _chemical_formula_sum 'C38 H26 Au2 F8 P2' _chemical_formula_weight 1090.46 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.9272(2) _cell_length_b 12.2979(2) _cell_length_c 14.2430(2) _cell_angle_alpha 71.7130(10) _cell_angle_beta 66.9410(10) _cell_angle_gamma 64.2670(10) _cell_volume 1705.37(5) _cell_formula_units_Z 2 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 100890 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 40.250 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.124 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1028 _exptl_absorpt_coefficient_mu 8.759 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.198 _exptl_absorpt_correction_T_max 0.457 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 66388 _diffrn_reflns_av_R_equivalents 0.0732 _diffrn_reflns_av_sigmaI/netI 0.0428 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -19 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.65 _diffrn_reflns_theta_max 35.00 _reflns_number_total 14975 _reflns_number_gt 12481 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0579P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 14975 _refine_ls_number_parameters 451 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0468 _refine_ls_R_factor_gt 0.0363 _refine_ls_wR_factor_ref 0.0936 _refine_ls_wR_factor_gt 0.0897 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.674247(10) 0.537357(9) 0.743516(8) 0.01483(3) Uani 1 1 d . . . Au2 Au 0.448810(10) 0.501330(9) 0.752941(9) 0.01692(3) Uani 1 1 d . . . P1 P 0.79003(7) 0.36122(7) 0.66914(6) 0.01562(13) Uani 1 1 d . . . P2 P 0.34121(8) 0.69837(7) 0.78518(6) 0.01580(13) Uani 1 1 d . . . F1 F 0.88135(19) 0.09031(18) 0.66308(17) 0.0259(4) Uani 1 1 d . . . F2 F 0.7403(2) -0.05221(18) 0.72335(19) 0.0301(5) Uani 1 1 d . . . F3 F 0.4756(2) 0.04725(19) 0.78264(18) 0.0298(5) Uani 1 1 d . . . F4 F 0.35279(19) 0.28580(19) 0.79198(17) 0.0254(4) Uani 1 1 d . . . F5 F 0.22764(18) 0.88146(18) 0.93251(16) 0.0235(4) Uani 1 1 d . . . F6 F 0.3504(2) 0.9349(2) 1.02340(17) 0.0270(4) Uani 1 1 d . . . F7 F 0.6132(2) 0.8257(2) 0.98562(18) 0.0299(5) Uani 1 1 d . . . F8 F 0.75135(19) 0.6575(2) 0.86080(17) 0.0261(4) Uani 1 1 d . . . C1 C 0.6906(3) 0.2667(3) 0.7068(2) 0.0177(5) Uani 1 1 d . . . C2 C 0.7504(3) 0.1434(3) 0.6991(3) 0.0204(5) Uani 1 1 d . . . C3 C 0.6801(3) 0.0681(3) 0.7272(3) 0.0219(6) Uani 1 1 d . . . C4 C 0.5452(3) 0.1182(3) 0.7581(3) 0.0215(6) Uani 1 1 d . . . C5 C 0.4846(3) 0.2430(3) 0.7621(3) 0.0201(5) Uani 1 1 d . . . C6 C 0.5516(3) 0.3200(3) 0.7380(2) 0.0175(5) Uani 1 1 d . . . C7 C 0.9294(3) 0.2761(3) 0.7180(2) 0.0163(5) Uani 1 1 d . . . C8 C 0.9287(3) 0.1807(3) 0.8023(2) 0.0200(5) Uani 1 1 d . . . H8 H 0.8590 0.1531 0.8308 0.024 Uiso 1 1 calc R . . C9 C 1.0325(3) 0.1266(3) 0.8439(3) 0.0231(6) Uani 1 1 d . . . H9 H 1.0313 0.0636 0.9009 0.028 Uiso 1 1 calc R . . C10 C 1.1375(3) 0.1659(3) 0.8008(3) 0.0246(6) Uani 1 1 d . . . H10 H 1.2074 0.1283 0.8280 0.029 Uiso 1 1 calc R . . C11 C 1.1382(3) 0.2618(3) 0.7168(3) 0.0248(6) Uani 1 1 d . . . H11 H 1.2089 0.2879 0.6878 0.030 Uiso 1 1 calc R . . C12 C 1.0340(3) 0.3186(3) 0.6762(3) 0.0207(6) Uani 1 1 d . . . H12 H 1.0334 0.3845 0.6215 0.025 Uiso 1 1 calc R . . C13 C 0.8493(3) 0.3745(3) 0.5288(2) 0.0191(5) Uani 1 1 d . . . C14 C 0.9743(4) 0.3067(4) 0.4759(3) 0.0278(7) Uani 1 1 d . . . H14 H 1.0332 0.2536 0.5124 0.033 Uiso 1 1 calc R . . C15 C 1.0124(4) 0.3171(4) 0.3693(3) 0.0338(8) Uani 1 1 d . . . H15 H 1.0971 0.2722 0.3345 0.041 Uiso 1 1 calc R . . C16 C 0.9241(4) 0.3947(4) 0.3135(3) 0.0330(8) Uani 1 1 d . . . H16 H 0.9494 0.4012 0.2420 0.040 Uiso 1 1 calc R . . C17 C 0.7986(4) 0.4617(3) 0.3662(3) 0.0304(8) Uani 1 1 d . . . H17 H 0.7392 0.5132 0.3297 0.036 Uiso 1 1 calc R . . C18 C 0.7608(4) 0.4524(3) 0.4733(3) 0.0250(6) Uani 1 1 d . . . H18 H 0.6765 0.4981 0.5080 0.030 Uiso 1 1 calc R . . C19 C 0.4256(3) 0.7348(3) 0.8480(2) 0.0159(5) Uani 1 1 d . . . C20 C 0.3582(3) 0.8216(3) 0.9128(2) 0.0172(5) Uani 1 1 d . . . C21 C 0.4185(3) 0.8517(3) 0.9603(2) 0.0192(5) Uani 1 1 d . . . C22 C 0.5524(3) 0.7961(3) 0.9411(3) 0.0215(6) Uani 1 1 d . . . C23 C 0.6207(3) 0.7102(3) 0.8762(2) 0.0190(5) Uani 1 1 d . . . C24 C 0.5620(3) 0.6768(3) 0.8286(2) 0.0165(5) Uani 1 1 d . . . C25 C 0.1765(3) 0.7118(3) 0.8686(2) 0.0178(5) Uani 1 1 d . . . C26 C 0.1607(3) 0.6128(3) 0.9471(3) 0.0254(6) Uani 1 1 d . . . H26 H 0.2338 0.5452 0.9573 0.030 Uiso 1 1 calc R . . C27 C 0.0385(4) 0.6138(4) 1.0097(3) 0.0351(8) Uani 1 1 d . . . H27 H 0.0292 0.5488 1.0635 0.042 Uiso 1 1 calc R . . C28 C -0.0722(4) 0.7137(5) 0.9920(3) 0.0369(9) Uani 1 1 d . . . H28 H -0.1552 0.7141 1.0328 0.044 Uiso 1 1 calc R . . C29 C -0.0572(3) 0.8101(4) 0.9144(3) 0.0328(8) Uani 1 1 d . . . H29 H -0.1307 0.8757 0.9025 0.039 Uiso 1 1 calc R . . C30 C 0.0659(3) 0.8123(3) 0.8528(3) 0.0253(6) Uani 1 1 d . . . H30 H 0.0746 0.8798 0.8018 0.030 Uiso 1 1 calc R . . C31 C 0.3199(3) 0.8222(3) 0.6753(2) 0.0186(5) Uani 1 1 d . . . C32 C 0.2521(4) 0.8226(4) 0.6149(3) 0.0299(7) Uani 1 1 d . . . H32 H 0.2252 0.7573 0.6280 0.036 Uiso 1 1 calc R . . C33 C 0.2242(5) 0.9201(4) 0.5349(3) 0.0361(9) Uani 1 1 d . . . H33 H 0.1757 0.9217 0.4965 0.043 Uiso 1 1 calc R . . C34 C 0.2689(4) 1.0146(4) 0.5130(3) 0.0334(8) Uani 1 1 d . . . H34 H 0.2529 1.0785 0.4581 0.040 Uiso 1 1 calc R . . C35 C 0.3367(4) 1.0145(3) 0.5717(3) 0.0272(7) Uani 1 1 d . . . H35 H 0.3662 1.0785 0.5566 0.033 Uiso 1 1 calc R . . C36 C 0.3616(4) 0.9193(3) 0.6533(3) 0.0239(6) Uani 1 1 d . . . H36 H 0.4063 0.9205 0.6936 0.029 Uiso 1 1 calc R . . C37 C 0.6931(4) 0.6681(3) 0.6055(3) 0.0249(6) Uani 1 1 d . . . H37A H 0.6264 0.6846 0.5759 0.037 Uiso 1 1 d R . . H37B H 0.7773 0.6365 0.5571 0.037 Uiso 1 1 d R . . H37C H 0.6842 0.7425 0.6210 0.037 Uiso 1 1 d R . . C38 C 0.6604(4) 0.4158(3) 0.8881(3) 0.0243(6) Uani 1 1 d . . . H38A H 0.7415 0.3847 0.9035 0.037 Uiso 1 1 d R . . H38B H 0.6420 0.3488 0.8844 0.037 Uiso 1 1 d R . . H38C H 0.5916 0.4589 0.9416 0.037 Uiso 1 1 d R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01247(5) 0.01309(5) 0.01840(5) -0.00234(4) -0.00466(4) -0.00431(4) Au2 0.01347(5) 0.01310(5) 0.02434(6) -0.00304(4) -0.00686(4) -0.00393(4) P1 0.0139(3) 0.0130(3) 0.0194(3) -0.0022(2) -0.0060(3) -0.0038(2) P2 0.0145(3) 0.0128(3) 0.0197(3) -0.0018(2) -0.0066(3) -0.0040(2) F1 0.0175(9) 0.0201(9) 0.0377(11) -0.0122(8) -0.0059(8) -0.0017(7) F2 0.0302(11) 0.0131(8) 0.0473(13) -0.0069(8) -0.0151(10) -0.0037(8) F3 0.0296(11) 0.0207(9) 0.0445(13) 0.0004(9) -0.0139(10) -0.0153(8) F4 0.0170(9) 0.0212(9) 0.0389(11) -0.0039(8) -0.0107(8) -0.0063(7) F5 0.0154(8) 0.0211(9) 0.0321(10) -0.0105(8) -0.0082(7) 0.0001(7) F6 0.0243(10) 0.0271(10) 0.0306(10) -0.0164(8) -0.0058(8) -0.0042(8) F7 0.0267(11) 0.0362(12) 0.0360(11) -0.0151(9) -0.0116(9) -0.0112(9) F8 0.0147(8) 0.0294(10) 0.0360(11) -0.0116(9) -0.0078(8) -0.0050(7) C1 0.0156(12) 0.0157(11) 0.0215(13) -0.0036(10) -0.0055(10) -0.0051(9) C2 0.0168(12) 0.0167(12) 0.0284(15) -0.0063(11) -0.0074(11) -0.0044(10) C3 0.0230(14) 0.0141(12) 0.0294(15) -0.0059(11) -0.0104(12) -0.0036(10) C4 0.0256(15) 0.0147(12) 0.0295(15) -0.0023(11) -0.0115(12) -0.0099(11) C5 0.0179(13) 0.0179(12) 0.0266(14) -0.0010(10) -0.0089(11) -0.0081(10) C6 0.0181(12) 0.0139(11) 0.0227(13) 0.0005(10) -0.0100(10) -0.0067(10) C7 0.0141(11) 0.0147(11) 0.0183(12) -0.0046(9) -0.0050(9) -0.0024(9) C8 0.0174(12) 0.0157(12) 0.0235(14) 0.0000(10) -0.0061(11) -0.0052(10) C9 0.0221(14) 0.0193(13) 0.0247(14) -0.0001(11) -0.0105(12) -0.0040(11) C10 0.0214(14) 0.0218(14) 0.0310(16) -0.0047(12) -0.0131(12) -0.0034(12) C11 0.0203(14) 0.0253(15) 0.0323(17) -0.0037(13) -0.0101(12) -0.0102(12) C12 0.0174(13) 0.0185(13) 0.0266(14) -0.0022(11) -0.0072(11) -0.0072(10) C13 0.0226(14) 0.0167(12) 0.0205(13) -0.0009(10) -0.0090(11) -0.0084(10) C14 0.0250(16) 0.0321(17) 0.0193(14) -0.0056(12) -0.0043(12) -0.0053(13) C15 0.037(2) 0.040(2) 0.0216(15) -0.0080(14) -0.0029(14) -0.0149(17) C16 0.050(2) 0.0351(19) 0.0234(16) -0.0031(14) -0.0115(16) -0.0245(18) C17 0.047(2) 0.0262(16) 0.0285(17) 0.0062(13) -0.0226(16) -0.0200(16) C18 0.0281(16) 0.0211(14) 0.0289(16) 0.0007(12) -0.0151(13) -0.0091(12) C19 0.0163(12) 0.0135(11) 0.0177(12) 0.0003(9) -0.0068(9) -0.0055(9) C20 0.0158(12) 0.0135(11) 0.0201(12) -0.0022(9) -0.0051(10) -0.0040(9) C21 0.0203(13) 0.0168(12) 0.0198(13) -0.0051(10) -0.0064(10) -0.0045(10) C22 0.0231(14) 0.0192(13) 0.0258(14) -0.0033(11) -0.0106(12) -0.0083(11) C23 0.0161(12) 0.0168(12) 0.0229(13) -0.0026(10) -0.0057(10) -0.0056(10) C24 0.0161(12) 0.0152(11) 0.0188(12) -0.0007(9) -0.0056(10) -0.0073(9) C25 0.0157(12) 0.0201(13) 0.0190(12) -0.0071(10) -0.0050(10) -0.0052(10) C26 0.0240(15) 0.0282(16) 0.0251(15) -0.0017(12) -0.0061(12) -0.0135(13) C27 0.0308(19) 0.046(2) 0.0313(18) -0.0071(16) 0.0002(15) -0.0247(18) C28 0.0219(16) 0.059(3) 0.0352(19) -0.0220(19) 0.0032(14) -0.0203(18) C29 0.0157(14) 0.045(2) 0.038(2) -0.0199(17) -0.0061(13) -0.0043(14) C30 0.0174(13) 0.0270(16) 0.0282(16) -0.0103(13) -0.0071(12) -0.0009(12) C31 0.0215(13) 0.0183(12) 0.0176(12) -0.0017(10) -0.0073(10) -0.0080(10) C32 0.044(2) 0.0297(17) 0.0251(16) 0.0007(13) -0.0161(15) -0.0196(16) C33 0.049(2) 0.040(2) 0.0276(18) 0.0027(15) -0.0236(18) -0.0180(19) C34 0.043(2) 0.0279(17) 0.0252(16) 0.0059(13) -0.0156(15) -0.0118(16) C35 0.0357(18) 0.0185(13) 0.0252(15) 0.0007(11) -0.0093(13) -0.0105(13) C36 0.0306(16) 0.0184(13) 0.0247(14) -0.0005(11) -0.0127(13) -0.0089(12) C37 0.0264(15) 0.0200(14) 0.0238(14) -0.0010(11) -0.0039(12) -0.0095(12) C38 0.0271(16) 0.0188(13) 0.0203(14) -0.0014(11) -0.0060(12) -0.0045(12) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.060(3) . ? Au1 C37 2.117(3) . ? Au1 C38 2.125(3) . ? Au1 P1 2.3276(8) . ? Au1 Au2 2.85632(16) . ? Au2 C6 2.060(3) . ? Au2 P2 2.2948(8) . ? P1 C7 1.811(3) . ? P1 C13 1.820(3) . ? P1 C1 1.831(3) . ? P2 C25 1.819(3) . ? P2 C31 1.821(3) . ? P2 C19 1.834(3) . ? F1 C2 1.351(4) . ? F2 C3 1.344(4) . ? F3 C4 1.335(4) . ? F4 C5 1.351(4) . ? F5 C20 1.355(3) . ? F6 C21 1.341(4) . ? F7 C22 1.339(4) . ? F8 C23 1.357(4) . ? C1 C2 1.387(4) . ? C1 C6 1.427(4) . ? C2 C3 1.378(5) . ? C3 C4 1.385(5) . ? C4 C5 1.392(4) . ? C5 C6 1.376(4) . ? C7 C8 1.391(4) . ? C7 C12 1.406(4) . ? C8 C9 1.393(4) . ? C8 H8 0.9300 . ? C9 C10 1.384(5) . ? C9 H9 0.9300 . ? C10 C11 1.392(5) . ? C10 H10 0.9300 . ? C11 C12 1.387(5) . ? C11 H11 0.9300 . ? C12 H12 0.9300 . ? C13 C14 1.386(5) . ? C13 C18 1.399(4) . ? C14 C15 1.385(5) . ? C14 H14 0.9300 . ? C15 C16 1.399(6) . ? C15 H15 0.9300 . ? C16 C17 1.385(6) . ? C16 H16 0.9300 . ? C17 C18 1.393(5) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? C19 C20 1.388(4) . ? C19 C24 1.413(4) . ? C20 C21 1.372(4) . ? C21 C22 1.386(5) . ? C22 C23 1.382(5) . ? C23 C24 1.383(4) . ? C25 C26 1.396(5) . ? C25 C30 1.400(4) . ? C26 C27 1.376(5) . ? C26 H26 0.9300 . ? C27 C28 1.404(6) . ? C27 H27 0.9300 . ? C28 C29 1.367(6) . ? C28 H28 0.9300 . ? C29 C30 1.391(5) . ? C29 H29 0.9300 . ? C30 H30 0.9300 . ? C31 C32 1.389(5) . ? C31 C36 1.389(5) . ? C32 C33 1.393(5) . ? C32 H32 0.9300 . ? C33 C34 1.382(6) . ? C33 H33 0.9300 . ? C34 C35 1.372(6) . ? C34 H34 0.9300 . ? C35 C36 1.388(5) . ? C35 H35 0.9300 . ? C36 H36 0.9300 . ? C37 H37A 0.9600 . ? C37 H37B 0.9600 . ? C37 H37C 0.9600 . ? C38 H38A 0.9600 . ? C38 H38B 0.9600 . ? C38 H38C 0.9600 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 C37 90.03(12) . . ? C24 Au1 C38 86.33(12) . . ? C37 Au1 C38 174.47(14) . . ? C24 Au1 P1 171.62(8) . . ? C37 Au1 P1 98.08(10) . . ? C38 Au1 P1 85.73(9) . . ? C24 Au1 Au2 91.81(8) . . ? C37 Au1 Au2 100.28(11) . . ? C38 Au1 Au2 84.01(11) . . ? P1 Au1 Au2 84.72(2) . . ? C6 Au2 P2 173.80(9) . . ? C6 Au2 Au1 92.47(8) . . ? P2 Au2 Au1 84.26(2) . . ? C7 P1 C13 107.79(14) . . ? C7 P1 C1 109.08(14) . . ? C13 P1 C1 102.23(14) . . ? C7 P1 Au1 106.50(10) . . ? C13 P1 Au1 119.78(10) . . ? C1 P1 Au1 111.12(10) . . ? C25 P2 C31 104.93(14) . . ? C25 P2 C19 110.27(14) . . ? C31 P2 C19 104.88(14) . . ? C25 P2 Au2 107.92(10) . . ? C31 P2 Au2 117.85(10) . . ? C19 P2 Au2 110.75(10) . . ? C2 C1 C6 119.3(3) . . ? C2 C1 P1 119.9(2) . . ? C6 C1 P1 120.7(2) . . ? F1 C2 C3 116.2(3) . . ? F1 C2 C1 121.7(3) . . ? C3 C2 C1 122.1(3) . . ? F2 C3 C2 121.1(3) . . ? F2 C3 C4 119.7(3) . . ? C2 C3 C4 119.2(3) . . ? F3 C4 C3 120.0(3) . . ? F3 C4 C5 121.2(3) . . ? C3 C4 C5 118.9(3) . . ? F4 C5 C6 120.8(3) . . ? F4 C5 C4 115.7(3) . . ? C6 C5 C4 123.5(3) . . ? C5 C6 C1 116.9(3) . . ? C5 C6 Au2 119.2(2) . . ? C1 C6 Au2 123.9(2) . . ? C8 C7 C12 119.8(3) . . ? C8 C7 P1 122.0(2) . . ? C12 C7 P1 117.7(2) . . ? C7 C8 C9 119.9(3) . . ? C7 C8 H8 120.0 . . ? C9 C8 H8 120.0 . . ? C10 C9 C8 120.3(3) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C9 C10 C11 119.9(3) . . ? C9 C10 H10 120.1 . . ? C11 C10 H10 120.1 . . ? C12 C11 C10 120.4(3) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C11 C12 C7 119.6(3) . . ? C11 C12 H12 120.2 . . ? C7 C12 H12 120.2 . . ? C14 C13 C18 119.2(3) . . ? C14 C13 P1 123.2(2) . . ? C18 C13 P1 117.5(3) . . ? C15 C14 C13 120.7(3) . . ? C15 C14 H14 119.7 . . ? C13 C14 H14 119.7 . . ? C14 C15 C16 120.3(4) . . ? C14 C15 H15 119.9 . . ? C16 C15 H15 119.9 . . ? C17 C16 C15 119.2(3) . . ? C17 C16 H16 120.4 . . ? C15 C16 H16 120.4 . . ? C16 C17 C18 120.5(3) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C17 C18 C13 120.1(3) . . ? C17 C18 H18 119.9 . . ? C13 C18 H18 119.9 . . ? C20 C19 C24 118.8(3) . . ? C20 C19 P2 121.1(2) . . ? C24 C19 P2 120.0(2) . . ? F5 C20 C21 116.2(3) . . ? F5 C20 C19 121.2(3) . . ? C21 C20 C19 122.6(3) . . ? F6 C21 C20 121.1(3) . . ? F6 C21 C22 119.8(3) . . ? C20 C21 C22 119.1(3) . . ? F7 C22 C23 121.3(3) . . ? F7 C22 C21 119.8(3) . . ? C23 C22 C21 118.9(3) . . ? F8 C23 C22 116.6(3) . . ? F8 C23 C24 120.2(3) . . ? C22 C23 C24 123.2(3) . . ? C23 C24 C19 117.4(3) . . ? C23 C24 Au1 118.7(2) . . ? C19 C24 Au1 123.7(2) . . ? C26 C25 C30 119.2(3) . . ? C26 C25 P2 117.6(2) . . ? C30 C25 P2 123.0(3) . . ? C27 C26 C25 120.8(4) . . ? C27 C26 H26 119.6 . . ? C25 C26 H26 119.6 . . ? C26 C27 C28 119.7(4) . . ? C26 C27 H27 120.2 . . ? C28 C27 H27 120.2 . . ? C29 C28 C27 119.6(4) . . ? C29 C28 H28 120.2 . . ? C27 C28 H28 120.2 . . ? C28 C29 C30 121.4(4) . . ? C28 C29 H29 119.3 . . ? C30 C29 H29 119.3 . . ? C29 C30 C25 119.3(4) . . ? C29 C30 H30 120.4 . . ? C25 C30 H30 120.4 . . ? C32 C31 C36 119.0(3) . . ? C32 C31 P2 118.1(3) . . ? C36 C31 P2 122.7(2) . . ? C31 C32 C33 120.4(4) . . ? C31 C32 H32 119.8 . . ? C33 C32 H32 119.8 . . ? C34 C33 C32 119.6(4) . . ? C34 C33 H33 120.2 . . ? C32 C33 H33 120.2 . . ? C35 C34 C33 120.3(3) . . ? C35 C34 H34 119.8 . . ? C33 C34 H34 119.8 . . ? C34 C35 C36 120.3(4) . . ? C34 C35 H35 119.9 . . ? C36 C35 H35 119.9 . . ? C35 C36 C31 120.3(3) . . ? C35 C36 H36 119.9 . . ? C31 C36 H36 119.9 . . ? Au1 C37 H37A 109.5 . . ? Au1 C37 H37B 109.5 . . ? H37A C37 H37B 109.5 . . ? Au1 C37 H37C 109.5 . . ? H37A C37 H37C 109.5 . . ? H37B C37 H37C 109.5 . . ? Au1 C38 H38A 109.5 . . ? Au1 C38 H38B 109.5 . . ? H38A C38 H38B 109.5 . . ? Au1 C38 H38C 109.5 . . ? H38A C38 H38C 109.5 . . ? H38B C38 H38C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -153.10(12) . . . . ? C37 Au1 Au2 C6 116.54(13) . . . . ? C38 Au1 Au2 C6 -66.98(13) . . . . ? P1 Au1 Au2 C6 19.26(9) . . . . ? C24 Au1 Au2 P2 21.62(8) . . . . ? C37 Au1 Au2 P2 -68.74(10) . . . . ? C38 Au1 Au2 P2 107.73(9) . . . . ? P1 Au1 Au2 P2 -166.02(3) . . . . ? C37 Au1 P1 C7 117.62(15) . . . . ? C38 Au1 P1 C7 -58.35(15) . . . . ? Au2 Au1 P1 C7 -142.72(11) . . . . ? C37 Au1 P1 C13 -4.84(17) . . . . ? C38 Au1 P1 C13 179.19(16) . . . . ? Au2 Au1 P1 C13 94.82(13) . . . . ? C37 Au1 P1 C1 -123.70(15) . . . . ? C38 Au1 P1 C1 60.33(15) . . . . ? Au2 Au1 P1 C1 -24.04(11) . . . . ? Au1 Au2 P2 C25 -148.62(11) . . . . ? Au1 Au2 P2 C31 92.88(12) . . . . ? Au1 Au2 P2 C19 -27.83(10) . . . . ? C7 P1 C1 C2 -42.6(3) . . . . ? C13 P1 C1 C2 71.3(3) . . . . ? Au1 P1 C1 C2 -159.7(2) . . . . ? C7 P1 C1 C6 141.2(2) . . . . ? C13 P1 C1 C6 -104.8(3) . . . . ? Au1 P1 C1 C6 24.1(3) . . . . ? C6 C1 C2 F1 175.4(3) . . . . ? P1 C1 C2 F1 -0.8(4) . . . . ? C6 C1 C2 C3 -4.4(5) . . . . ? P1 C1 C2 C3 179.4(3) . . . . ? F1 C2 C3 F2 3.2(5) . . . . ? C1 C2 C3 F2 -177.0(3) . . . . ? F1 C2 C3 C4 -175.7(3) . . . . ? C1 C2 C3 C4 4.1(5) . . . . ? F2 C3 C4 F3 -0.8(5) . . . . ? C2 C3 C4 F3 178.0(3) . . . . ? F2 C3 C4 C5 179.7(3) . . . . ? C2 C3 C4 C5 -1.5(5) . . . . ? F3 C4 C5 F4 -0.1(5) . . . . ? C3 C4 C5 F4 179.5(3) . . . . ? F3 C4 C5 C6 179.7(3) . . . . ? C3 C4 C5 C6 -0.8(5) . . . . ? F4 C5 C6 C1 -179.7(3) . . . . ? C4 C5 C6 C1 0.6(5) . . . . ? F4 C5 C6 Au2 2.1(4) . . . . ? C4 C5 C6 Au2 -177.6(3) . . . . ? C2 C1 C6 C5 2.0(4) . . . . ? P1 C1 C6 C5 178.1(2) . . . . ? C2 C1 C6 Au2 -180.0(2) . . . . ? P1 C1 C6 Au2 -3.8(4) . . . . ? Au1 Au2 C6 C5 164.5(2) . . . . ? Au1 Au2 C6 C1 -13.5(3) . . . . ? C13 P1 C7 C8 -133.7(3) . . . . ? C1 P1 C7 C8 -23.4(3) . . . . ? Au1 P1 C7 C8 96.6(3) . . . . ? C13 P1 C7 C12 53.9(3) . . . . ? C1 P1 C7 C12 164.2(2) . . . . ? Au1 P1 C7 C12 -75.8(2) . . . . ? C12 C7 C8 C9 -1.0(5) . . . . ? P1 C7 C8 C9 -173.2(2) . . . . ? C7 C8 C9 C10 -1.0(5) . . . . ? C8 C9 C10 C11 1.4(5) . . . . ? C9 C10 C11 C12 0.2(5) . . . . ? C10 C11 C12 C7 -2.2(5) . . . . ? C8 C7 C12 C11 2.5(5) . . . . ? P1 C7 C12 C11 175.1(3) . . . . ? C7 P1 C13 C14 12.8(3) . . . . ? C1 P1 C13 C14 -102.1(3) . . . . ? Au1 P1 C13 C14 134.7(3) . . . . ? C7 P1 C13 C18 -170.8(3) . . . . ? C1 P1 C13 C18 74.4(3) . . . . ? Au1 P1 C13 C18 -48.9(3) . . . . ? C18 C13 C14 C15 1.1(6) . . . . ? P1 C13 C14 C15 177.4(3) . . . . ? C13 C14 C15 C16 -1.2(6) . . . . ? C14 C15 C16 C17 0.6(6) . . . . ? C15 C16 C17 C18 0.3(6) . . . . ? C16 C17 C18 C13 -0.4(6) . . . . ? C14 C13 C18 C17 -0.3(5) . . . . ? P1 C13 C18 C17 -176.8(3) . . . . ? C25 P2 C19 C20 -33.2(3) . . . . ? C31 P2 C19 C20 79.3(3) . . . . ? Au2 P2 C19 C20 -152.6(2) . . . . ? C25 P2 C19 C24 148.6(2) . . . . ? C31 P2 C19 C24 -98.9(2) . . . . ? Au2 P2 C19 C24 29.2(3) . . . . ? C24 C19 C20 F5 178.8(3) . . . . ? P2 C19 C20 F5 0.6(4) . . . . ? C24 C19 C20 C21 -1.2(4) . . . . ? P2 C19 C20 C21 -179.4(2) . . . . ? F5 C20 C21 F6 0.8(4) . . . . ? C19 C20 C21 F6 -179.2(3) . . . . ? F5 C20 C21 C22 -178.3(3) . . . . ? C19 C20 C21 C22 1.7(5) . . . . ? F6 C21 C22 F7 0.0(5) . . . . ? C20 C21 C22 F7 179.1(3) . . . . ? F6 C21 C22 C23 179.7(3) . . . . ? C20 C21 C22 C23 -1.3(5) . . . . ? F7 C22 C23 F8 0.4(5) . . . . ? C21 C22 C23 F8 -179.3(3) . . . . ? F7 C22 C23 C24 179.9(3) . . . . ? C21 C22 C23 C24 0.3(5) . . . . ? F8 C23 C24 C19 179.8(3) . . . . ? C22 C23 C24 C19 0.3(4) . . . . ? F8 C23 C24 Au1 4.5(4) . . . . ? C22 C23 C24 Au1 -175.1(2) . . . . ? C20 C19 C24 C23 0.2(4) . . . . ? P2 C19 C24 C23 178.4(2) . . . . ? C20 C19 C24 Au1 175.3(2) . . . . ? P2 C19 C24 Au1 -6.5(3) . . . . ? C37 Au1 C24 C23 -98.4(3) . . . . ? C38 Au1 C24 C23 77.5(3) . . . . ? Au2 Au1 C24 C23 161.3(2) . . . . ? C37 Au1 C24 C19 86.6(3) . . . . ? C38 Au1 C24 C19 -97.6(3) . . . . ? Au2 Au1 C24 C19 -13.7(2) . . . . ? C31 P2 C25 C26 165.6(3) . . . . ? C19 P2 C25 C26 -81.9(3) . . . . ? Au2 P2 C25 C26 39.2(3) . . . . ? C31 P2 C25 C30 -9.8(3) . . . . ? C19 P2 C25 C30 102.6(3) . . . . ? Au2 P2 C25 C30 -136.3(3) . . . . ? C30 C25 C26 C27 -1.0(5) . . . . ? P2 C25 C26 C27 -176.6(3) . . . . ? C25 C26 C27 C28 2.4(6) . . . . ? C26 C27 C28 C29 -1.6(7) . . . . ? C27 C28 C29 C30 -0.6(6) . . . . ? C28 C29 C30 C25 2.1(6) . . . . ? C26 C25 C30 C29 -1.3(5) . . . . ? P2 C25 C30 C29 174.1(3) . . . . ? C25 P2 C31 C32 -60.7(3) . . . . ? C19 P2 C31 C32 -176.9(3) . . . . ? Au2 P2 C31 C32 59.4(3) . . . . ? C25 P2 C31 C36 115.4(3) . . . . ? C19 P2 C31 C36 -0.9(3) . . . . ? Au2 P2 C31 C36 -124.6(3) . . . . ? C36 C31 C32 C33 -1.2(6) . . . . ? P2 C31 C32 C33 175.0(3) . . . . ? C31 C32 C33 C34 2.6(7) . . . . ? C32 C33 C34 C35 -2.1(7) . . . . ? C33 C34 C35 C36 0.3(6) . . . . ? C34 C35 C36 C31 1.1(6) . . . . ? C32 C31 C36 C35 -0.6(5) . . . . ? P2 C31 C36 C35 -176.6(3) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 5.705 _refine_diff_density_min -3.880 _refine_diff_density_rms 0.230 # Attachment 'neda00602.cif.txt' data_neda00602 _database_code_depnum_ccdc_archive 'CCDC 725995' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C50 H30 Au2 F8 O4 P2, 0.5(C6 H14)' _chemical_formula_sum 'C53 H37 Au2 F8 O4 P2' _chemical_formula_weight 1345.70 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall -P2yn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 12.14090(10) _cell_length_b 15.8124(2) _cell_length_c 24.6158(3) _cell_angle_alpha 90.00 _cell_angle_beta 99.8870(10) _cell_angle_gamma 90.00 _cell_volume 4655.48(9) _cell_formula_units_Z 4 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 278761 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 38.568 _exptl_crystal_description piece _exptl_crystal_colour yellow _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.920 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2588 _exptl_absorpt_coefficient_mu 6.444 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.390 _exptl_absorpt_correction_T_max 0.522 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 154997 _diffrn_reflns_av_R_equivalents 0.0754 _diffrn_reflns_av_sigmaI/netI 0.0453 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 40 _diffrn_reflns_theta_min 2.71 _diffrn_reflns_theta_max 36.00 _reflns_number_total 22018 _reflns_number_gt 17210 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; CHECKCIF/PLATON reports an unusually large C-atom of a phenl group in the molecule. This phenyl group seems to be more susceptible to thermal motion than the other groups, the thermal ellipsoids do not indicate any meaningful disorder. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0260P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 22018 _refine_ls_number_parameters 623 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0529 _refine_ls_R_factor_gt 0.0312 _refine_ls_wR_factor_ref 0.0594 _refine_ls_wR_factor_gt 0.0557 _refine_ls_goodness_of_fit_ref 1.042 _refine_ls_restrained_S_all 1.042 _refine_ls_shift/su_max 0.005 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.183002(7) 0.544732(5) 0.667068(3) 0.01281(2) Uani 1 1 d . . . Au2 Au 0.050322(7) 0.567799(5) 0.734028(3) 0.01239(2) Uani 1 1 d . . . P1 P 0.24973(5) 0.43166(3) 0.72445(2) 0.01432(10) Uani 1 1 d . . . P2 P -0.07713(5) 0.59174(4) 0.65288(2) 0.01403(10) Uani 1 1 d . . . F1 F 0.40548(12) 0.38585(9) 0.83527(6) 0.0238(3) Uani 1 1 d . . . F2 F 0.42358(12) 0.47329(10) 0.93064(6) 0.0261(3) Uani 1 1 d . . . F3 F 0.28774(13) 0.60633(10) 0.93869(6) 0.0277(3) Uani 1 1 d . . . F4 F 0.13028(12) 0.65096(9) 0.85527(6) 0.0226(3) Uani 1 1 d . . . F5 F -0.16037(12) 0.73623(9) 0.56675(6) 0.0266(3) Uani 1 1 d . . . F6 F -0.03048(12) 0.83542(9) 0.51573(6) 0.0278(3) Uani 1 1 d . . . F7 F 0.19527(12) 0.82067(8) 0.53915(6) 0.0219(3) Uani 1 1 d . . . F8 F 0.29183(11) 0.69966(8) 0.60681(6) 0.0200(3) Uani 1 1 d . . . O1 O 0.30184(13) 0.52107(10) 0.61554(7) 0.0185(3) Uani 1 1 d . . . O2 O 0.17244(15) 0.43068(11) 0.57432(7) 0.0248(4) Uani 1 1 d . . . O3 O -0.05789(13) 0.59045(10) 0.79046(7) 0.0188(3) Uani 1 1 d . . . O4 O -0.13780(17) 0.46583(12) 0.76492(8) 0.0301(4) Uani 1 1 d . . . C1 C 0.25637(18) 0.47480(14) 0.79322(9) 0.0155(4) Uani 1 1 d . . . C2 C 0.33573(19) 0.45151(14) 0.83804(10) 0.0185(4) Uani 1 1 d . . . C3 C 0.34638(19) 0.49552(16) 0.88745(9) 0.0199(4) Uani 1 1 d . . . C4 C 0.2769(2) 0.56266(15) 0.89161(10) 0.0200(4) Uani 1 1 d . . . C5 C 0.19461(19) 0.58457(14) 0.84713(9) 0.0168(4) Uani 1 1 d . . . C6 C 0.18088(18) 0.54141(13) 0.79791(9) 0.0146(4) Uani 1 1 d . . . C7 C 0.38967(18) 0.40405(14) 0.71547(9) 0.0165(4) Uani 1 1 d . . . C8 C 0.4715(2) 0.46709(15) 0.72084(10) 0.0220(5) Uani 1 1 d . . . H8 H 0.4537 0.5229 0.7307 0.026 Uiso 1 1 calc R . . C9 C 0.5775(2) 0.44871(16) 0.71194(11) 0.0254(5) Uani 1 1 d . . . H9 H 0.6337 0.4912 0.7169 0.030 Uiso 1 1 calc R . . C10 C 0.6025(2) 0.36780(18) 0.69561(11) 0.0273(5) Uani 1 1 d . . . H10 H 0.6751 0.3555 0.6883 0.033 Uiso 1 1 calc R . . C11 C 0.5222(2) 0.30534(17) 0.69003(12) 0.0303(6) Uani 1 1 d . . . H11 H 0.5400 0.2498 0.6796 0.036 Uiso 1 1 calc R . . C12 C 0.4151(2) 0.32351(15) 0.69961(11) 0.0230(5) Uani 1 1 d . . . H12 H 0.3595 0.2806 0.6953 0.028 Uiso 1 1 calc R . . C13 C 0.17087(18) 0.33440(13) 0.71761(9) 0.0167(4) Uani 1 1 d . . . C14 C 0.1742(2) 0.27988(15) 0.76296(10) 0.0209(4) Uani 1 1 d . . . H14 H 0.2126 0.2962 0.7983 0.025 Uiso 1 1 calc R . . C15 C 0.1209(2) 0.20189(15) 0.75570(11) 0.0236(5) Uani 1 1 d . . . H15 H 0.1226 0.1649 0.7862 0.028 Uiso 1 1 calc R . . C16 C 0.0653(2) 0.17796(15) 0.70404(11) 0.0254(5) Uani 1 1 d . . . H16 H 0.0293 0.1245 0.6993 0.030 Uiso 1 1 calc R . . C17 C 0.0621(2) 0.23135(16) 0.65945(11) 0.0275(5) Uani 1 1 d . . . H17 H 0.0242 0.2143 0.6241 0.033 Uiso 1 1 calc R . . C18 C 0.1143(2) 0.31035(16) 0.66599(10) 0.0249(5) Uani 1 1 d . . . H18 H 0.1112 0.3473 0.6354 0.030 Uiso 1 1 calc R . . C19 C -0.00127(18) 0.66158(13) 0.61378(9) 0.0156(4) Uani 1 1 d . . . C20 C -0.04982(19) 0.72412(14) 0.57765(9) 0.0186(4) Uani 1 1 d . . . C21 C 0.0162(2) 0.77694(14) 0.55154(9) 0.0190(4) Uani 1 1 d . . . C22 C 0.13081(19) 0.76793(14) 0.56322(9) 0.0171(4) Uani 1 1 d . . . C23 C 0.17880(18) 0.70428(13) 0.59822(9) 0.0143(4) Uani 1 1 d . . . C24 C 0.11564(18) 0.64909(13) 0.62321(8) 0.0144(4) Uani 1 1 d . . . C25 C -0.20664(18) 0.64180(14) 0.66129(10) 0.0184(4) Uani 1 1 d . . . C26 C -0.2007(2) 0.71246(17) 0.69571(11) 0.0291(6) Uani 1 1 d . . . H26 H -0.1304 0.7313 0.7149 0.035 Uiso 1 1 calc R . . C27 C -0.2976(2) 0.75504(18) 0.70172(12) 0.0339(6) Uani 1 1 d . . . H27 H -0.2936 0.8038 0.7245 0.041 Uiso 1 1 calc R . . C28 C -0.3997(2) 0.72668(17) 0.67469(12) 0.0319(6) Uani 1 1 d . . . H28 H -0.4660 0.7557 0.6793 0.038 Uiso 1 1 calc R . . C29 C -0.4063(2) 0.65623(19) 0.64093(15) 0.0388(7) Uani 1 1 d . . . H29 H -0.4770 0.6370 0.6225 0.047 Uiso 1 1 calc R . . C30 C -0.3093(2) 0.61348(17) 0.63401(12) 0.0294(6) Uani 1 1 d . . . H30 H -0.3135 0.5652 0.6107 0.035 Uiso 1 1 calc R . . C31 C -0.11032(17) 0.49722(14) 0.61179(9) 0.0151(4) Uani 1 1 d . . . C32 C -0.1355(2) 0.42394(15) 0.63851(10) 0.0204(4) Uani 1 1 d . . . H32 H -0.1348 0.4242 0.6772 0.024 Uiso 1 1 calc R . . C33 C -0.1617(2) 0.35021(15) 0.60810(10) 0.0229(5) Uani 1 1 d . . . H33 H -0.1804 0.3002 0.6258 0.027 Uiso 1 1 calc R . . C34 C -0.1605(2) 0.34990(15) 0.55193(10) 0.0228(5) Uani 1 1 d . . . H34 H -0.1780 0.2994 0.5313 0.027 Uiso 1 1 calc R . . C35 C -0.1339(2) 0.42250(15) 0.52563(10) 0.0234(5) Uani 1 1 d . . . H35 H -0.1327 0.4215 0.4871 0.028 Uiso 1 1 calc R . . C36 C -0.1088(2) 0.49717(15) 0.55531(9) 0.0197(4) Uani 1 1 d . . . H36 H -0.0909 0.5472 0.5373 0.024 Uiso 1 1 calc R . . C37 C 0.2696(2) 0.45739(15) 0.58332(9) 0.0190(4) Uani 1 1 d . . . C38 C 0.3599(2) 0.41511(16) 0.55835(10) 0.0233(5) Uani 1 1 d . . . C39 C 0.3363(3) 0.3384(2) 0.53193(14) 0.0455(8) Uani 1 1 d . . . H39 H 0.2636 0.3146 0.5285 0.055 Uiso 1 1 calc R . . C40 C 0.4201(3) 0.2962(3) 0.51023(16) 0.0644(12) Uani 1 1 d . . . H40 H 0.4043 0.2434 0.4922 0.077 Uiso 1 1 calc R . . C41 C 0.5250(3) 0.3305(2) 0.51483(13) 0.0488(9) Uani 1 1 d . . . H41 H 0.5813 0.3018 0.4995 0.059 Uiso 1 1 calc R . . C42 C 0.5487(3) 0.4059(2) 0.54138(13) 0.0387(7) Uani 1 1 d . . . H42 H 0.6215 0.4295 0.5448 0.046 Uiso 1 1 calc R . . C43 C 0.4656(2) 0.44834(18) 0.56355(12) 0.0318(6) Uani 1 1 d . . . H43 H 0.4824 0.5005 0.5823 0.038 Uiso 1 1 calc R . . C44 C -0.12689(18) 0.52966(15) 0.79431(9) 0.0178(4) Uani 1 1 d . . . C45 C -0.19548(19) 0.54070(15) 0.83958(9) 0.0188(4) Uani 1 1 d . . . C46 C -0.1795(2) 0.60963(15) 0.87523(10) 0.0239(5) Uani 1 1 d . . . H46 H -0.1258 0.6516 0.8708 0.029 Uiso 1 1 calc R . . C47 C -0.2418(2) 0.61705(18) 0.91722(11) 0.0306(6) Uani 1 1 d . . . H47 H -0.2306 0.6643 0.9414 0.037 Uiso 1 1 calc R . . C48 C -0.3202(2) 0.55629(18) 0.92418(12) 0.0311(6) Uani 1 1 d . . . H48 H -0.3630 0.5618 0.9529 0.037 Uiso 1 1 calc R . . C49 C -0.3358(2) 0.4872(2) 0.88890(12) 0.0333(6) Uani 1 1 d . . . H49 H -0.3894 0.4452 0.8935 0.040 Uiso 1 1 calc R . . C50 C -0.2733(2) 0.47912(18) 0.84680(11) 0.0287(6) Uani 1 1 d . . . H50 H -0.2839 0.4315 0.8230 0.034 Uiso 1 1 calc R . . C51 C -0.0507(2) 0.60783(18) 1.10305(12) 0.0332(6) Uani 1 1 d . . . H51A H 0.0270 0.6080 1.1223 0.050 Uiso 1 1 calc R . . H51B H -0.1010 0.6014 1.1300 0.050 Uiso 1 1 calc R . . H51C H -0.0669 0.6612 1.0831 0.050 Uiso 1 1 calc R . . C52 C -0.0680(2) 0.53486(18) 1.06259(12) 0.0292(6) Uani 1 1 d . . . H52A H -0.1467 0.5351 1.0435 0.035 Uiso 1 1 calc R . . H52B H -0.0550 0.4811 1.0833 0.035 Uiso 1 1 calc R . . C53 C 0.0085(2) 0.53789(16) 1.01959(11) 0.0263(5) Uani 1 1 d . . . H53A H 0.0872 0.5392 1.0386 0.032 Uiso 1 1 calc R . . H53B H -0.0061 0.5906 0.9979 0.032 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01418(4) 0.01227(4) 0.01280(4) 0.00087(3) 0.00466(3) 0.00107(3) Au2 0.01306(4) 0.01248(4) 0.01229(4) -0.00034(3) 0.00399(3) -0.00019(3) P1 0.0160(3) 0.0128(2) 0.0149(2) 0.00155(19) 0.0049(2) 0.00169(19) P2 0.0135(2) 0.0142(2) 0.0145(2) -0.00091(19) 0.00262(19) -0.00012(18) F1 0.0230(7) 0.0266(7) 0.0217(7) 0.0056(6) 0.0035(6) 0.0091(6) F2 0.0215(7) 0.0378(9) 0.0169(7) 0.0057(6) -0.0026(5) 0.0011(6) F3 0.0313(8) 0.0330(8) 0.0171(7) -0.0070(6) -0.0007(6) -0.0042(6) F4 0.0279(7) 0.0184(7) 0.0213(7) -0.0045(5) 0.0033(6) 0.0028(5) F5 0.0175(7) 0.0289(8) 0.0309(8) 0.0097(6) -0.0035(6) 0.0003(6) F6 0.0306(8) 0.0229(7) 0.0262(8) 0.0127(6) -0.0054(6) -0.0013(6) F7 0.0288(8) 0.0185(7) 0.0192(7) 0.0049(5) 0.0062(5) -0.0054(5) F8 0.0166(7) 0.0206(7) 0.0241(7) 0.0032(5) 0.0072(5) -0.0003(5) O1 0.0205(8) 0.0188(8) 0.0184(8) -0.0005(6) 0.0094(6) 0.0021(6) O2 0.0247(9) 0.0287(9) 0.0212(9) -0.0016(7) 0.0050(7) 0.0002(7) O3 0.0186(8) 0.0199(8) 0.0202(8) -0.0026(6) 0.0097(6) -0.0021(6) O4 0.0376(11) 0.0293(10) 0.0278(10) -0.0126(8) 0.0183(8) -0.0134(8) C1 0.0155(10) 0.0172(10) 0.0146(9) 0.0016(7) 0.0044(7) -0.0001(7) C2 0.0170(10) 0.0198(11) 0.0190(11) 0.0039(8) 0.0043(8) 0.0018(8) C3 0.0165(10) 0.0270(12) 0.0153(10) 0.0039(8) 0.0001(8) -0.0025(8) C4 0.0210(11) 0.0224(11) 0.0157(10) -0.0018(8) 0.0012(8) -0.0060(8) C5 0.0190(10) 0.0145(10) 0.0173(10) -0.0005(7) 0.0044(8) 0.0002(7) C6 0.0135(9) 0.0151(9) 0.0153(9) 0.0018(7) 0.0034(7) -0.0008(7) C7 0.0179(10) 0.0163(10) 0.0158(10) 0.0026(8) 0.0048(8) 0.0020(8) C8 0.0222(12) 0.0181(11) 0.0265(12) -0.0028(9) 0.0067(9) -0.0001(8) C9 0.0199(12) 0.0288(13) 0.0279(13) 0.0041(10) 0.0058(10) -0.0033(9) C10 0.0197(12) 0.0334(14) 0.0310(14) 0.0071(11) 0.0103(10) 0.0054(10) C11 0.0269(13) 0.0247(13) 0.0420(16) -0.0018(11) 0.0139(11) 0.0071(10) C12 0.0234(12) 0.0170(11) 0.0307(13) -0.0011(9) 0.0105(10) 0.0016(8) C13 0.0169(10) 0.0123(9) 0.0208(10) 0.0027(8) 0.0030(8) 0.0011(7) C14 0.0226(11) 0.0195(11) 0.0207(11) 0.0018(8) 0.0042(9) -0.0009(8) C15 0.0285(13) 0.0166(11) 0.0268(12) 0.0059(9) 0.0081(10) -0.0013(9) C16 0.0248(13) 0.0162(11) 0.0357(14) 0.0004(10) 0.0067(10) -0.0014(9) C17 0.0326(14) 0.0221(12) 0.0257(13) -0.0013(10) -0.0015(10) -0.0039(10) C18 0.0321(14) 0.0197(11) 0.0221(12) 0.0039(9) 0.0023(10) -0.0018(9) C19 0.0181(10) 0.0137(9) 0.0147(9) -0.0012(7) 0.0024(8) -0.0004(7) C20 0.0191(11) 0.0188(11) 0.0165(10) 0.0000(8) -0.0009(8) 0.0010(8) C21 0.0251(11) 0.0146(10) 0.0157(10) 0.0020(8) -0.0011(8) -0.0011(8) C22 0.0229(11) 0.0157(10) 0.0131(9) 0.0007(7) 0.0040(8) -0.0043(8) C23 0.0155(10) 0.0136(9) 0.0142(9) -0.0009(7) 0.0034(7) 0.0011(7) C24 0.0190(10) 0.0128(9) 0.0111(9) -0.0014(7) 0.0015(7) -0.0005(7) C25 0.0158(10) 0.0180(10) 0.0224(11) 0.0018(8) 0.0060(8) 0.0020(8) C26 0.0257(13) 0.0283(13) 0.0337(14) -0.0089(11) 0.0064(11) 0.0053(10) C27 0.0357(16) 0.0272(14) 0.0410(17) -0.0063(12) 0.0128(13) 0.0096(11) C28 0.0282(14) 0.0283(14) 0.0432(17) 0.0094(12) 0.0175(12) 0.0114(11) C29 0.0163(12) 0.0364(16) 0.064(2) -0.0013(14) 0.0067(13) 0.0037(11) C30 0.0177(12) 0.0239(13) 0.0465(17) -0.0047(11) 0.0057(11) 0.0015(9) C31 0.0133(9) 0.0171(10) 0.0150(9) -0.0013(7) 0.0027(7) -0.0005(7) C32 0.0249(12) 0.0205(11) 0.0168(10) -0.0015(8) 0.0063(9) -0.0027(8) C33 0.0308(13) 0.0164(11) 0.0236(12) -0.0027(9) 0.0107(10) -0.0038(9) C34 0.0270(12) 0.0193(11) 0.0233(12) -0.0077(9) 0.0080(9) -0.0039(9) C35 0.0309(13) 0.0247(12) 0.0156(10) -0.0048(9) 0.0068(9) -0.0013(9) C36 0.0252(12) 0.0187(11) 0.0155(10) -0.0003(8) 0.0043(8) -0.0013(8) C37 0.0212(11) 0.0227(11) 0.0134(10) 0.0036(8) 0.0036(8) 0.0069(8) C38 0.0257(12) 0.0283(13) 0.0163(11) -0.0003(9) 0.0047(9) 0.0101(9) C39 0.0327(16) 0.051(2) 0.050(2) -0.0275(16) -0.0008(14) 0.0103(14) C40 0.053(2) 0.071(3) 0.068(3) -0.046(2) 0.0052(19) 0.0211(19) C41 0.0388(18) 0.072(2) 0.0348(17) -0.0152(16) 0.0056(13) 0.0294(17) C42 0.0291(15) 0.056(2) 0.0345(16) -0.0009(14) 0.0139(12) 0.0144(13) C43 0.0305(15) 0.0334(15) 0.0340(15) 0.0000(11) 0.0129(12) 0.0068(11) C44 0.0157(10) 0.0232(11) 0.0150(10) 0.0000(8) 0.0041(8) 0.0004(8) C45 0.0195(11) 0.0220(11) 0.0163(10) -0.0004(8) 0.0071(8) 0.0004(8) C46 0.0312(13) 0.0193(11) 0.0245(12) -0.0022(9) 0.0140(10) -0.0030(9) C47 0.0405(16) 0.0270(13) 0.0286(14) -0.0022(10) 0.0182(12) 0.0029(11) C48 0.0285(14) 0.0446(17) 0.0246(13) 0.0011(11) 0.0168(11) 0.0031(11) C49 0.0272(14) 0.0472(17) 0.0289(14) -0.0048(12) 0.0148(11) -0.0128(12) C50 0.0261(13) 0.0368(15) 0.0253(13) -0.0090(11) 0.0105(10) -0.0126(11) C51 0.0344(15) 0.0344(15) 0.0320(15) -0.0040(12) 0.0094(12) 0.0032(11) C52 0.0271(14) 0.0325(14) 0.0295(14) -0.0012(11) 0.0095(11) 0.0014(10) C53 0.0260(13) 0.0268(13) 0.0275(13) 0.0004(10) 0.0085(10) -0.0022(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.063(2) . ? Au1 O1 2.1116(15) . ? Au1 P1 2.3356(6) . ? Au1 Au2 2.52120(11) . ? Au2 C6 2.075(2) . ? Au2 O3 2.1002(15) . ? Au2 P2 2.3380(6) . ? P1 C7 1.804(2) . ? P1 C13 1.804(2) . ? P1 C1 1.814(2) . ? P2 C25 1.804(2) . ? P2 C31 1.811(2) . ? P2 C19 1.816(2) . ? F1 C2 1.349(3) . ? F2 C3 1.338(3) . ? F3 C4 1.336(3) . ? F4 C5 1.344(3) . ? F5 C20 1.337(3) . ? F6 C21 1.335(2) . ? F7 C22 1.348(2) . ? F8 C23 1.354(2) . ? O1 C37 1.300(3) . ? O2 C37 1.236(3) . ? O3 C44 1.289(3) . ? O4 C44 1.236(3) . ? C1 C2 1.384(3) . ? C1 C6 1.414(3) . ? C2 C3 1.388(3) . ? C3 C4 1.371(3) . ? C4 C5 1.393(3) . ? C5 C6 1.375(3) . ? C7 C12 1.383(3) . ? C7 C8 1.398(3) . ? C8 C9 1.373(3) . ? C8 H8 0.9500 . ? C9 C10 1.390(4) . ? C9 H9 0.9500 . ? C10 C11 1.378(4) . ? C10 H10 0.9500 . ? C11 C12 1.390(3) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.390(3) . ? C13 C14 1.406(3) . ? C14 C15 1.390(3) . ? C14 H14 0.9500 . ? C15 C16 1.386(4) . ? C15 H15 0.9500 . ? C16 C17 1.380(4) . ? C16 H16 0.9500 . ? C17 C18 1.398(3) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.392(3) . ? C19 C24 1.412(3) . ? C20 C21 1.389(3) . ? C21 C22 1.379(3) . ? C22 C23 1.387(3) . ? C23 C24 1.375(3) . ? C25 C30 1.385(3) . ? C25 C26 1.396(3) . ? C26 C27 1.385(4) . ? C26 H26 0.9500 . ? C27 C28 1.377(4) . ? C27 H27 0.9500 . ? C28 C29 1.384(4) . ? C28 H28 0.9500 . ? C29 C30 1.393(4) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.392(3) . ? C31 C36 1.393(3) . ? C32 C33 1.393(3) . ? C32 H32 0.9500 . ? C33 C34 1.385(3) . ? C33 H33 0.9500 . ? C34 C35 1.383(3) . ? C34 H34 0.9500 . ? C35 C36 1.394(3) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C37 C38 1.504(3) . ? C38 C43 1.372(4) . ? C38 C39 1.382(4) . ? C39 C40 1.397(4) . ? C39 H39 0.9500 . ? C40 C41 1.371(5) . ? C40 H40 0.9500 . ? C41 C42 1.366(5) . ? C41 H41 0.9500 . ? C42 C43 1.398(4) . ? C42 H42 0.9500 . ? C43 H43 0.9500 . ? C44 C45 1.511(3) . ? C45 C50 1.390(3) . ? C45 C46 1.392(3) . ? C46 C47 1.387(3) . ? C46 H46 0.9500 . ? C47 C48 1.384(4) . ? C47 H47 0.9500 . ? C48 C49 1.388(4) . ? C48 H48 0.9500 . ? C49 C50 1.391(4) . ? C49 H49 0.9500 . ? C50 H50 0.9500 . ? C51 C52 1.515(4) . ? C51 H51A 0.9800 . ? C51 H51B 0.9800 . ? C51 H51C 0.9800 . ? C52 C53 1.524(4) . ? C52 H52A 0.9900 . ? C52 H52B 0.9900 . ? C53 C53 1.530(5) 3_567 ? C53 H53A 0.9900 . ? C53 H53B 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 O1 94.46(7) . . ? C24 Au1 P1 173.81(6) . . ? O1 Au1 P1 91.48(5) . . ? C24 Au1 Au2 89.20(6) . . ? O1 Au1 Au2 175.93(4) . . ? P1 Au1 Au2 84.815(14) . . ? C6 Au2 O3 90.93(8) . . ? C6 Au2 P2 171.00(6) . . ? O3 Au2 P2 98.05(5) . . ? C6 Au2 Au1 88.61(6) . . ? O3 Au2 Au1 178.31(5) . . ? P2 Au2 Au1 82.433(14) . . ? C7 P1 C13 106.15(10) . . ? C7 P1 C1 108.26(10) . . ? C13 P1 C1 110.21(10) . . ? C7 P1 Au1 110.33(7) . . ? C13 P1 Au1 118.21(7) . . ? C1 P1 Au1 103.40(7) . . ? C25 P2 C31 108.15(10) . . ? C25 P2 C19 108.99(10) . . ? C31 P2 C19 106.87(10) . . ? C25 P2 Au2 115.79(8) . . ? C31 P2 Au2 113.25(7) . . ? C19 P2 Au2 103.28(7) . . ? C37 O1 Au1 109.76(14) . . ? C44 O3 Au2 114.19(14) . . ? C2 C1 C6 120.3(2) . . ? C2 C1 P1 123.86(17) . . ? C6 C1 P1 115.52(16) . . ? F1 C2 C1 121.4(2) . . ? F1 C2 C3 117.7(2) . . ? C1 C2 C3 120.8(2) . . ? F2 C3 C4 120.0(2) . . ? F2 C3 C2 120.8(2) . . ? C4 C3 C2 119.2(2) . . ? F3 C4 C3 119.7(2) . . ? F3 C4 C5 120.2(2) . . ? C3 C4 C5 120.1(2) . . ? F4 C5 C6 122.2(2) . . ? F4 C5 C4 115.7(2) . . ? C6 C5 C4 122.1(2) . . ? C5 C6 C1 117.4(2) . . ? C5 C6 Au2 121.95(16) . . ? C1 C6 Au2 120.63(16) . . ? C12 C7 C8 119.6(2) . . ? C12 C7 P1 121.22(18) . . ? C8 C7 P1 119.02(17) . . ? C9 C8 C7 120.3(2) . . ? C9 C8 H8 119.8 . . ? C7 C8 H8 119.8 . . ? C8 C9 C10 119.9(2) . . ? C8 C9 H9 120.1 . . ? C10 C9 H9 120.1 . . ? C11 C10 C9 120.2(2) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C10 C11 C12 120.1(2) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C7 C12 C11 120.0(2) . . ? C7 C12 H12 120.0 . . ? C11 C12 H12 120.0 . . ? C18 C13 C14 120.0(2) . . ? C18 C13 P1 119.31(17) . . ? C14 C13 P1 120.42(18) . . ? C15 C14 C13 119.5(2) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C16 C15 C14 120.2(2) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C17 C16 C15 120.4(2) . . ? C17 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? C16 C17 C18 120.3(2) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C13 C18 C17 119.5(2) . . ? C13 C18 H18 120.2 . . ? C17 C18 H18 120.2 . . ? C20 C19 C24 120.5(2) . . ? C20 C19 P2 124.97(17) . . ? C24 C19 P2 114.50(16) . . ? F5 C20 C21 117.4(2) . . ? F5 C20 C19 122.0(2) . . ? C21 C20 C19 120.5(2) . . ? F6 C21 C22 120.5(2) . . ? F6 C21 C20 120.6(2) . . ? C22 C21 C20 118.9(2) . . ? F7 C22 C21 119.04(19) . . ? F7 C22 C23 120.6(2) . . ? C21 C22 C23 120.4(2) . . ? F8 C23 C24 121.60(19) . . ? F8 C23 C22 116.28(19) . . ? C24 C23 C22 122.1(2) . . ? C23 C24 C19 117.37(19) . . ? C23 C24 Au1 122.73(16) . . ? C19 C24 Au1 119.66(15) . . ? C30 C25 C26 120.1(2) . . ? C30 C25 P2 122.14(19) . . ? C26 C25 P2 117.73(18) . . ? C27 C26 C25 119.8(3) . . ? C27 C26 H26 120.1 . . ? C25 C26 H26 120.1 . . ? C28 C27 C26 120.0(3) . . ? C28 C27 H27 120.0 . . ? C26 C27 H27 120.0 . . ? C27 C28 C29 120.4(2) . . ? C27 C28 H28 119.8 . . ? C29 C28 H28 119.8 . . ? C28 C29 C30 120.1(3) . . ? C28 C29 H29 120.0 . . ? C30 C29 H29 120.0 . . ? C25 C30 C29 119.5(3) . . ? C25 C30 H30 120.2 . . ? C29 C30 H30 120.2 . . ? C32 C31 C36 120.8(2) . . ? C32 C31 P2 117.96(17) . . ? C36 C31 P2 121.19(17) . . ? C31 C32 C33 119.4(2) . . ? C31 C32 H32 120.3 . . ? C33 C32 H32 120.3 . . ? C34 C33 C32 119.9(2) . . ? C34 C33 H33 120.0 . . ? C32 C33 H33 120.0 . . ? C35 C34 C33 120.5(2) . . ? C35 C34 H34 119.7 . . ? C33 C34 H34 119.7 . . ? C34 C35 C36 120.3(2) . . ? C34 C35 H35 119.8 . . ? C36 C35 H35 119.8 . . ? C31 C36 C35 119.0(2) . . ? C31 C36 H36 120.5 . . ? C35 C36 H36 120.5 . . ? O2 C37 O1 123.5(2) . . ? O2 C37 C38 121.0(2) . . ? O1 C37 C38 115.4(2) . . ? C43 C38 C39 119.7(2) . . ? C43 C38 C37 121.9(2) . . ? C39 C38 C37 118.4(3) . . ? C38 C39 C40 119.6(3) . . ? C38 C39 H39 120.2 . . ? C40 C39 H39 120.2 . . ? C41 C40 C39 120.4(3) . . ? C41 C40 H40 119.8 . . ? C39 C40 H40 119.8 . . ? C42 C41 C40 120.1(3) . . ? C42 C41 H41 120.0 . . ? C40 C41 H41 120.0 . . ? C41 C42 C43 119.9(3) . . ? C41 C42 H42 120.0 . . ? C43 C42 H42 120.0 . . ? C38 C43 C42 120.4(3) . . ? C38 C43 H43 119.8 . . ? C42 C43 H43 119.8 . . ? O4 C44 O3 124.9(2) . . ? O4 C44 C45 120.6(2) . . ? O3 C44 C45 114.5(2) . . ? C50 C45 C46 119.5(2) . . ? C50 C45 C44 119.1(2) . . ? C46 C45 C44 121.4(2) . . ? C47 C46 C45 120.1(2) . . ? C47 C46 H46 120.0 . . ? C45 C46 H46 120.0 . . ? C48 C47 C46 120.6(3) . . ? C48 C47 H47 119.7 . . ? C46 C47 H47 119.7 . . ? C47 C48 C49 119.5(2) . . ? C47 C48 H48 120.3 . . ? C49 C48 H48 120.3 . . ? C48 C49 C50 120.3(3) . . ? C48 C49 H49 119.8 . . ? C50 C49 H49 119.8 . . ? C45 C50 C49 120.0(2) . . ? C45 C50 H50 120.0 . . ? C49 C50 H50 120.0 . . ? C52 C51 H51A 109.5 . . ? C52 C51 H51B 109.5 . . ? H51A C51 H51B 109.5 . . ? C52 C51 H51C 109.5 . . ? H51A C51 H51C 109.5 . . ? H51B C51 H51C 109.5 . . ? C51 C52 C53 113.6(2) . . ? C51 C52 H52A 108.8 . . ? C53 C52 H52A 108.8 . . ? C51 C52 H52B 108.8 . . ? C53 C52 H52B 108.8 . . ? H52A C52 H52B 107.7 . . ? C52 C53 C53 112.4(3) . 3_567 ? C52 C53 H53A 109.1 . . ? C53 C53 H53A 109.1 3_567 . ? C52 C53 H53B 109.1 . . ? C53 C53 H53B 109.1 3_567 . ? H53A C53 H53B 107.9 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -137.76(8) . . . . ? P1 Au1 Au2 C6 40.67(6) . . . . ? C24 Au1 Au2 P2 43.13(6) . . . . ? P1 Au1 Au2 P2 -138.44(2) . . . . ? O1 Au1 P1 C7 20.10(9) . . . . ? Au2 Au1 P1 C7 -158.23(8) . . . . ? O1 Au1 P1 C13 -102.27(10) . . . . ? Au2 Au1 P1 C13 79.40(9) . . . . ? O1 Au1 P1 C1 135.68(9) . . . . ? Au2 Au1 P1 C1 -42.65(7) . . . . ? O3 Au2 P2 C25 13.09(10) . . . . ? Au1 Au2 P2 C25 -165.27(9) . . . . ? O3 Au2 P2 C31 -112.66(9) . . . . ? Au1 Au2 P2 C31 68.98(8) . . . . ? O3 Au2 P2 C19 132.13(8) . . . . ? Au1 Au2 P2 C19 -46.24(7) . . . . ? C24 Au1 O1 C37 -103.75(15) . . . . ? P1 Au1 O1 C37 77.99(14) . . . . ? C6 Au2 O3 C44 -103.26(16) . . . . ? P2 Au2 O3 C44 76.11(16) . . . . ? C7 P1 C1 C2 -30.1(2) . . . . ? C13 P1 C1 C2 85.6(2) . . . . ? Au1 P1 C1 C2 -147.10(18) . . . . ? C7 P1 C1 C6 143.91(17) . . . . ? C13 P1 C1 C6 -100.39(18) . . . . ? Au1 P1 C1 C6 26.88(17) . . . . ? C6 C1 C2 F1 177.1(2) . . . . ? P1 C1 C2 F1 -9.2(3) . . . . ? C6 C1 C2 C3 -3.2(3) . . . . ? P1 C1 C2 C3 170.52(18) . . . . ? F1 C2 C3 F2 0.1(3) . . . . ? C1 C2 C3 F2 -179.6(2) . . . . ? F1 C2 C3 C4 179.9(2) . . . . ? C1 C2 C3 C4 0.2(4) . . . . ? F2 C3 C4 F3 0.9(3) . . . . ? C2 C3 C4 F3 -178.9(2) . . . . ? F2 C3 C4 C5 -178.4(2) . . . . ? C2 C3 C4 C5 1.8(4) . . . . ? F3 C4 C5 F4 0.4(3) . . . . ? C3 C4 C5 F4 179.6(2) . . . . ? F3 C4 C5 C6 179.8(2) . . . . ? C3 C4 C5 C6 -0.9(4) . . . . ? F4 C5 C6 C1 177.40(19) . . . . ? C4 C5 C6 C1 -2.0(3) . . . . ? F4 C5 C6 Au2 -5.7(3) . . . . ? C4 C5 C6 Au2 174.90(17) . . . . ? C2 C1 C6 C5 4.0(3) . . . . ? P1 C1 C6 C5 -170.19(17) . . . . ? C2 C1 C6 Au2 -172.94(17) . . . . ? P1 C1 C6 Au2 12.9(2) . . . . ? O3 Au2 C6 C5 -36.64(18) . . . . ? Au1 Au2 C6 C5 141.74(18) . . . . ? O3 Au2 C6 C1 140.18(17) . . . . ? Au1 Au2 C6 C1 -41.45(17) . . . . ? C13 P1 C7 C12 7.2(2) . . . . ? C1 P1 C7 C12 125.5(2) . . . . ? Au1 P1 C7 C12 -122.04(19) . . . . ? C13 P1 C7 C8 -177.49(19) . . . . ? C1 P1 C7 C8 -59.2(2) . . . . ? Au1 P1 C7 C8 53.3(2) . . . . ? C12 C7 C8 C9 -1.8(4) . . . . ? P1 C7 C8 C9 -177.2(2) . . . . ? C7 C8 C9 C10 2.3(4) . . . . ? C8 C9 C10 C11 -2.0(4) . . . . ? C9 C10 C11 C12 1.3(4) . . . . ? C8 C7 C12 C11 1.1(4) . . . . ? P1 C7 C12 C11 176.4(2) . . . . ? C10 C11 C12 C7 -0.9(4) . . . . ? C7 P1 C13 C18 -90.9(2) . . . . ? C1 P1 C13 C18 152.07(19) . . . . ? Au1 P1 C13 C18 33.5(2) . . . . ? C7 P1 C13 C14 83.7(2) . . . . ? C1 P1 C13 C14 -33.3(2) . . . . ? Au1 P1 C13 C14 -151.86(16) . . . . ? C18 C13 C14 C15 0.2(4) . . . . ? P1 C13 C14 C15 -174.36(19) . . . . ? C13 C14 C15 C16 0.3(4) . . . . ? C14 C15 C16 C17 -0.2(4) . . . . ? C15 C16 C17 C18 -0.3(4) . . . . ? C14 C13 C18 C17 -0.7(4) . . . . ? P1 C13 C18 C17 173.9(2) . . . . ? C16 C17 C18 C13 0.8(4) . . . . ? C25 P2 C19 C20 -24.2(2) . . . . ? C31 P2 C19 C20 92.5(2) . . . . ? Au2 P2 C19 C20 -147.82(18) . . . . ? C25 P2 C19 C24 154.85(16) . . . . ? C31 P2 C19 C24 -88.49(17) . . . . ? Au2 P2 C19 C24 31.21(17) . . . . ? C24 C19 C20 F5 178.3(2) . . . . ? P2 C19 C20 F5 -2.7(3) . . . . ? C24 C19 C20 C21 -1.9(3) . . . . ? P2 C19 C20 C21 177.04(17) . . . . ? F5 C20 C21 F6 -2.1(3) . . . . ? C19 C20 C21 F6 178.2(2) . . . . ? F5 C20 C21 C22 177.9(2) . . . . ? C19 C20 C21 C22 -1.8(3) . . . . ? F6 C21 C22 F7 1.9(3) . . . . ? C20 C21 C22 F7 -178.1(2) . . . . ? F6 C21 C22 C23 -176.6(2) . . . . ? C20 C21 C22 C23 3.3(3) . . . . ? F7 C22 C23 F8 0.8(3) . . . . ? C21 C22 C23 F8 179.29(19) . . . . ? F7 C22 C23 C24 -179.63(19) . . . . ? C21 C22 C23 C24 -1.1(3) . . . . ? F8 C23 C24 C19 176.99(18) . . . . ? C22 C23 C24 C19 -2.6(3) . . . . ? F8 C23 C24 Au1 -8.7(3) . . . . ? C22 C23 C24 Au1 171.75(16) . . . . ? C20 C19 C24 C23 4.1(3) . . . . ? P2 C19 C24 C23 -175.01(16) . . . . ? C20 C19 C24 Au1 -170.43(16) . . . . ? P2 C19 C24 Au1 10.5(2) . . . . ? O1 Au1 C24 C23 -34.70(18) . . . . ? Au2 Au1 C24 C23 143.52(17) . . . . ? O1 Au1 C24 C19 139.49(16) . . . . ? Au2 Au1 C24 C19 -42.29(16) . . . . ? C31 P2 C25 C30 -6.7(2) . . . . ? C19 P2 C25 C30 109.1(2) . . . . ? Au2 P2 C25 C30 -135.0(2) . . . . ? C31 P2 C25 C26 174.8(2) . . . . ? C19 P2 C25 C26 -69.4(2) . . . . ? Au2 P2 C25 C26 46.5(2) . . . . ? C30 C25 C26 C27 -1.1(4) . . . . ? P2 C25 C26 C27 177.4(2) . . . . ? C25 C26 C27 C28 1.3(4) . . . . ? C26 C27 C28 C29 -0.7(5) . . . . ? C27 C28 C29 C30 -0.1(5) . . . . ? C26 C25 C30 C29 0.3(4) . . . . ? P2 C25 C30 C29 -178.2(2) . . . . ? C28 C29 C30 C25 0.3(5) . . . . ? C25 P2 C31 C32 -83.1(2) . . . . ? C19 P2 C31 C32 159.74(18) . . . . ? Au2 P2 C31 C32 46.7(2) . . . . ? C25 P2 C31 C36 98.1(2) . . . . ? C19 P2 C31 C36 -19.1(2) . . . . ? Au2 P2 C31 C36 -132.16(17) . . . . ? C36 C31 C32 C33 -1.3(4) . . . . ? P2 C31 C32 C33 179.81(19) . . . . ? C31 C32 C33 C34 1.2(4) . . . . ? C32 C33 C34 C35 -0.3(4) . . . . ? C33 C34 C35 C36 -0.5(4) . . . . ? C32 C31 C36 C35 0.5(3) . . . . ? P2 C31 C36 C35 179.34(18) . . . . ? C34 C35 C36 C31 0.4(4) . . . . ? Au1 O1 C37 O2 17.6(3) . . . . ? Au1 O1 C37 C38 -160.47(16) . . . . ? O2 C37 C38 C43 173.7(2) . . . . ? O1 C37 C38 C43 -8.1(3) . . . . ? O2 C37 C38 C39 -9.6(4) . . . . ? O1 C37 C38 C39 168.5(2) . . . . ? C43 C38 C39 C40 -0.8(5) . . . . ? C37 C38 C39 C40 -177.5(3) . . . . ? C38 C39 C40 C41 -0.3(6) . . . . ? C39 C40 C41 C42 0.9(6) . . . . ? C40 C41 C42 C43 -0.4(5) . . . . ? C39 C38 C43 C42 1.2(4) . . . . ? C37 C38 C43 C42 177.9(3) . . . . ? C41 C42 C43 C38 -0.6(5) . . . . ? Au2 O3 C44 O4 -6.0(3) . . . . ? Au2 O3 C44 C45 173.00(14) . . . . ? O4 C44 C45 C50 -1.7(4) . . . . ? O3 C44 C45 C50 179.3(2) . . . . ? O4 C44 C45 C46 176.0(2) . . . . ? O3 C44 C45 C46 -3.0(3) . . . . ? C50 C45 C46 C47 -0.7(4) . . . . ? C44 C45 C46 C47 -178.4(2) . . . . ? C45 C46 C47 C48 0.0(4) . . . . ? C46 C47 C48 C49 0.4(5) . . . . ? C47 C48 C49 C50 -0.1(5) . . . . ? C46 C45 C50 C49 0.9(4) . . . . ? C44 C45 C50 C49 178.7(2) . . . . ? C48 C49 C50 C45 -0.5(5) . . . . ? C51 C52 C53 C53 178.3(3) . . . 3_567 ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 36.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.125 _refine_diff_density_min -2.019 _refine_diff_density_rms 0.172 # Attachment 'neda01001.cif.txt' data_neda01001 _database_code_depnum_ccdc_archive 'CCDC 725996' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 Cl4 F8 P2, C H2 Cl2' _chemical_formula_sum 'C37 H22 Au2 Cl6 F8 P2' _chemical_formula_weight 1287.12 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.7369(2) _cell_length_b 14.4038(2) _cell_length_c 14.5209(2) _cell_angle_alpha 60.9030(10) _cell_angle_beta 82.7430(10) _cell_angle_gamma 88.0100(10) _cell_volume 1945.64(6) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 99774 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 45.294 _exptl_crystal_description piece _exptl_crystal_colour yellow _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.197 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1212 _exptl_absorpt_coefficient_mu 8.094 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.179 _exptl_absorpt_correction_T_max 0.377 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 80292 _diffrn_reflns_av_R_equivalents 0.0631 _diffrn_reflns_av_sigmaI/netI 0.0412 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 38.00 _reflns_number_total 21176 _reflns_number_gt 18335 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0469P)^2^+2.8162P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 21176 _refine_ls_number_parameters 496 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0419 _refine_ls_R_factor_gt 0.0338 _refine_ls_wR_factor_ref 0.0868 _refine_ls_wR_factor_gt 0.0838 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.020 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.706302(8) 0.072265(6) 0.285977(6) 0.01097(2) Uani 1 1 d . . . Au2 Au 0.802458(8) -0.255239(7) 0.170384(7) 0.01412(2) Uani 1 1 d . . . P1 P 0.72581(6) 0.25743(5) 0.20069(5) 0.01194(9) Uani 1 1 d . . . P2 P 0.67161(6) -0.15705(5) 0.22792(5) 0.01205(9) Uani 1 1 d . . . Cl1 Cl 0.48894(6) 0.05101(5) 0.33187(6) 0.01922(10) Uani 1 1 d . . . Cl2 Cl 0.92640(7) -0.35056(6) 0.10342(6) 0.02349(12) Uani 1 1 d . . . Cl3 Cl 0.68779(7) -0.19163(6) 0.03043(5) 0.02312(12) Uani 1 1 d . . . Cl4 Cl 0.92423(7) -0.30591(7) 0.30393(6) 0.02575(13) Uani 1 1 d . . . F1 F 1.00451(17) 0.39930(13) 0.10916(14) 0.0195(3) Uani 1 1 d . . . F2 F 1.22412(16) 0.29562(14) 0.13424(14) 0.0203(3) Uani 1 1 d . . . F3 F 1.22396(16) 0.08163(15) 0.22967(15) 0.0224(3) Uani 1 1 d . . . F4 F 1.00828(16) -0.03539(13) 0.29752(14) 0.0198(3) Uani 1 1 d . . . F5 F 0.65488(17) -0.35877(12) 0.42278(14) 0.0189(3) Uani 1 1 d . . . F6 F 0.67749(19) -0.40440(14) 0.62251(14) 0.0241(3) Uani 1 1 d . . . F7 F 0.7300(2) -0.24711(15) 0.66495(13) 0.0237(3) Uani 1 1 d . . . F8 F 0.75913(18) -0.04484(14) 0.50819(13) 0.0199(3) Uani 1 1 d . . . C1 C 0.8912(2) 0.23378(18) 0.19070(18) 0.0128(3) Uani 1 1 d . . . C2 C 1.0026(2) 0.29311(19) 0.15574(19) 0.0144(4) Uani 1 1 d . . . C3 C 1.1155(2) 0.2412(2) 0.1685(2) 0.0159(4) Uani 1 1 d . . . C4 C 1.1152(2) 0.1303(2) 0.2176(2) 0.0165(4) Uani 1 1 d . . . C5 C 1.0026(2) 0.07100(19) 0.25338(19) 0.0147(4) Uani 1 1 d . . . C6 C 0.8893(2) 0.12174(18) 0.24106(18) 0.0126(3) Uani 1 1 d . . . C7 C 0.6704(2) 0.34025(18) 0.07530(18) 0.0133(3) Uani 1 1 d . . . C8 C 0.7509(3) 0.4101(2) -0.0145(2) 0.0175(4) Uani 1 1 d . . . H8 H 0.8378 0.4151 -0.0102 0.021 Uiso 1 1 calc R . . C9 C 0.7026(3) 0.4723(2) -0.1104(2) 0.0207(5) Uani 1 1 d . . . H9 H 0.7564 0.5203 -0.1716 0.025 Uiso 1 1 calc R . . C10 C 0.5756(3) 0.4640(2) -0.1162(2) 0.0203(5) Uani 1 1 d . . . H10 H 0.5433 0.5062 -0.1818 0.024 Uiso 1 1 calc R . . C11 C 0.4950(3) 0.3946(2) -0.0274(2) 0.0191(4) Uani 1 1 d . . . H11 H 0.4083 0.3900 -0.0325 0.023 Uiso 1 1 calc R . . C12 C 0.5417(3) 0.3318(2) 0.0690(2) 0.0173(4) Uani 1 1 d . . . H12 H 0.4874 0.2837 0.1298 0.021 Uiso 1 1 calc R . . C13 C 0.6858(2) 0.31158(19) 0.28873(18) 0.0138(4) Uani 1 1 d . . . C14 C 0.6323(2) 0.2448(2) 0.3934(2) 0.0174(4) Uani 1 1 d . . . H14 H 0.6116 0.1726 0.4162 0.021 Uiso 1 1 calc R . . C15 C 0.6100(3) 0.2846(2) 0.4635(2) 0.0211(5) Uani 1 1 d . . . H15 H 0.5740 0.2396 0.5346 0.025 Uiso 1 1 calc R . . C16 C 0.6397(3) 0.3893(3) 0.4304(3) 0.0247(5) Uani 1 1 d . . . H16 H 0.6229 0.4161 0.4788 0.030 Uiso 1 1 calc R . . C17 C 0.6943(3) 0.4567(3) 0.3264(3) 0.0246(5) Uani 1 1 d . . . H17 H 0.7160 0.5284 0.3047 0.029 Uiso 1 1 calc R . . C18 C 0.7166(3) 0.4178(2) 0.2548(2) 0.0173(4) Uani 1 1 d . . . H18 H 0.7524 0.4631 0.1837 0.021 Uiso 1 1 calc R . . C19 C 0.6962(2) -0.17430(18) 0.35706(18) 0.0129(3) Uani 1 1 d . . . C20 C 0.6836(2) -0.27871(19) 0.44031(19) 0.0148(4) Uani 1 1 d . . . C21 C 0.6949(3) -0.3039(2) 0.54348(19) 0.0171(4) Uani 1 1 d . . . C22 C 0.7211(3) -0.2236(2) 0.56481(19) 0.0172(4) Uani 1 1 d . . . C23 C 0.7343(2) -0.11999(19) 0.48254(19) 0.0149(4) Uani 1 1 d . . . C24 C 0.7205(2) -0.09110(18) 0.37813(18) 0.0125(3) Uani 1 1 d . . . C25 C 0.7130(2) -0.02285(19) 0.12765(18) 0.0140(4) Uani 1 1 d . . . C26 C 0.8421(3) 0.0033(2) 0.1039(2) 0.0173(4) Uani 1 1 d . . . H26 H 0.9003 -0.0473 0.1434 0.021 Uiso 1 1 calc R . . C27 C 0.8846(3) 0.1032(2) 0.0226(2) 0.0202(5) Uani 1 1 d . . . H27 H 0.9719 0.1212 0.0067 0.024 Uiso 1 1 calc R . . C28 C 0.7991(3) 0.1769(2) -0.0354(2) 0.0212(5) Uani 1 1 d . . . H28 H 0.8280 0.2455 -0.0904 0.025 Uiso 1 1 calc R . . C29 C 0.6713(3) 0.1502(2) -0.0129(2) 0.0211(5) Uani 1 1 d . . . H29 H 0.6136 0.2006 -0.0534 0.025 Uiso 1 1 calc R . . C30 C 0.6270(3) 0.0504(2) 0.0685(2) 0.0181(4) Uani 1 1 d . . . H30 H 0.5398 0.0323 0.0835 0.022 Uiso 1 1 calc R . . C31 C 0.5093(2) -0.19568(19) 0.24232(18) 0.0137(3) Uani 1 1 d . . . C32 C 0.4132(2) -0.1306(2) 0.2508(2) 0.0171(4) Uani 1 1 d . . . H32 H 0.4332 -0.0626 0.2415 0.021 Uiso 1 1 calc R . . C33 C 0.2886(3) -0.1663(2) 0.2728(2) 0.0211(5) Uani 1 1 d . . . H33 H 0.2232 -0.1217 0.2766 0.025 Uiso 1 1 calc R . . C34 C 0.2592(3) -0.2668(2) 0.2891(2) 0.0209(5) Uani 1 1 d . . . H34 H 0.1741 -0.2912 0.3054 0.025 Uiso 1 1 calc R . . C35 C 0.3543(3) -0.3317(2) 0.2816(2) 0.0195(4) Uani 1 1 d . . . H35 H 0.3339 -0.4005 0.2931 0.023 Uiso 1 1 calc R . . C36 C 0.4787(2) -0.2965(2) 0.2576(2) 0.0169(4) Uani 1 1 d . . . H36 H 0.5433 -0.3406 0.2514 0.020 Uiso 1 1 calc R . . Cl5 Cl 0.04677(10) 0.84024(9) 0.54750(8) 0.03798(19) Uani 1 1 d . . . Cl6 Cl -0.01257(11) 0.61628(10) 0.62744(12) 0.0537(3) Uani 1 1 d . . . C37 C 0.0449(4) 0.7371(3) 0.5157(3) 0.0337(7) Uani 1 1 d . . . H37A H 0.1311 0.7276 0.4887 0.040 Uiso 1 1 calc R . . H37B H -0.0088 0.7566 0.4587 0.040 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01132(4) 0.00882(3) 0.01185(3) -0.00442(3) -0.00084(2) 0.00001(2) Au2 0.01418(4) 0.01265(4) 0.01610(4) -0.00814(3) 0.00181(3) -0.00217(3) P1 0.0131(2) 0.0093(2) 0.0122(2) -0.00447(18) -0.00081(17) 0.00034(17) P2 0.0130(2) 0.0105(2) 0.0119(2) -0.00488(18) -0.00051(17) -0.00120(17) Cl1 0.0126(2) 0.0185(2) 0.0276(3) -0.0126(2) 0.00001(19) -0.00036(18) Cl2 0.0243(3) 0.0198(3) 0.0279(3) -0.0151(2) 0.0076(2) -0.0020(2) Cl3 0.0278(3) 0.0271(3) 0.0177(2) -0.0134(2) -0.0031(2) 0.0013(2) Cl4 0.0177(3) 0.0346(4) 0.0319(3) -0.0209(3) -0.0083(2) 0.0084(2) F1 0.0214(7) 0.0117(6) 0.0237(8) -0.0076(6) -0.0008(6) -0.0025(5) F2 0.0138(7) 0.0227(8) 0.0227(7) -0.0101(6) 0.0009(5) -0.0058(6) F3 0.0136(7) 0.0220(8) 0.0282(8) -0.0096(7) -0.0038(6) 0.0041(6) F4 0.0177(7) 0.0114(6) 0.0265(8) -0.0063(6) -0.0037(6) 0.0042(5) F5 0.0250(8) 0.0093(6) 0.0210(7) -0.0057(5) -0.0047(6) -0.0023(5) F6 0.0350(10) 0.0123(7) 0.0152(7) 0.0014(5) -0.0044(6) -0.0023(6) F7 0.0347(10) 0.0225(8) 0.0112(6) -0.0056(6) -0.0045(6) 0.0010(7) F8 0.0286(8) 0.0170(7) 0.0168(7) -0.0103(6) -0.0033(6) 0.0001(6) C1 0.0141(9) 0.0091(8) 0.0145(8) -0.0055(7) 0.0000(7) -0.0005(6) C2 0.0157(9) 0.0123(8) 0.0145(9) -0.0062(7) -0.0001(7) -0.0015(7) C3 0.0137(9) 0.0171(10) 0.0161(9) -0.0077(8) -0.0004(7) -0.0024(7) C4 0.0133(9) 0.0183(10) 0.0173(10) -0.0082(8) -0.0021(7) 0.0017(7) C5 0.0146(9) 0.0129(9) 0.0153(9) -0.0059(7) -0.0020(7) 0.0028(7) C6 0.0117(8) 0.0126(8) 0.0133(8) -0.0063(7) -0.0008(6) 0.0010(6) C7 0.0169(9) 0.0104(8) 0.0128(8) -0.0057(7) -0.0022(7) 0.0017(7) C8 0.0185(10) 0.0154(10) 0.0150(9) -0.0046(8) -0.0010(7) -0.0015(8) C9 0.0243(12) 0.0183(11) 0.0143(9) -0.0041(8) -0.0012(8) -0.0008(9) C10 0.0255(12) 0.0185(11) 0.0166(10) -0.0076(9) -0.0068(9) 0.0045(9) C11 0.0195(11) 0.0193(11) 0.0200(10) -0.0101(9) -0.0063(8) 0.0034(8) C12 0.0182(10) 0.0155(9) 0.0159(9) -0.0057(8) -0.0028(7) 0.0005(8) C13 0.0142(9) 0.0141(9) 0.0136(8) -0.0074(7) -0.0013(7) 0.0024(7) C14 0.0184(10) 0.0171(10) 0.0146(9) -0.0068(8) 0.0017(7) -0.0010(8) C15 0.0205(11) 0.0269(13) 0.0157(10) -0.0109(9) 0.0003(8) 0.0024(9) C16 0.0191(12) 0.0361(16) 0.0255(13) -0.0214(12) 0.0023(9) 0.0031(10) C17 0.0276(13) 0.0214(12) 0.0304(14) -0.0171(11) -0.0027(11) -0.0018(10) C18 0.0214(11) 0.0134(9) 0.0175(10) -0.0081(8) -0.0007(8) 0.0008(8) C19 0.0149(9) 0.0094(8) 0.0126(8) -0.0040(7) -0.0014(6) -0.0001(6) C20 0.0169(10) 0.0110(8) 0.0147(9) -0.0046(7) -0.0028(7) -0.0005(7) C21 0.0209(11) 0.0117(9) 0.0131(9) -0.0016(7) -0.0022(7) -0.0014(7) C22 0.0211(11) 0.0167(10) 0.0109(8) -0.0041(7) -0.0032(7) 0.0010(8) C23 0.0176(10) 0.0123(9) 0.0146(9) -0.0063(7) -0.0022(7) 0.0004(7) C24 0.0130(8) 0.0099(8) 0.0135(8) -0.0049(7) -0.0010(6) 0.0000(6) C25 0.0164(9) 0.0117(8) 0.0120(8) -0.0046(7) -0.0001(7) -0.0017(7) C26 0.0190(10) 0.0140(9) 0.0165(9) -0.0060(8) 0.0006(8) -0.0043(8) C27 0.0223(11) 0.0177(10) 0.0170(10) -0.0064(8) 0.0024(8) -0.0063(9) C28 0.0319(14) 0.0138(10) 0.0154(10) -0.0058(8) 0.0016(9) -0.0058(9) C29 0.0302(13) 0.0129(9) 0.0146(10) -0.0025(8) -0.0028(9) 0.0016(9) C30 0.0206(11) 0.0157(10) 0.0155(9) -0.0058(8) -0.0016(8) -0.0002(8) C31 0.0136(9) 0.0127(8) 0.0137(8) -0.0058(7) -0.0003(7) -0.0013(7) C32 0.0176(10) 0.0159(10) 0.0179(10) -0.0087(8) 0.0005(8) -0.0008(8) C33 0.0155(10) 0.0232(12) 0.0243(12) -0.0120(10) 0.0002(8) 0.0013(8) C34 0.0147(10) 0.0251(12) 0.0217(11) -0.0106(10) 0.0003(8) -0.0045(9) C35 0.0195(11) 0.0170(10) 0.0202(11) -0.0076(9) -0.0014(8) -0.0047(8) C36 0.0178(10) 0.0136(9) 0.0186(10) -0.0072(8) -0.0012(8) -0.0036(7) Cl5 0.0380(4) 0.0509(5) 0.0340(4) -0.0258(4) -0.0132(3) 0.0055(4) Cl6 0.0335(5) 0.0426(6) 0.0647(8) -0.0094(5) -0.0109(5) 0.0055(4) C37 0.0280(16) 0.044(2) 0.0328(16) -0.0221(15) -0.0043(12) 0.0041(14) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.029(2) . ? Au1 C24 2.077(2) . ? Au1 Cl1 2.3329(6) . ? Au1 P1 2.3348(6) . ? Au2 Cl4 2.2804(7) . ? Au2 Cl3 2.2866(7) . ? Au2 P2 2.3209(6) . ? Au2 Cl2 2.3337(7) . ? P1 C7 1.790(2) . ? P1 C1 1.798(2) . ? P1 C13 1.799(2) . ? P2 C25 1.792(2) . ? P2 C31 1.803(2) . ? P2 C19 1.821(2) . ? F1 C2 1.338(3) . ? F2 C3 1.327(3) . ? F3 C4 1.327(3) . ? F4 C5 1.346(3) . ? F5 C20 1.349(3) . ? F6 C21 1.340(3) . ? F7 C22 1.339(3) . ? F8 C23 1.349(3) . ? C1 C2 1.384(3) . ? C1 C6 1.411(3) . ? C2 C3 1.386(4) . ? C3 C4 1.397(4) . ? C4 C5 1.394(4) . ? C5 C6 1.382(3) . ? C7 C8 1.400(4) . ? C7 C12 1.409(4) . ? C8 C9 1.396(4) . ? C8 H8 0.9500 . ? C9 C10 1.390(4) . ? C9 H9 0.9500 . ? C10 C11 1.391(4) . ? C10 H10 0.9500 . ? C11 C12 1.394(4) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.398(4) . ? C13 C14 1.400(3) . ? C14 C15 1.385(4) . ? C14 H14 0.9500 . ? C15 C16 1.377(5) . ? C15 H15 0.9500 . ? C16 C17 1.399(5) . ? C16 H16 0.9500 . ? C17 C18 1.394(4) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.395(3) . ? C19 C24 1.413(3) . ? C20 C21 1.380(4) . ? C21 C22 1.380(4) . ? C22 C23 1.383(4) . ? C23 C24 1.390(3) . ? C25 C30 1.398(4) . ? C25 C26 1.404(4) . ? C26 C27 1.389(4) . ? C26 H26 0.9500 . ? C27 C28 1.392(4) . ? C27 H27 0.9500 . ? C28 C29 1.392(4) . ? C28 H28 0.9500 . ? C29 C30 1.394(4) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.403(3) . ? C31 C32 1.404(4) . ? C32 C33 1.392(4) . ? C32 H32 0.9500 . ? C33 C34 1.390(4) . ? C33 H33 0.9500 . ? C34 C35 1.389(4) . ? C34 H34 0.9500 . ? C35 C36 1.387(4) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? Cl5 C37 1.759(4) . ? Cl6 C37 1.765(4) . ? C37 H37A 0.9900 . ? C37 H37B 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 C24 102.01(9) . . ? C6 Au1 Cl1 168.12(7) . . ? C24 Au1 Cl1 88.80(7) . . ? C6 Au1 P1 68.87(7) . . ? C24 Au1 P1 167.75(7) . . ? Cl1 Au1 P1 99.70(2) . . ? Cl4 Au2 Cl3 175.55(3) . . ? Cl4 Au2 P2 93.44(2) . . ? Cl3 Au2 P2 85.38(2) . . ? Cl4 Au2 Cl2 90.26(3) . . ? Cl3 Au2 Cl2 90.92(3) . . ? P2 Au2 Cl2 176.30(3) . . ? C7 P1 C1 113.80(11) . . ? C7 P1 C13 110.38(11) . . ? C1 P1 C13 110.52(11) . . ? C7 P1 Au1 122.26(8) . . ? C1 P1 Au1 83.72(7) . . ? C13 P1 Au1 113.32(8) . . ? C25 P2 C31 114.83(11) . . ? C25 P2 C19 109.40(11) . . ? C31 P2 C19 105.16(11) . . ? C25 P2 Au2 102.63(8) . . ? C31 P2 Au2 110.62(8) . . ? C19 P2 Au2 114.50(8) . . ? C2 C1 C6 121.8(2) . . ? C2 C1 P1 137.48(19) . . ? C6 C1 P1 100.58(16) . . ? F1 C2 C1 121.9(2) . . ? F1 C2 C3 119.0(2) . . ? C1 C2 C3 119.1(2) . . ? F2 C3 C2 120.8(2) . . ? F2 C3 C4 119.5(2) . . ? C2 C3 C4 119.8(2) . . ? F3 C4 C5 120.1(2) . . ? F3 C4 C3 119.1(2) . . ? C5 C4 C3 120.8(2) . . ? F4 C5 C6 121.9(2) . . ? F4 C5 C4 118.1(2) . . ? C6 C5 C4 120.1(2) . . ? C5 C6 C1 118.5(2) . . ? C5 C6 Au1 134.62(18) . . ? C1 C6 Au1 106.83(16) . . ? C8 C7 C12 120.5(2) . . ? C8 C7 P1 121.96(19) . . ? C12 C7 P1 117.58(18) . . ? C9 C8 C7 119.5(2) . . ? C9 C8 H8 120.3 . . ? C7 C8 H8 120.3 . . ? C10 C9 C8 119.9(3) . . ? C10 C9 H9 120.0 . . ? C8 C9 H9 120.0 . . ? C9 C10 C11 120.9(2) . . ? C9 C10 H10 119.5 . . ? C11 C10 H10 119.5 . . ? C10 C11 C12 119.9(3) . . ? C10 C11 H11 120.1 . . ? C12 C11 H11 120.1 . . ? C11 C12 C7 119.3(2) . . ? C11 C12 H12 120.3 . . ? C7 C12 H12 120.3 . . ? C18 C13 C14 120.4(2) . . ? C18 C13 P1 119.89(18) . . ? C14 C13 P1 119.54(19) . . ? C15 C14 C13 119.6(3) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C16 C15 C14 120.2(3) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C15 C16 C17 120.8(3) . . ? C15 C16 H16 119.6 . . ? C17 C16 H16 119.6 . . ? C18 C17 C16 119.5(3) . . ? C18 C17 H17 120.2 . . ? C16 C17 H17 120.2 . . ? C17 C18 C13 119.4(2) . . ? C17 C18 H18 120.3 . . ? C13 C18 H18 120.3 . . ? C20 C19 C24 119.5(2) . . ? C20 C19 P2 115.23(18) . . ? C24 C19 P2 125.16(17) . . ? F5 C20 C21 117.5(2) . . ? F5 C20 C19 120.5(2) . . ? C21 C20 C19 122.0(2) . . ? F6 C21 C20 120.7(2) . . ? F6 C21 C22 120.2(2) . . ? C20 C21 C22 119.1(2) . . ? F7 C22 C21 119.5(2) . . ? F7 C22 C23 121.3(2) . . ? C21 C22 C23 119.2(2) . . ? F8 C23 C22 116.6(2) . . ? F8 C23 C24 120.0(2) . . ? C22 C23 C24 123.4(2) . . ? C23 C24 C19 116.7(2) . . ? C23 C24 Au1 111.64(17) . . ? C19 C24 Au1 130.50(17) . . ? C30 C25 C26 120.4(2) . . ? C30 C25 P2 124.00(19) . . ? C26 C25 P2 115.40(18) . . ? C27 C26 C25 119.9(3) . . ? C27 C26 H26 120.0 . . ? C25 C26 H26 120.0 . . ? C26 C27 C28 119.9(3) . . ? C26 C27 H27 120.1 . . ? C28 C27 H27 120.1 . . ? C27 C28 C29 120.1(2) . . ? C27 C28 H28 119.9 . . ? C29 C28 H28 119.9 . . ? C28 C29 C30 120.7(3) . . ? C28 C29 H29 119.6 . . ? C30 C29 H29 119.6 . . ? C29 C30 C25 119.0(3) . . ? C29 C30 H30 120.5 . . ? C25 C30 H30 120.5 . . ? C36 C31 C32 119.7(2) . . ? C36 C31 P2 119.75(19) . . ? C32 C31 P2 120.16(19) . . ? C33 C32 C31 119.6(2) . . ? C33 C32 H32 120.2 . . ? C31 C32 H32 120.2 . . ? C34 C33 C32 120.4(3) . . ? C34 C33 H33 119.8 . . ? C32 C33 H33 119.8 . . ? C35 C34 C33 120.1(2) . . ? C35 C34 H34 119.9 . . ? C33 C34 H34 119.9 . . ? C36 C35 C34 120.3(3) . . ? C36 C35 H35 119.9 . . ? C34 C35 H35 119.9 . . ? C35 C36 C31 120.0(3) . . ? C35 C36 H36 120.0 . . ? C31 C36 H36 120.0 . . ? Cl5 C37 Cl6 111.4(2) . . ? Cl5 C37 H37A 109.4 . . ? Cl6 C37 H37A 109.4 . . ? Cl5 C37 H37B 109.4 . . ? Cl6 C37 H37B 109.4 . . ? H37A C37 H37B 108.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 Au1 P1 C7 114.23(12) . . . . ? C24 Au1 P1 C7 157.5(3) . . . . ? Cl1 Au1 P1 C7 -69.14(10) . . . . ? C6 Au1 P1 C1 0.00(10) . . . . ? C24 Au1 P1 C1 43.2(3) . . . . ? Cl1 Au1 P1 C1 176.62(8) . . . . ? C6 Au1 P1 C13 -109.67(11) . . . . ? C24 Au1 P1 C13 -66.5(3) . . . . ? Cl1 Au1 P1 C13 66.95(9) . . . . ? Cl4 Au2 P2 C25 109.29(8) . . . . ? Cl3 Au2 P2 C25 -66.41(8) . . . . ? Cl4 Au2 P2 C31 -127.75(9) . . . . ? Cl3 Au2 P2 C31 56.56(8) . . . . ? Cl4 Au2 P2 C19 -9.15(9) . . . . ? Cl3 Au2 P2 C19 175.16(9) . . . . ? C7 P1 C1 C2 62.3(3) . . . . ? C13 P1 C1 C2 -62.6(3) . . . . ? Au1 P1 C1 C2 -175.2(3) . . . . ? C7 P1 C1 C6 -122.56(16) . . . . ? C13 P1 C1 C6 112.58(16) . . . . ? Au1 P1 C1 C6 0.01(14) . . . . ? C6 C1 C2 F1 -179.1(2) . . . . ? P1 C1 C2 F1 -4.7(4) . . . . ? C6 C1 C2 C3 1.4(4) . . . . ? P1 C1 C2 C3 175.8(2) . . . . ? F1 C2 C3 F2 -0.6(4) . . . . ? C1 C2 C3 F2 178.8(2) . . . . ? F1 C2 C3 C4 179.6(2) . . . . ? C1 C2 C3 C4 -1.0(4) . . . . ? F2 C3 C4 F3 0.5(4) . . . . ? C2 C3 C4 F3 -179.7(2) . . . . ? F2 C3 C4 C5 -179.3(2) . . . . ? C2 C3 C4 C5 0.5(4) . . . . ? F3 C4 C5 F4 -1.6(4) . . . . ? C3 C4 C5 F4 178.3(2) . . . . ? F3 C4 C5 C6 179.8(2) . . . . ? C3 C4 C5 C6 -0.4(4) . . . . ? F4 C5 C6 C1 -177.8(2) . . . . ? C4 C5 C6 C1 0.8(4) . . . . ? F4 C5 C6 Au1 5.6(4) . . . . ? C4 C5 C6 Au1 -175.82(19) . . . . ? C2 C1 C6 C5 -1.3(4) . . . . ? P1 C1 C6 C5 -177.47(19) . . . . ? C2 C1 C6 Au1 176.15(19) . . . . ? P1 C1 C6 Au1 -0.01(17) . . . . ? C24 Au1 C6 C5 5.4(3) . . . . ? Cl1 Au1 C6 C5 160.5(2) . . . . ? P1 Au1 C6 C5 176.9(3) . . . . ? C24 Au1 C6 C1 -171.45(16) . . . . ? Cl1 Au1 C6 C1 -16.4(4) . . . . ? P1 Au1 C6 C1 0.01(14) . . . . ? C1 P1 C7 C8 -22.2(2) . . . . ? C13 P1 C7 C8 102.7(2) . . . . ? Au1 P1 C7 C8 -120.1(2) . . . . ? C1 P1 C7 C12 156.72(19) . . . . ? C13 P1 C7 C12 -78.4(2) . . . . ? Au1 P1 C7 C12 58.9(2) . . . . ? C12 C7 C8 C9 0.6(4) . . . . ? P1 C7 C8 C9 179.6(2) . . . . ? C7 C8 C9 C10 -0.4(4) . . . . ? C8 C9 C10 C11 0.3(4) . . . . ? C9 C10 C11 C12 -0.4(4) . . . . ? C10 C11 C12 C7 0.6(4) . . . . ? C8 C7 C12 C11 -0.7(4) . . . . ? P1 C7 C12 C11 -179.7(2) . . . . ? C7 P1 C13 C18 -51.7(2) . . . . ? C1 P1 C13 C18 75.1(2) . . . . ? Au1 P1 C13 C18 167.06(18) . . . . ? C7 P1 C13 C14 133.1(2) . . . . ? C1 P1 C13 C14 -100.1(2) . . . . ? Au1 P1 C13 C14 -8.2(2) . . . . ? C18 C13 C14 C15 0.1(4) . . . . ? P1 C13 C14 C15 175.3(2) . . . . ? C13 C14 C15 C16 0.2(4) . . . . ? C14 C15 C16 C17 -0.9(5) . . . . ? C15 C16 C17 C18 1.3(5) . . . . ? C16 C17 C18 C13 -1.0(4) . . . . ? C14 C13 C18 C17 0.3(4) . . . . ? P1 C13 C18 C17 -174.9(2) . . . . ? C25 P2 C19 C20 -171.82(19) . . . . ? C31 P2 C19 C20 64.4(2) . . . . ? Au2 P2 C19 C20 -57.3(2) . . . . ? C25 P2 C19 C24 11.2(2) . . . . ? C31 P2 C19 C24 -112.6(2) . . . . ? Au2 P2 C19 C24 125.78(19) . . . . ? C24 C19 C20 F5 177.0(2) . . . . ? P2 C19 C20 F5 -0.1(3) . . . . ? C24 C19 C20 C21 -0.4(4) . . . . ? P2 C19 C20 C21 -177.5(2) . . . . ? F5 C20 C21 F6 -0.1(4) . . . . ? C19 C20 C21 F6 177.4(2) . . . . ? F5 C20 C21 C22 -178.4(2) . . . . ? C19 C20 C21 C22 -0.9(4) . . . . ? F6 C21 C22 F7 0.5(4) . . . . ? C20 C21 C22 F7 178.8(2) . . . . ? F6 C21 C22 C23 -177.7(2) . . . . ? C20 C21 C22 C23 0.6(4) . . . . ? F7 C22 C23 F8 1.4(4) . . . . ? C21 C22 C23 F8 179.6(2) . . . . ? F7 C22 C23 C24 -177.1(2) . . . . ? C21 C22 C23 C24 1.1(4) . . . . ? F8 C23 C24 C19 179.2(2) . . . . ? C22 C23 C24 C19 -2.3(4) . . . . ? F8 C23 C24 Au1 -11.7(3) . . . . ? C22 C23 C24 Au1 166.8(2) . . . . ? C20 C19 C24 C23 2.0(3) . . . . ? P2 C19 C24 C23 178.77(19) . . . . ? C20 C19 C24 Au1 -164.72(19) . . . . ? P2 C19 C24 Au1 12.1(3) . . . . ? C6 Au1 C24 C23 85.10(19) . . . . ? Cl1 Au1 C24 C23 -89.92(17) . . . . ? P1 Au1 C24 C23 44.3(4) . . . . ? C6 Au1 C24 C19 -107.7(2) . . . . ? Cl1 Au1 C24 C19 77.3(2) . . . . ? P1 Au1 C24 C19 -148.5(2) . . . . ? C31 P2 C25 C30 3.9(3) . . . . ? C19 P2 C25 C30 -114.0(2) . . . . ? Au2 P2 C25 C30 124.0(2) . . . . ? C31 P2 C25 C26 -170.38(19) . . . . ? C19 P2 C25 C26 71.7(2) . . . . ? Au2 P2 C25 C26 -50.3(2) . . . . ? C30 C25 C26 C27 1.3(4) . . . . ? P2 C25 C26 C27 175.9(2) . . . . ? C25 C26 C27 C28 -0.4(4) . . . . ? C26 C27 C28 C29 -0.7(4) . . . . ? C27 C28 C29 C30 0.8(4) . . . . ? C28 C29 C30 C25 0.2(4) . . . . ? C26 C25 C30 C29 -1.3(4) . . . . ? P2 C25 C30 C29 -175.3(2) . . . . ? C25 P2 C31 C36 138.6(2) . . . . ? C19 P2 C31 C36 -101.1(2) . . . . ? Au2 P2 C31 C36 23.0(2) . . . . ? C25 P2 C31 C32 -48.8(2) . . . . ? C19 P2 C31 C32 71.5(2) . . . . ? Au2 P2 C31 C32 -164.39(18) . . . . ? C36 C31 C32 C33 -0.9(4) . . . . ? P2 C31 C32 C33 -173.4(2) . . . . ? C31 C32 C33 C34 1.7(4) . . . . ? C32 C33 C34 C35 -1.2(4) . . . . ? C33 C34 C35 C36 -0.2(4) . . . . ? C34 C35 C36 C31 1.0(4) . . . . ? C32 C31 C36 C35 -0.5(4) . . . . ? P2 C31 C36 C35 172.1(2) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 38.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 5.374 _refine_diff_density_min -5.879 _refine_diff_density_rms 0.234 # Attachment 'neda01201.cif.txt' data_neda01201 _database_code_depnum_ccdc_archive 'CCDC 725997' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H20 Au2 Br4 F8 P2, C H2 Cl2' _chemical_formula_sum 'C37 H22 Au2 Br4 Cl2 F8 P2' _chemical_formula_weight 1464.96 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 10.9022(3) _cell_length_b 14.5683(4) _cell_length_c 14.5702(4) _cell_angle_alpha 119.3830(10) _cell_angle_beta 94.2110(10) _cell_angle_gamma 92.7670(10) _cell_volume 2001.51(10) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 83882 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description polyhedron _exptl_crystal_colour red _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.431 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1356 _exptl_absorpt_coefficient_mu 11.594 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.128 _exptl_absorpt_correction_T_max 0.314 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 50246 _diffrn_reflns_av_R_equivalents 0.0611 _diffrn_reflns_av_sigmaI/netI 0.0431 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 33.00 _reflns_number_total 15094 _reflns_number_gt 13531 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0354P)^2^+28.0509P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00053(11) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 15094 _refine_ls_number_parameters 497 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0560 _refine_ls_R_factor_gt 0.0493 _refine_ls_wR_factor_ref 0.1174 _refine_ls_wR_factor_gt 0.1151 _refine_ls_goodness_of_fit_ref 1.123 _refine_ls_restrained_S_all 1.123 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl 0.9499(2) 0.39442(15) 0.54513(16) 0.0355(4) Uani 1 1 d . . . Cl2 Cl 1.0036(2) 0.2497(2) 0.6247(2) 0.0482(6) Uani 1 1 d . . . C37 C 0.9499(7) 0.2616(6) 0.5145(6) 0.0294(14) Uani 1 1 d . . . H37A H 0.8649 0.2262 0.4879 0.035 Uiso 1 1 calc R . . H37B H 1.0030 0.2248 0.4572 0.035 Uiso 1 1 calc R . . Au1 Au 0.705720(18) 0.643814(15) 0.714118(15) 0.01202(5) Uani 1 1 d . . . Au2 Au 0.805211(19) 1.081969(16) 0.823683(17) 0.01486(5) Uani 1 1 d . . . Br1 Br 0.48052(5) 0.61472(5) 0.66579(5) 0.01893(11) Uani 1 1 d . . . Br2 Br 0.93385(6) 1.25026(5) 0.89062(5) 0.02307(12) Uani 1 1 d . . . Br3 Br 0.69251(6) 1.16153(5) 0.97811(5) 0.02323(12) Uani 1 1 d . . . Br4 Br 0.92907(6) 0.99927(5) 0.67787(6) 0.02587(13) Uani 1 1 d . . . P1 P 0.72328(13) 0.54287(11) 0.79775(11) 0.0127(2) Uani 1 1 d . . . P2 P 0.67367(13) 0.92876(11) 0.76984(11) 0.0132(2) Uani 1 1 d . . . F1 F 0.9961(4) 0.4892(3) 0.8849(3) 0.0214(7) Uani 1 1 d . . . F2 F 1.2141(3) 0.5675(3) 0.8589(3) 0.0220(7) Uani 1 1 d . . . F3 F 1.2167(3) 0.6871(3) 0.7643(3) 0.0236(8) Uani 1 1 d . . . F4 F 1.0059(4) 0.7404(3) 0.7022(3) 0.0213(7) Uani 1 1 d . . . F5 F 0.6522(4) 0.9322(3) 0.5721(3) 0.0198(7) Uani 1 1 d . . . F6 F 0.6817(4) 0.7816(4) 0.3740(3) 0.0268(8) Uani 1 1 d . . . F7 F 0.7357(4) 0.5866(3) 0.3355(3) 0.0242(8) Uani 1 1 d . . . F8 F 0.7612(4) 0.5427(3) 0.4936(3) 0.0203(7) Uani 1 1 d . . . C1 C 0.8863(5) 0.5760(4) 0.8063(4) 0.0136(9) Uani 1 1 d . . . C2 C 0.9965(5) 0.5499(4) 0.8394(4) 0.0154(9) Uani 1 1 d . . . C3 C 1.1073(5) 0.5897(5) 0.8262(5) 0.0165(9) Uani 1 1 d . . . C4 C 1.1081(5) 0.6515(5) 0.7784(5) 0.0173(10) Uani 1 1 d . . . C5 C 0.9978(5) 0.6757(5) 0.7442(5) 0.0167(9) Uani 1 1 d . . . C6 C 0.8870(5) 0.6387(4) 0.7576(4) 0.0131(8) Uani 1 1 d . . . C7 C 0.6834(5) 0.4032(4) 0.7096(4) 0.0147(9) Uani 1 1 d . . . C8 C 0.7108(6) 0.3313(5) 0.7440(5) 0.0189(10) Uani 1 1 d . . . H8 H 0.7442 0.3561 0.8152 0.023 Uiso 1 1 calc R . . C9 C 0.6890(7) 0.2248(5) 0.6740(5) 0.0235(12) Uani 1 1 d . . . H9 H 0.7102 0.1759 0.6966 0.028 Uiso 1 1 calc R . . C10 C 0.6359(6) 0.1868(5) 0.5694(6) 0.0250(13) Uani 1 1 d . . . H10 H 0.6183 0.1129 0.5224 0.030 Uiso 1 1 calc R . . C11 C 0.6092(6) 0.2590(5) 0.5355(5) 0.0240(12) Uani 1 1 d . . . H11 H 0.5752 0.2342 0.4645 0.029 Uiso 1 1 calc R . . C12 C 0.6324(6) 0.3669(5) 0.6055(5) 0.0195(10) Uani 1 1 d . . . H12 H 0.6135 0.4160 0.5826 0.023 Uiso 1 1 calc R . . C13 C 0.6681(5) 0.5833(4) 0.9237(4) 0.0150(9) Uani 1 1 d . . . C14 C 0.5431(6) 0.5992(5) 0.9319(5) 0.0188(10) Uani 1 1 d . . . H14 H 0.4904 0.5876 0.8715 0.023 Uiso 1 1 calc R . . C15 C 0.4952(6) 0.6320(5) 1.0283(5) 0.0220(11) Uani 1 1 d . . . H15 H 0.4100 0.6418 1.0339 0.026 Uiso 1 1 calc R . . C16 C 0.5750(6) 0.6503(5) 1.1174(5) 0.0216(11) Uani 1 1 d . . . H16 H 0.5441 0.6745 1.1839 0.026 Uiso 1 1 calc R . . C17 C 0.6994(7) 0.6330(5) 1.1081(5) 0.0241(12) Uani 1 1 d . . . H17 H 0.7525 0.6436 1.1679 0.029 Uiso 1 1 calc R . . C18 C 0.7458(6) 0.6004(5) 1.0117(5) 0.0195(10) Uani 1 1 d . . . H18 H 0.8308 0.5898 1.0059 0.023 Uiso 1 1 calc R . . C19 C 0.6945(5) 0.8172(4) 0.6407(4) 0.0145(9) Uani 1 1 d . . . C20 C 0.6821(5) 0.8373(5) 0.5563(4) 0.0158(9) Uani 1 1 d . . . C21 C 0.6971(6) 0.7608(5) 0.4544(5) 0.0180(10) Uani 1 1 d . . . C22 C 0.7250(6) 0.6624(5) 0.4346(4) 0.0183(10) Uani 1 1 d . . . C23 C 0.7369(6) 0.6409(4) 0.5179(5) 0.0170(10) Uani 1 1 d . . . C24 C 0.7207(5) 0.7153(4) 0.6214(4) 0.0131(8) Uani 1 1 d . . . C25 C 0.7139(5) 0.8943(4) 0.8704(4) 0.0163(9) Uani 1 1 d . . . C26 C 0.6282(6) 0.8791(5) 0.9300(5) 0.0198(10) Uani 1 1 d . . . H26 H 0.5426 0.8819 0.9150 0.024 Uiso 1 1 calc R . . C27 C 0.6691(6) 0.8600(5) 1.0112(5) 0.0217(11) Uani 1 1 d . . . H27 H 0.6116 0.8493 1.0518 0.026 Uiso 1 1 calc R . . C28 C 0.7942(6) 0.8565(5) 1.0326(5) 0.0213(11) Uani 1 1 d . . . H28 H 0.8218 0.8432 1.0879 0.026 Uiso 1 1 calc R . . C29 C 0.8800(6) 0.8722(5) 0.9744(5) 0.0228(12) Uani 1 1 d . . . H29 H 0.9655 0.8703 0.9905 0.027 Uiso 1 1 calc R . . C30 C 0.8404(6) 0.8905(5) 0.8933(5) 0.0185(10) Uani 1 1 d . . . H30 H 0.8987 0.9006 0.8529 0.022 Uiso 1 1 calc R . . C31 C 0.5140(5) 0.9539(4) 0.7577(4) 0.0145(9) Uani 1 1 d . . . C32 C 0.4180(5) 0.8834(5) 0.7516(5) 0.0181(10) Uani 1 1 d . . . H32 H 0.4358 0.8253 0.7615 0.022 Uiso 1 1 calc R . . C33 C 0.2958(6) 0.8987(5) 0.7311(5) 0.0230(12) Uani 1 1 d . . . H33 H 0.2303 0.8519 0.7289 0.028 Uiso 1 1 calc R . . C34 C 0.2690(6) 0.9812(5) 0.7138(5) 0.0228(12) Uani 1 1 d . . . H34 H 0.1856 0.9902 0.6986 0.027 Uiso 1 1 calc R . . C35 C 0.3642(6) 1.0511(5) 0.7187(5) 0.0221(11) Uani 1 1 d . . . H35 H 0.3457 1.1074 0.7062 0.027 Uiso 1 1 calc R . . C36 C 0.4861(5) 1.0388(5) 0.7419(5) 0.0187(10) Uani 1 1 d . . . H36 H 0.5508 1.0878 0.7470 0.022 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0407(10) 0.0252(8) 0.0335(9) 0.0077(7) 0.0125(7) 0.0079(7) Cl2 0.0349(10) 0.0752(17) 0.0555(14) 0.0474(14) 0.0119(9) 0.0092(10) C37 0.031(3) 0.024(3) 0.029(3) 0.009(3) 0.004(3) 0.004(3) Au1 0.01275(8) 0.01029(8) 0.01340(9) 0.00618(6) 0.00121(6) 0.00124(6) Au2 0.01440(9) 0.01117(9) 0.01809(10) 0.00701(7) -0.00135(6) 0.00065(6) Br1 0.0132(2) 0.0171(2) 0.0274(3) 0.0120(2) -0.00002(19) 0.00084(18) Br2 0.0240(3) 0.0155(2) 0.0279(3) 0.0113(2) -0.0066(2) -0.0052(2) Br3 0.0273(3) 0.0158(2) 0.0193(3) 0.0032(2) 0.0031(2) 0.0014(2) Br4 0.0186(3) 0.0212(3) 0.0329(3) 0.0089(2) 0.0088(2) 0.0009(2) P1 0.0147(6) 0.0106(5) 0.0133(5) 0.0064(5) 0.0014(4) 0.0012(4) P2 0.0140(6) 0.0111(5) 0.0141(6) 0.0059(5) 0.0013(4) 0.0018(4) F1 0.0243(18) 0.0193(17) 0.0247(18) 0.0147(15) -0.0022(14) 0.0024(14) F2 0.0153(15) 0.0227(18) 0.0237(18) 0.0084(15) -0.0019(13) 0.0062(13) F3 0.0120(15) 0.029(2) 0.030(2) 0.0145(16) 0.0039(13) -0.0022(13) F4 0.0200(17) 0.0233(18) 0.0265(18) 0.0170(15) 0.0036(14) -0.0009(13) F5 0.0279(18) 0.0164(16) 0.0206(16) 0.0126(14) 0.0051(14) 0.0080(13) F6 0.041(2) 0.030(2) 0.0163(17) 0.0152(16) 0.0069(15) 0.0087(17) F7 0.036(2) 0.0193(17) 0.0130(15) 0.0045(13) 0.0048(14) 0.0051(15) F8 0.0284(19) 0.0117(15) 0.0185(16) 0.0054(13) 0.0038(13) 0.0028(13) C1 0.016(2) 0.011(2) 0.013(2) 0.0052(17) 0.0010(16) 0.0010(16) C2 0.018(2) 0.012(2) 0.017(2) 0.0071(18) 0.0014(17) 0.0027(17) C3 0.014(2) 0.016(2) 0.018(2) 0.0068(19) -0.0006(17) 0.0025(17) C4 0.011(2) 0.019(2) 0.019(2) 0.007(2) 0.0012(17) 0.0001(17) C5 0.018(2) 0.020(2) 0.017(2) 0.012(2) 0.0047(18) 0.0056(19) C6 0.011(2) 0.011(2) 0.016(2) 0.0070(17) -0.0013(16) 0.0020(16) C7 0.016(2) 0.011(2) 0.015(2) 0.0060(17) -0.0001(17) 0.0000(17) C8 0.023(3) 0.013(2) 0.020(2) 0.008(2) 0.000(2) -0.0013(19) C9 0.031(3) 0.013(2) 0.026(3) 0.009(2) 0.006(2) 0.003(2) C10 0.022(3) 0.015(3) 0.028(3) 0.003(2) 0.004(2) 0.003(2) C11 0.028(3) 0.018(3) 0.019(3) 0.003(2) 0.000(2) 0.000(2) C12 0.019(2) 0.020(3) 0.017(2) 0.007(2) -0.0016(19) -0.002(2) C13 0.019(2) 0.012(2) 0.015(2) 0.0071(18) 0.0032(17) 0.0010(17) C14 0.020(2) 0.018(2) 0.021(3) 0.011(2) 0.0048(19) 0.0049(19) C15 0.024(3) 0.021(3) 0.023(3) 0.011(2) 0.009(2) 0.006(2) C16 0.031(3) 0.016(2) 0.018(2) 0.008(2) 0.009(2) 0.004(2) C17 0.028(3) 0.024(3) 0.017(3) 0.008(2) 0.001(2) 0.001(2) C18 0.019(2) 0.023(3) 0.016(2) 0.011(2) -0.0018(19) -0.001(2) C19 0.015(2) 0.016(2) 0.013(2) 0.0066(18) 0.0005(16) 0.0013(17) C20 0.019(2) 0.015(2) 0.016(2) 0.0099(19) -0.0002(18) 0.0014(18) C21 0.024(3) 0.018(2) 0.014(2) 0.0091(19) 0.0028(19) 0.004(2) C22 0.023(3) 0.016(2) 0.012(2) 0.0044(19) 0.0019(18) 0.0014(19) C23 0.022(2) 0.013(2) 0.017(2) 0.0073(19) 0.0050(19) 0.0042(18) C24 0.014(2) 0.013(2) 0.013(2) 0.0068(17) 0.0019(16) 0.0029(16) C25 0.020(2) 0.014(2) 0.012(2) 0.0041(18) -0.0012(17) 0.0030(18) C26 0.023(3) 0.019(3) 0.018(2) 0.009(2) 0.0013(19) 0.002(2) C27 0.027(3) 0.021(3) 0.020(3) 0.013(2) 0.003(2) 0.002(2) C28 0.032(3) 0.018(3) 0.014(2) 0.009(2) 0.000(2) 0.005(2) C29 0.025(3) 0.018(3) 0.022(3) 0.008(2) -0.003(2) 0.006(2) C30 0.021(3) 0.017(2) 0.016(2) 0.008(2) 0.0009(19) 0.0020(19) C31 0.014(2) 0.014(2) 0.015(2) 0.0068(18) 0.0013(16) 0.0026(17) C32 0.017(2) 0.016(2) 0.020(2) 0.007(2) 0.0007(18) 0.0010(18) C33 0.014(2) 0.024(3) 0.026(3) 0.010(2) -0.004(2) 0.003(2) C34 0.015(2) 0.026(3) 0.024(3) 0.009(2) -0.002(2) 0.005(2) C35 0.020(3) 0.023(3) 0.025(3) 0.013(2) -0.001(2) 0.007(2) C36 0.016(2) 0.021(3) 0.021(3) 0.012(2) 0.0013(19) 0.0038(19) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cl1 C37 1.760(8) . ? Cl2 C37 1.759(8) . ? C37 H37A 0.9900 . ? C37 H37B 0.9900 . ? Au1 C6 2.046(5) . ? Au1 C24 2.081(5) . ? Au1 P1 2.3315(14) . ? Au1 Br1 2.4609(6) . ? Au2 P2 2.3369(14) . ? Au2 Br4 2.4198(7) . ? Au2 Br3 2.4290(7) . ? Au2 Br2 2.4596(6) . ? P1 C13 1.792(6) . ? P1 C1 1.797(6) . ? P1 C7 1.802(6) . ? P2 C25 1.799(6) . ? P2 C31 1.810(6) . ? P2 C19 1.825(6) . ? F1 C2 1.339(7) . ? F2 C3 1.339(7) . ? F3 C4 1.338(6) . ? F4 C5 1.356(7) . ? F5 C20 1.345(7) . ? F6 C21 1.347(7) . ? F7 C22 1.338(7) . ? F8 C23 1.339(7) . ? C1 C2 1.400(8) . ? C1 C6 1.406(8) . ? C2 C3 1.382(8) . ? C3 C4 1.383(9) . ? C4 C5 1.395(8) . ? C5 C6 1.365(8) . ? C7 C12 1.396(8) . ? C7 C8 1.402(8) . ? C8 C9 1.371(8) . ? C8 H8 0.9500 . ? C9 C10 1.405(10) . ? C9 H9 0.9500 . ? C10 C11 1.399(10) . ? C10 H10 0.9500 . ? C11 C12 1.387(9) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.389(8) . ? C13 C14 1.397(8) . ? C14 C15 1.396(9) . ? C14 H14 0.9500 . ? C15 C16 1.408(10) . ? C15 H15 0.9500 . ? C16 C17 1.396(10) . ? C16 H16 0.9500 . ? C17 C18 1.388(9) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.397(8) . ? C19 C24 1.417(8) . ? C20 C21 1.380(8) . ? C21 C22 1.372(8) . ? C22 C23 1.393(8) . ? C23 C24 1.392(8) . ? C25 C26 1.401(9) . ? C25 C30 1.405(8) . ? C26 C27 1.391(9) . ? C26 H26 0.9500 . ? C27 C28 1.385(10) . ? C27 H27 0.9500 . ? C28 C29 1.389(10) . ? C28 H28 0.9500 . ? C29 C30 1.379(9) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.398(8) . ? C31 C36 1.407(8) . ? C32 C33 1.397(8) . ? C32 H32 0.9500 . ? C33 C34 1.384(10) . ? C33 H33 0.9500 . ? C34 C35 1.390(10) . ? C34 H34 0.9500 . ? C35 C36 1.389(8) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl2 C37 Cl1 112.4(4) . . ? Cl2 C37 H37A 109.1 . . ? Cl1 C37 H37A 109.1 . . ? Cl2 C37 H37B 109.1 . . ? Cl1 C37 H37B 109.1 . . ? H37A C37 H37B 107.9 . . ? C6 Au1 C24 102.1(2) . . ? C6 Au1 P1 68.91(16) . . ? C24 Au1 P1 167.48(15) . . ? C6 Au1 Br1 167.23(15) . . ? C24 Au1 Br1 89.12(15) . . ? P1 Au1 Br1 99.03(4) . . ? P2 Au2 Br4 94.61(4) . . ? P2 Au2 Br3 85.61(4) . . ? Br4 Au2 Br3 175.49(3) . . ? P2 Au2 Br2 175.79(4) . . ? Br4 Au2 Br2 89.58(2) . . ? Br3 Au2 Br2 90.24(2) . . ? C13 P1 C1 113.7(3) . . ? C13 P1 C7 110.6(3) . . ? C1 P1 C7 110.4(3) . . ? C13 P1 Au1 121.87(19) . . ? C1 P1 Au1 83.79(18) . . ? C7 P1 Au1 113.53(19) . . ? C25 P2 C31 114.9(3) . . ? C25 P2 C19 108.8(3) . . ? C31 P2 C19 104.7(3) . . ? C25 P2 Au2 103.0(2) . . ? C31 P2 Au2 110.53(19) . . ? C19 P2 Au2 115.25(19) . . ? C2 C1 C6 121.2(5) . . ? C2 C1 P1 137.4(4) . . ? C6 C1 P1 101.2(4) . . ? F1 C2 C3 119.9(5) . . ? F1 C2 C1 121.4(5) . . ? C3 C2 C1 118.7(5) . . ? F2 C3 C2 119.9(5) . . ? F2 C3 C4 119.9(5) . . ? C2 C3 C4 120.1(5) . . ? F3 C4 C3 119.0(5) . . ? F3 C4 C5 120.3(6) . . ? C3 C4 C5 120.7(5) . . ? F4 C5 C6 122.2(5) . . ? F4 C5 C4 117.4(5) . . ? C6 C5 C4 120.4(5) . . ? C5 C6 C1 118.8(5) . . ? C5 C6 Au1 135.0(4) . . ? C1 C6 Au1 106.1(4) . . ? C12 C7 C8 120.3(5) . . ? C12 C7 P1 119.9(4) . . ? C8 C7 P1 119.7(4) . . ? C9 C8 C7 119.4(6) . . ? C9 C8 H8 120.3 . . ? C7 C8 H8 120.3 . . ? C8 C9 C10 121.0(6) . . ? C8 C9 H9 119.5 . . ? C10 C9 H9 119.5 . . ? C11 C10 C9 119.2(6) . . ? C11 C10 H10 120.4 . . ? C9 C10 H10 120.4 . . ? C12 C11 C10 120.0(6) . . ? C12 C11 H11 120.0 . . ? C10 C11 H11 120.0 . . ? C11 C12 C7 119.9(6) . . ? C11 C12 H12 120.0 . . ? C7 C12 H12 120.0 . . ? C18 C13 C14 120.2(5) . . ? C18 C13 P1 122.0(5) . . ? C14 C13 P1 117.8(4) . . ? C15 C14 C13 120.3(6) . . ? C15 C14 H14 119.8 . . ? C13 C14 H14 119.8 . . ? C14 C15 C16 119.1(6) . . ? C14 C15 H15 120.5 . . ? C16 C15 H15 120.5 . . ? C17 C16 C15 120.2(6) . . ? C17 C16 H16 119.9 . . ? C15 C16 H16 119.9 . . ? C18 C17 C16 120.1(6) . . ? C18 C17 H17 120.0 . . ? C16 C17 H17 120.0 . . ? C17 C18 C13 120.1(6) . . ? C17 C18 H18 119.9 . . ? C13 C18 H18 119.9 . . ? C20 C19 C24 119.5(5) . . ? C20 C19 P2 115.1(4) . . ? C24 C19 P2 125.3(4) . . ? F5 C20 C21 117.9(5) . . ? F5 C20 C19 120.5(5) . . ? C21 C20 C19 121.6(5) . . ? F6 C21 C22 120.0(5) . . ? F6 C21 C20 120.3(5) . . ? C22 C21 C20 119.7(5) . . ? F7 C22 C21 120.1(5) . . ? F7 C22 C23 120.4(5) . . ? C21 C22 C23 119.4(5) . . ? F8 C23 C24 120.4(5) . . ? F8 C23 C22 116.9(5) . . ? C24 C23 C22 122.7(5) . . ? C23 C24 C19 117.1(5) . . ? C23 C24 Au1 110.8(4) . . ? C19 C24 Au1 130.9(4) . . ? C26 C25 C30 119.9(5) . . ? C26 C25 P2 123.7(5) . . ? C30 C25 P2 116.2(5) . . ? C27 C26 C25 119.6(6) . . ? C27 C26 H26 120.2 . . ? C25 C26 H26 120.2 . . ? C28 C27 C26 119.7(6) . . ? C28 C27 H27 120.2 . . ? C26 C27 H27 120.2 . . ? C27 C28 C29 121.1(6) . . ? C27 C28 H28 119.4 . . ? C29 C28 H28 119.4 . . ? C30 C29 C28 119.7(6) . . ? C30 C29 H29 120.1 . . ? C28 C29 H29 120.1 . . ? C29 C30 C25 120.0(6) . . ? C29 C30 H30 120.0 . . ? C25 C30 H30 120.0 . . ? C32 C31 C36 119.5(5) . . ? C32 C31 P2 120.8(4) . . ? C36 C31 P2 119.4(4) . . ? C33 C32 C31 119.6(6) . . ? C33 C32 H32 120.2 . . ? C31 C32 H32 120.2 . . ? C34 C33 C32 120.7(6) . . ? C34 C33 H33 119.7 . . ? C32 C33 H33 119.7 . . ? C33 C34 C35 120.0(6) . . ? C33 C34 H34 120.0 . . ? C35 C34 H34 120.0 . . ? C36 C35 C34 120.1(6) . . ? C36 C35 H35 119.9 . . ? C34 C35 H35 119.9 . . ? C35 C36 C31 120.1(6) . . ? C35 C36 H36 119.9 . . ? C31 C36 H36 119.9 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 Au1 P1 C13 113.9(3) . . . . ? C24 Au1 P1 C13 159.6(7) . . . . ? Br1 Au1 P1 C13 -70.4(2) . . . . ? C6 Au1 P1 C1 -0.2(2) . . . . ? C24 Au1 P1 C1 45.5(7) . . . . ? Br1 Au1 P1 C1 175.50(17) . . . . ? C6 Au1 P1 C7 -109.8(3) . . . . ? C24 Au1 P1 C7 -64.1(7) . . . . ? Br1 Au1 P1 C7 65.9(2) . . . . ? Br4 Au2 P2 C25 111.0(2) . . . . ? Br3 Au2 P2 C25 -64.5(2) . . . . ? Br4 Au2 P2 C31 -125.8(2) . . . . ? Br3 Au2 P2 C31 58.7(2) . . . . ? Br4 Au2 P2 C19 -7.4(2) . . . . ? Br3 Au2 P2 C19 177.1(2) . . . . ? C13 P1 C1 C2 63.3(7) . . . . ? C7 P1 C1 C2 -61.7(7) . . . . ? Au1 P1 C1 C2 -174.5(6) . . . . ? C13 P1 C1 C6 -121.9(4) . . . . ? C7 P1 C1 C6 113.1(4) . . . . ? Au1 P1 C1 C6 0.2(3) . . . . ? C6 C1 C2 F1 -179.3(5) . . . . ? P1 C1 C2 F1 -5.3(9) . . . . ? C6 C1 C2 C3 1.9(8) . . . . ? P1 C1 C2 C3 175.9(5) . . . . ? F1 C2 C3 F2 0.0(8) . . . . ? C1 C2 C3 F2 178.8(5) . . . . ? F1 C2 C3 C4 179.4(5) . . . . ? C1 C2 C3 C4 -1.8(8) . . . . ? F2 C3 C4 F3 0.9(8) . . . . ? C2 C3 C4 F3 -178.5(5) . . . . ? F2 C3 C4 C5 -179.8(5) . . . . ? C2 C3 C4 C5 0.8(9) . . . . ? F3 C4 C5 F4 -3.5(8) . . . . ? C3 C4 C5 F4 177.2(5) . . . . ? F3 C4 C5 C6 179.4(5) . . . . ? C3 C4 C5 C6 0.1(9) . . . . ? F4 C5 C6 C1 -177.0(5) . . . . ? C4 C5 C6 C1 0.0(8) . . . . ? F4 C5 C6 Au1 7.7(9) . . . . ? C4 C5 C6 Au1 -175.4(4) . . . . ? C2 C1 C6 C5 -1.0(8) . . . . ? P1 C1 C6 C5 -176.9(4) . . . . ? C2 C1 C6 Au1 175.6(4) . . . . ? P1 C1 C6 Au1 -0.3(4) . . . . ? C24 Au1 C6 C5 5.1(6) . . . . ? P1 Au1 C6 C5 176.0(6) . . . . ? Br1 Au1 C6 C5 156.3(5) . . . . ? C24 Au1 C6 C1 -170.6(4) . . . . ? P1 Au1 C6 C1 0.2(3) . . . . ? Br1 Au1 C6 C1 -19.5(10) . . . . ? C13 P1 C7 C12 133.5(5) . . . . ? C1 P1 C7 C12 -99.7(5) . . . . ? Au1 P1 C7 C12 -7.7(5) . . . . ? C13 P1 C7 C8 -50.4(6) . . . . ? C1 P1 C7 C8 76.4(5) . . . . ? Au1 P1 C7 C8 168.4(4) . . . . ? C12 C7 C8 C9 1.1(9) . . . . ? P1 C7 C8 C9 -175.0(5) . . . . ? C7 C8 C9 C10 -2.1(10) . . . . ? C8 C9 C10 C11 2.4(10) . . . . ? C9 C10 C11 C12 -1.6(10) . . . . ? C10 C11 C12 C7 0.6(10) . . . . ? C8 C7 C12 C11 -0.3(9) . . . . ? P1 C7 C12 C11 175.7(5) . . . . ? C1 P1 C13 C18 -23.0(6) . . . . ? C7 P1 C13 C18 101.9(5) . . . . ? Au1 P1 C13 C18 -120.7(5) . . . . ? C1 P1 C13 C14 156.0(4) . . . . ? C7 P1 C13 C14 -79.1(5) . . . . ? Au1 P1 C13 C14 58.3(5) . . . . ? C18 C13 C14 C15 -0.2(9) . . . . ? P1 C13 C14 C15 -179.2(5) . . . . ? C13 C14 C15 C16 0.9(9) . . . . ? C14 C15 C16 C17 -1.7(10) . . . . ? C15 C16 C17 C18 1.7(10) . . . . ? C16 C17 C18 C13 -1.0(10) . . . . ? C14 C13 C18 C17 0.2(9) . . . . ? P1 C13 C18 C17 179.2(5) . . . . ? C25 P2 C19 C20 -172.1(4) . . . . ? C31 P2 C19 C20 64.6(5) . . . . ? Au2 P2 C19 C20 -57.0(5) . . . . ? C25 P2 C19 C24 8.3(6) . . . . ? C31 P2 C19 C24 -115.0(5) . . . . ? Au2 P2 C19 C24 123.3(4) . . . . ? C24 C19 C20 F5 177.2(5) . . . . ? P2 C19 C20 F5 -2.5(7) . . . . ? C24 C19 C20 C21 -1.3(9) . . . . ? P2 C19 C20 C21 179.1(5) . . . . ? F5 C20 C21 F6 -0.1(9) . . . . ? C19 C20 C21 F6 178.4(5) . . . . ? F5 C20 C21 C22 -178.6(5) . . . . ? C19 C20 C21 C22 -0.1(9) . . . . ? F6 C21 C22 F7 -0.7(9) . . . . ? C20 C21 C22 F7 177.8(6) . . . . ? F6 C21 C22 C23 -178.0(6) . . . . ? C20 C21 C22 C23 0.4(9) . . . . ? F7 C22 C23 F8 1.1(9) . . . . ? C21 C22 C23 F8 178.4(5) . . . . ? F7 C22 C23 C24 -176.8(6) . . . . ? C21 C22 C23 C24 0.5(9) . . . . ? F8 C23 C24 C19 -179.6(5) . . . . ? C22 C23 C24 C19 -1.8(9) . . . . ? F8 C23 C24 Au1 -10.9(7) . . . . ? C22 C23 C24 Au1 166.9(5) . . . . ? C20 C19 C24 C23 2.1(8) . . . . ? P2 C19 C24 C23 -178.3(4) . . . . ? C20 C19 C24 Au1 -163.8(4) . . . . ? P2 C19 C24 Au1 15.8(8) . . . . ? C6 Au1 C24 C23 83.8(4) . . . . ? P1 Au1 C24 C23 40.7(10) . . . . ? Br1 Au1 C24 C23 -90.1(4) . . . . ? C6 Au1 C24 C19 -109.6(5) . . . . ? P1 Au1 C24 C19 -152.7(5) . . . . ? Br1 Au1 C24 C19 76.5(5) . . . . ? C31 P2 C25 C26 5.0(6) . . . . ? C19 P2 C25 C26 -112.0(5) . . . . ? Au2 P2 C25 C26 125.2(5) . . . . ? C31 P2 C25 C30 -170.4(4) . . . . ? C19 P2 C25 C30 72.6(5) . . . . ? Au2 P2 C25 C30 -50.1(5) . . . . ? C30 C25 C26 C27 -0.3(9) . . . . ? P2 C25 C26 C27 -175.5(5) . . . . ? C25 C26 C27 C28 0.2(9) . . . . ? C26 C27 C28 C29 0.2(10) . . . . ? C27 C28 C29 C30 -0.6(10) . . . . ? C28 C29 C30 C25 0.6(9) . . . . ? C26 C25 C30 C29 -0.2(9) . . . . ? P2 C25 C30 C29 175.4(5) . . . . ? C25 P2 C31 C32 -48.5(6) . . . . ? C19 P2 C31 C32 70.8(5) . . . . ? Au2 P2 C31 C32 -164.5(4) . . . . ? C25 P2 C31 C36 138.9(5) . . . . ? C19 P2 C31 C36 -101.8(5) . . . . ? Au2 P2 C31 C36 22.9(5) . . . . ? C36 C31 C32 C33 -0.6(9) . . . . ? P2 C31 C32 C33 -173.3(5) . . . . ? C31 C32 C33 C34 1.8(10) . . . . ? C32 C33 C34 C35 -1.2(10) . . . . ? C33 C34 C35 C36 -0.6(10) . . . . ? C34 C35 C36 C31 1.7(10) . . . . ? C32 C31 C36 C35 -1.1(9) . . . . ? P2 C31 C36 C35 171.7(5) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 33.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 5.481 _refine_diff_density_min -2.992 _refine_diff_density_rms 0.301 # Attachment 'neda01301.cif.txt' data_neda01301 _database_code_depnum_ccdc_archive 'CCDC 725998' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 F2 P2' _chemical_formula_sum 'C36 H26 Au2 F2 P2' _chemical_formula_weight 952.44 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.0115(2) _cell_length_b 9.5208(2) _cell_length_c 10.0842(2) _cell_angle_alpha 89.7260(10) _cell_angle_beta 78.8100(10) _cell_angle_gamma 63.1070(10) _cell_volume 753.54(3) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 22536 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 40.250 _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.099 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 448 _exptl_absorpt_coefficient_mu 9.867 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.147 _exptl_absorpt_correction_T_max 0.373 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 33955 _diffrn_reflns_av_R_equivalents 0.0637 _diffrn_reflns_av_sigmaI/netI 0.0422 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.60 _diffrn_reflns_theta_max 40.00 _reflns_number_total 9335 _reflns_number_gt 8579 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect' _computing_cell_refinement DENZO-SMN _computing_data_reduction Scalepack _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0316P)^2^+0.3017P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0037(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 9335 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0315 _refine_ls_R_factor_gt 0.0271 _refine_ls_wR_factor_ref 0.0663 _refine_ls_wR_factor_gt 0.0650 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.067 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.375855(8) 0.622039(8) 0.438769(7) 0.01155(3) Uani 1 1 d . . . P1 P 0.21573(7) 0.69679(6) 0.65697(5) 0.01169(8) Uani 1 1 d . . . F1 F 0.6822(2) 0.23614(19) 0.84285(16) 0.0222(3) Uani 1 1 d . . . C1 C 0.2946(3) 0.5548(2) 0.7794(2) 0.0132(3) Uani 1 1 d . . . C2 C 0.1830(3) 0.5752(3) 0.9057(2) 0.0162(3) Uani 1 1 d . . . H2 H 0.0677 0.6545 0.9210 0.019 Uiso 1 1 calc R . . C3 C 0.2417(3) 0.4796(3) 1.0072(2) 0.0182(4) Uani 1 1 d . . . H3 H 0.1666 0.4920 1.0917 0.022 Uiso 1 1 calc R . . C4 C 0.4110(3) 0.3655(3) 0.9848(2) 0.0177(4) Uani 1 1 d . . . H4 H 0.4538 0.3004 1.0539 0.021 Uiso 1 1 calc R . . C5 C 0.5160(3) 0.3486(2) 0.8598(2) 0.0150(3) Uani 1 1 d . . . C6 C 0.4661(3) 0.4371(2) 0.7514(2) 0.0130(3) Uani 1 1 d . . . C7 C -0.0061(3) 0.7396(3) 0.6754(2) 0.0146(3) Uani 1 1 d . . . C8 C -0.0395(3) 0.6132(3) 0.6501(2) 0.0194(4) Uani 1 1 d . . . H8 H 0.0515 0.5089 0.6278 0.023 Uiso 1 1 calc R . . C9 C -0.2065(4) 0.6411(4) 0.6577(3) 0.0251(5) Uani 1 1 d . . . H9 H -0.2295 0.5554 0.6416 0.030 Uiso 1 1 calc R . . C10 C -0.3399(3) 0.7935(4) 0.6889(3) 0.0282(5) Uani 1 1 d . . . H10 H -0.4535 0.8119 0.6925 0.034 Uiso 1 1 calc R . . C11 C -0.3072(3) 0.9190(4) 0.7147(3) 0.0258(5) Uani 1 1 d . . . H11 H -0.3987 1.0231 0.7368 0.031 Uiso 1 1 calc R . . C12 C -0.1398(3) 0.8923(3) 0.7082(3) 0.0194(4) Uani 1 1 d . . . H12 H -0.1174 0.9780 0.7261 0.023 Uiso 1 1 calc R . . C13 C 0.2072(3) 0.8792(2) 0.7218(2) 0.0136(3) Uani 1 1 d . . . C14 C 0.2067(3) 0.9125(3) 0.8563(2) 0.0164(3) Uani 1 1 d . . . H14 H 0.2062 0.8398 0.9210 0.020 Uiso 1 1 calc R . . C15 C 0.2071(3) 1.0525(3) 0.8962(3) 0.0210(4) Uani 1 1 d . . . H15 H 0.2097 1.0735 0.9874 0.025 Uiso 1 1 calc R . . C16 C 0.2035(4) 1.1612(3) 0.8032(3) 0.0252(5) Uani 1 1 d . . . H16 H 0.2020 1.2571 0.8310 0.030 Uiso 1 1 calc R . . C17 C 0.2022(5) 1.1294(3) 0.6697(3) 0.0302(6) Uani 1 1 d . . . H17 H 0.1995 1.2039 0.6060 0.036 Uiso 1 1 calc R . . C18 C 0.2048(4) 0.9892(3) 0.6283(3) 0.0230(4) Uani 1 1 d . . . H18 H 0.2049 0.9678 0.5364 0.028 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01133(3) 0.01135(3) 0.01031(3) 0.00026(2) -0.00185(2) -0.00396(2) P1 0.01148(19) 0.01155(19) 0.01059(18) 0.00064(15) -0.00167(15) -0.00433(15) F1 0.0173(6) 0.0215(6) 0.0173(6) 0.0032(5) -0.0044(5) 0.0003(5) C1 0.0134(7) 0.0117(7) 0.0127(7) -0.0001(5) -0.0016(6) -0.0047(6) C2 0.0164(8) 0.0164(8) 0.0128(7) 0.0020(6) 0.0003(6) -0.0062(6) C3 0.0191(9) 0.0205(9) 0.0136(8) 0.0040(7) -0.0016(7) -0.0089(7) C4 0.0208(9) 0.0177(8) 0.0127(7) 0.0035(6) -0.0027(7) -0.0075(7) C5 0.0149(7) 0.0142(7) 0.0130(7) 0.0008(6) -0.0035(6) -0.0042(6) C6 0.0134(7) 0.0129(7) 0.0119(7) 0.0014(6) -0.0019(6) -0.0057(6) C7 0.0135(7) 0.0174(8) 0.0126(7) 0.0011(6) -0.0023(6) -0.0071(6) C8 0.0226(9) 0.0217(9) 0.0177(9) 0.0011(7) -0.0041(7) -0.0136(8) C9 0.0266(11) 0.0387(14) 0.0207(10) 0.0037(9) -0.0053(8) -0.0239(11) C10 0.0178(10) 0.0492(17) 0.0219(11) 0.0067(10) -0.0049(8) -0.0189(11) C11 0.0130(8) 0.0332(13) 0.0259(11) 0.0015(9) -0.0026(8) -0.0066(8) C12 0.0124(8) 0.0206(9) 0.0204(9) -0.0002(7) -0.0014(7) -0.0042(7) C13 0.0142(7) 0.0138(7) 0.0124(7) 0.0001(6) -0.0035(6) -0.0059(6) C14 0.0177(8) 0.0161(8) 0.0144(8) 0.0002(6) -0.0023(6) -0.0074(7) C15 0.0227(10) 0.0208(9) 0.0193(9) -0.0034(7) -0.0040(8) -0.0102(8) C16 0.0301(12) 0.0186(9) 0.0267(11) -0.0049(8) -0.0010(9) -0.0130(9) C17 0.0525(18) 0.0175(10) 0.0230(11) 0.0031(8) -0.0059(11) -0.0191(11) C18 0.0386(13) 0.0165(9) 0.0163(9) 0.0026(7) -0.0073(9) -0.0141(9) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.061(2) 2_666 ? Au1 P1 2.2987(5) . ? Au1 Au1 2.87624(14) 2_666 ? P1 C1 1.820(2) . ? P1 C7 1.821(2) . ? P1 C13 1.823(2) . ? F1 C5 1.367(3) . ? C1 C6 1.411(3) . ? C1 C2 1.413(3) . ? C2 C3 1.387(3) . ? C2 H2 0.9500 . ? C3 C4 1.388(3) . ? C3 H3 0.9500 . ? C4 C5 1.383(3) . ? C4 H4 0.9500 . ? C5 C6 1.395(3) . ? C6 Au1 2.061(2) 2_666 ? C7 C12 1.393(3) . ? C7 C8 1.402(3) . ? C8 C9 1.391(4) . ? C8 H8 0.9500 . ? C9 C10 1.389(5) . ? C9 H9 0.9500 . ? C10 C11 1.391(5) . ? C10 H10 0.9500 . ? C11 C12 1.400(3) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.393(3) . ? C13 C18 1.401(3) . ? C14 C15 1.396(3) . ? C14 H14 0.9500 . ? C15 C16 1.387(4) . ? C15 H15 0.9500 . ? C16 C17 1.385(4) . ? C16 H16 0.9500 . ? C17 C18 1.389(4) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 P1 174.62(6) 2_666 . ? C6 Au1 Au1 94.01(6) 2_666 2_666 ? P1 Au1 Au1 84.260(14) . 2_666 ? C1 P1 C7 104.70(10) . . ? C1 P1 C13 105.96(10) . . ? C7 P1 C13 104.95(10) . . ? C1 P1 Au1 115.31(7) . . ? C7 P1 Au1 115.05(7) . . ? C13 P1 Au1 109.98(7) . . ? C6 C1 C2 121.97(19) . . ? C6 C1 P1 120.04(15) . . ? C2 C1 P1 117.80(15) . . ? C3 C2 C1 120.0(2) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C2 C3 C4 119.6(2) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C5 C4 C3 118.6(2) . . ? C5 C4 H4 120.7 . . ? C3 C4 H4 120.7 . . ? F1 C5 C4 116.60(19) . . ? F1 C5 C6 118.08(19) . . ? C4 C5 C6 125.3(2) . . ? C5 C6 C1 114.36(19) . . ? C5 C6 Au1 121.44(15) . 2_666 ? C1 C6 Au1 123.75(15) . 2_666 ? C12 C7 C8 120.0(2) . . ? C12 C7 P1 122.30(17) . . ? C8 C7 P1 117.62(17) . . ? C9 C8 C7 119.7(2) . . ? C9 C8 H8 120.2 . . ? C7 C8 H8 120.2 . . ? C10 C9 C8 120.4(3) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C9 C10 C11 120.0(2) . . ? C9 C10 H10 120.0 . . ? C11 C10 H10 120.0 . . ? C10 C11 C12 120.1(3) . . ? C10 C11 H11 119.9 . . ? C12 C11 H11 119.9 . . ? C7 C12 C11 119.7(2) . . ? C7 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C14 C13 C18 119.2(2) . . ? C14 C13 P1 123.84(16) . . ? C18 C13 P1 116.93(16) . . ? C13 C14 C15 120.1(2) . . ? C13 C14 H14 120.0 . . ? C15 C14 H14 120.0 . . ? C16 C15 C14 120.4(2) . . ? C16 C15 H15 119.8 . . ? C14 C15 H15 119.8 . . ? C17 C16 C15 119.7(2) . . ? C17 C16 H16 120.1 . . ? C15 C16 H16 120.1 . . ? C16 C17 C18 120.4(2) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C17 C18 C13 120.2(2) . . ? C17 C18 H18 119.9 . . ? C13 C18 H18 119.9 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag Au1 Au1 P1 C1 -12.23(8) 2_666 . . . ? Au1 Au1 P1 C7 -134.30(8) 2_666 . . . ? Au1 Au1 P1 C13 107.48(7) 2_666 . . . ? C7 P1 C1 C6 147.28(17) . . . . ? C13 P1 C1 C6 -102.09(18) . . . . ? Au1 P1 C1 C6 19.8(2) . . . . ? C7 P1 C1 C2 -37.8(2) . . . . ? C13 P1 C1 C2 72.88(19) . . . . ? Au1 P1 C1 C2 -165.22(15) . . . . ? C6 C1 C2 C3 1.0(3) . . . . ? P1 C1 C2 C3 -173.89(18) . . . . ? C1 C2 C3 C4 0.9(4) . . . . ? C2 C3 C4 C5 -1.2(4) . . . . ? C3 C4 C5 F1 179.2(2) . . . . ? C3 C4 C5 C6 -0.4(4) . . . . ? F1 C5 C6 C1 -177.44(19) . . . . ? C4 C5 C6 C1 2.1(3) . . . . ? F1 C5 C6 Au1 10.0(3) . . . 2_666 ? C4 C5 C6 Au1 -170.44(19) . . . 2_666 ? C2 C1 C6 C5 -2.4(3) . . . . ? P1 C1 C6 C5 172.39(15) . . . . ? C2 C1 C6 Au1 169.99(17) . . . 2_666 ? P1 C1 C6 Au1 -15.3(3) . . . 2_666 ? C1 P1 C7 C12 122.10(19) . . . . ? C13 P1 C7 C12 10.7(2) . . . . ? Au1 P1 C7 C12 -110.27(19) . . . . ? C1 P1 C7 C8 -60.31(19) . . . . ? C13 P1 C7 C8 -171.68(17) . . . . ? Au1 P1 C7 C8 67.31(19) . . . . ? C12 C7 C8 C9 0.1(4) . . . . ? P1 C7 C8 C9 -177.54(19) . . . . ? C7 C8 C9 C10 0.7(4) . . . . ? C8 C9 C10 C11 -1.0(4) . . . . ? C9 C10 C11 C12 0.6(4) . . . . ? C8 C7 C12 C11 -0.5(4) . . . . ? P1 C7 C12 C11 177.0(2) . . . . ? C10 C11 C12 C7 0.2(4) . . . . ? C1 P1 C13 C14 -18.9(2) . . . . ? C7 P1 C13 C14 91.6(2) . . . . ? Au1 P1 C13 C14 -144.12(17) . . . . ? C1 P1 C13 C18 159.74(19) . . . . ? C7 P1 C13 C18 -89.8(2) . . . . ? Au1 P1 C13 C18 34.5(2) . . . . ? C18 C13 C14 C15 -1.2(3) . . . . ? P1 C13 C14 C15 177.37(18) . . . . ? C13 C14 C15 C16 1.6(4) . . . . ? C14 C15 C16 C17 -1.0(4) . . . . ? C15 C16 C17 C18 -0.1(5) . . . . ? C16 C17 C18 C13 0.6(5) . . . . ? C14 C13 C18 C17 0.1(4) . . . . ? P1 C13 C18 C17 -178.6(2) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 40.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 3.972 _refine_diff_density_min -3.023 _refine_diff_density_rms 0.218 # Attachment 'neda01401.cif.txt' data_neda01401 _database_code_depnum_ccdc_archive 'CCDC 725999' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H39 Au3 Br2 F3 P3, C6 H6, 1.5(C H2 Cl2)' _chemical_formula_sum 'C61.50 H48 Au3 Br2 Cl3 F3 P3' _chemical_formula_weight 1793.98 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall -P2yn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 19.0219(3) _cell_length_b 11.9992(2) _cell_length_c 26.0829(4) _cell_angle_alpha 90.00 _cell_angle_beta 103.3430(10) _cell_angle_gamma 90.00 _cell_volume 5792.65(16) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 141422 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 29.131 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.057 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3388 _exptl_absorpt_coefficient_mu 9.229 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.243 _exptl_absorpt_correction_T_max 0.524 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 67386 _diffrn_reflns_av_R_equivalents 0.0697 _diffrn_reflns_av_sigmaI/netI 0.0501 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -35 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 29.00 _reflns_number_total 15370 _reflns_number_gt 12246 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; The structure bears 1 benzene molecule and 1.5 dichloromethane molecules in the asym. unit, which are disordered. The DCM sites are either occupied by two well-defined DCM molecules (50 percent probability) or by one very mobile DCM molecule (50 percent probability). According to this variability the benzene molecule in the closer proximity is also disordered in 50 : 50 ratio. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0659P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 15370 _refine_ls_number_parameters 715 _refine_ls_number_restraints 61 _refine_ls_R_factor_all 0.0592 _refine_ls_R_factor_gt 0.0413 _refine_ls_wR_factor_ref 0.1079 _refine_ls_wR_factor_gt 0.1017 _refine_ls_goodness_of_fit_ref 1.040 _refine_ls_restrained_S_all 1.043 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.725749(11) 0.430661(16) 0.066386(8) 0.01589(6) Uani 1 1 d . . . Au2 Au 0.809833(11) 0.269500(16) 0.050048(8) 0.01630(6) Uani 1 1 d . . . Au3 Au 0.928318(12) 0.387197(17) 0.130094(9) 0.02079(6) Uani 1 1 d . . . Br1 Br 0.62208(3) 0.56298(4) 0.07188(2) 0.02247(12) Uani 1 1 d . . . Br2 Br 0.89847(3) 0.58331(5) 0.12246(3) 0.02838(14) Uani 1 1 d . . . P1 P 0.72744(8) 0.47311(11) -0.01947(6) 0.0186(3) Uani 1 1 d . . . P2 P 0.72743(8) 0.17298(11) 0.08916(5) 0.0165(3) Uani 1 1 d . . . P3 P 0.96969(8) 0.21158(12) 0.14236(6) 0.0203(3) Uani 1 1 d . . . F1 F 0.97483(18) 0.2806(3) 0.02095(14) 0.0286(8) Uani 1 1 d . . . F2 F 0.75036(18) 0.5404(2) 0.18611(12) 0.0227(7) Uani 1 1 d . . . F3 F 0.79316(19) 0.0676(3) -0.02599(14) 0.0308(8) Uani 1 1 d . . . C1 C 0.8177(3) 0.4520(4) -0.0285(2) 0.0204(11) Uani 1 1 d . . . C2 C 0.8436(4) 0.5164(5) -0.0653(3) 0.0314(14) Uani 1 1 d . . . H2 H 0.8137 0.5716 -0.0855 0.038 Uiso 1 1 calc R . . C3 C 0.9123(4) 0.4992(5) -0.0719(3) 0.0375(17) Uani 1 1 d . . . H3 H 0.9302 0.5426 -0.0966 0.045 Uiso 1 1 calc R . . C4 C 0.9557(3) 0.4180(5) -0.0422(2) 0.0290(14) Uani 1 1 d . . . H4 H 1.0034 0.4054 -0.0464 0.035 Uiso 1 1 calc R . . C5 C 0.9287(3) 0.3565(4) -0.0068(2) 0.0214(11) Uani 1 1 d . . . C6 C 0.8595(3) 0.3684(4) 0.0018(2) 0.0190(11) Uani 1 1 d . . . C7 C 0.7037(3) 0.6166(4) -0.0396(2) 0.0218(12) Uani 1 1 d . . . C8 C 0.7295(4) 0.7009(5) -0.0046(2) 0.0285(13) Uani 1 1 d . . . H8 H 0.7589 0.6834 0.0291 0.034 Uiso 1 1 calc R . . C9 C 0.7127(4) 0.8119(5) -0.0181(3) 0.0320(14) Uani 1 1 d . . . H9 H 0.7311 0.8698 0.0061 0.038 Uiso 1 1 calc R . . C10 C 0.6694(4) 0.8372(5) -0.0668(3) 0.0327(15) Uani 1 1 d . . . H10 H 0.6576 0.9126 -0.0760 0.039 Uiso 1 1 calc R . . C11 C 0.6433(4) 0.7532(5) -0.1020(3) 0.0338(15) Uani 1 1 d . . . H11 H 0.6139 0.7714 -0.1356 0.041 Uiso 1 1 calc R . . C12 C 0.6592(3) 0.6426(5) -0.0892(2) 0.0266(13) Uani 1 1 d . . . H12 H 0.6404 0.5851 -0.1136 0.032 Uiso 1 1 calc R . . C13 C 0.6683(3) 0.3867(4) -0.0673(2) 0.0223(12) Uani 1 1 d . . . C14 C 0.6942(3) 0.3153(5) -0.1010(2) 0.0269(13) Uani 1 1 d . . . H14 H 0.7446 0.3100 -0.0987 0.032 Uiso 1 1 calc R . . C15 C 0.6468(4) 0.2527(5) -0.1377(3) 0.0328(15) Uani 1 1 d . . . H15 H 0.6650 0.2032 -0.1600 0.039 Uiso 1 1 calc R . . C16 C 0.5724(4) 0.2610(6) -0.1425(3) 0.0333(15) Uani 1 1 d . . . H16 H 0.5398 0.2198 -0.1687 0.040 Uiso 1 1 calc R . . C17 C 0.5470(3) 0.3300(5) -0.1085(2) 0.0303(14) Uani 1 1 d . . . H17 H 0.4964 0.3348 -0.1112 0.036 Uiso 1 1 calc R . . C18 C 0.5933(3) 0.3922(4) -0.0708(2) 0.0228(12) Uani 1 1 d . . . H18 H 0.5749 0.4385 -0.0474 0.027 Uiso 1 1 calc R . . C19 C 0.7256(3) 0.2511(4) 0.1480(2) 0.0173(10) Uani 1 1 d . . . C20 C 0.7187(3) 0.2026(5) 0.1945(2) 0.0199(11) Uani 1 1 d . . . H20 H 0.7107 0.1246 0.1963 0.024 Uiso 1 1 calc R . . C21 C 0.7233(3) 0.2679(4) 0.2381(2) 0.0227(12) Uani 1 1 d . . . H21 H 0.7193 0.2354 0.2705 0.027 Uiso 1 1 calc R . . C22 C 0.7340(3) 0.3837(4) 0.2348(2) 0.0212(11) Uani 1 1 d . . . H22 H 0.7377 0.4300 0.2649 0.025 Uiso 1 1 calc R . . C23 C 0.7392(3) 0.4285(4) 0.1870(2) 0.0203(11) Uani 1 1 d . . . C24 C 0.7342(3) 0.3674(4) 0.1416(2) 0.0172(10) Uani 1 1 d . . . C25 C 0.6369(3) 0.1796(4) 0.0471(2) 0.0206(11) Uani 1 1 d . . . C26 C 0.5827(3) 0.2402(5) 0.0624(2) 0.0242(12) Uani 1 1 d . . . H26 H 0.5932 0.2840 0.0936 0.029 Uiso 1 1 calc R . . C27 C 0.5119(3) 0.2349(5) 0.0306(3) 0.0312(14) Uani 1 1 d . . . H27 H 0.4744 0.2760 0.0404 0.037 Uiso 1 1 calc R . . C28 C 0.4969(4) 0.1717(5) -0.0138(3) 0.0363(16) Uani 1 1 d . . . H28 H 0.4488 0.1682 -0.0345 0.044 Uiso 1 1 calc R . . C29 C 0.5514(4) 0.1118(5) -0.0296(3) 0.0357(15) Uani 1 1 d . . . H29 H 0.5404 0.0673 -0.0605 0.043 Uiso 1 1 calc R . . C30 C 0.6211(4) 0.1182(5) 0.0005(2) 0.0268(13) Uani 1 1 d . . . H30 H 0.6588 0.0803 -0.0107 0.032 Uiso 1 1 calc R . . C31 C 0.7369(3) 0.0262(4) 0.1061(2) 0.0198(11) Uani 1 1 d . . . C32 C 0.6758(3) -0.0403(5) 0.1030(2) 0.0273(13) Uani 1 1 d . . . H32 H 0.6289 -0.0083 0.0931 0.033 Uiso 1 1 calc R . . C33 C 0.6836(4) -0.1524(5) 0.1144(2) 0.0307(14) Uani 1 1 d . . . H33 H 0.6417 -0.1966 0.1127 0.037 Uiso 1 1 calc R . . C34 C 0.7510(4) -0.2020(5) 0.1281(2) 0.0255(13) Uani 1 1 d . . . H34 H 0.7554 -0.2801 0.1339 0.031 Uiso 1 1 calc R . . C35 C 0.8113(4) -0.1366(5) 0.1333(2) 0.0275(13) Uani 1 1 d . . . H35 H 0.8578 -0.1695 0.1436 0.033 Uiso 1 1 calc R . . C36 C 0.8052(3) -0.0234(5) 0.1236(2) 0.0256(13) Uani 1 1 d . . . H36 H 0.8475 0.0213 0.1289 0.031 Uiso 1 1 calc R . . C37 C 0.9408(3) 0.1144(4) 0.0874(2) 0.0205(11) Uani 1 1 d . . . C38 C 0.9808(3) 0.0180(5) 0.0854(2) 0.0251(12) Uani 1 1 d . . . H38 H 1.0248 0.0068 0.1109 0.030 Uiso 1 1 calc R . . C39 C 0.9577(4) -0.0620(5) 0.0466(3) 0.0317(15) Uani 1 1 d . . . H39 H 0.9855 -0.1275 0.0458 0.038 Uiso 1 1 calc R . . C40 C 0.8939(3) -0.0459(5) 0.0092(2) 0.0279(13) Uani 1 1 d . . . H40 H 0.8765 -0.1002 -0.0171 0.033 Uiso 1 1 calc R . . C41 C 0.8562(3) 0.0522(5) 0.0115(2) 0.0241(12) Uani 1 1 d . . . C42 C 0.8774(3) 0.1333(4) 0.0495(2) 0.0192(11) Uani 1 1 d . . . C43 C 0.9482(3) 0.1450(5) 0.1996(2) 0.0249(12) Uani 1 1 d . . . C44 C 0.9059(3) 0.2012(5) 0.2284(2) 0.0279(13) Uani 1 1 d . . . H44 H 0.8864 0.2725 0.2174 0.033 Uiso 1 1 calc R . . C45 C 0.8925(3) 0.1511(6) 0.2738(2) 0.0339(15) Uani 1 1 d . . . H45 H 0.8645 0.1897 0.2940 0.041 Uiso 1 1 calc R . . C46 C 0.9191(3) 0.0476(6) 0.2896(2) 0.0328(15) Uani 1 1 d . . . H46 H 0.9096 0.0146 0.3204 0.039 Uiso 1 1 calc R . . C47 C 0.9599(4) -0.0086(6) 0.2605(3) 0.0422(18) Uani 1 1 d . . . H47 H 0.9782 -0.0806 0.2712 0.051 Uiso 1 1 calc R . . C48 C 0.9744(4) 0.0395(5) 0.2155(3) 0.0372(16) Uani 1 1 d . . . H48 H 1.0024 0.0001 0.1956 0.045 Uiso 1 1 calc R . . C49 C 1.0685(3) 0.2105(4) 0.1579(2) 0.0216(12) Uani 1 1 d . . . C50 C 1.1062(4) 0.2190(6) 0.2091(3) 0.0359(15) Uani 1 1 d . . . H50 H 1.0815 0.2191 0.2369 0.043 Uiso 1 1 calc R . . C51 C 1.1812(4) 0.2274(7) 0.2201(3) 0.049(2) Uani 1 1 d . . . H51 H 1.2076 0.2348 0.2556 0.059 Uiso 1 1 calc R . . C52 C 1.2183(4) 0.2253(6) 0.1798(3) 0.0365(16) Uani 1 1 d . . . H52 H 1.2695 0.2292 0.1878 0.044 Uiso 1 1 calc R . . C53 C 1.1803(3) 0.2175(5) 0.1291(2) 0.0278(13) Uani 1 1 d . . . H53 H 1.2052 0.2169 0.1015 0.033 Uiso 1 1 calc R . . C54 C 1.1053(3) 0.2103(5) 0.1172(2) 0.0239(12) Uani 1 1 d . . . H54 H 1.0792 0.2053 0.0816 0.029 Uiso 1 1 calc R . . C1SA C 0.1288(8) 0.8222(15) 0.1240(6) 0.0511(12) Uani 0.50 1 d PGD A 1 H1SA H 0.1309 0.8035 0.0890 0.061 Uiso 0.50 1 calc PR A 1 C2SA C 0.0729(8) 0.7788(12) 0.1443(5) 0.0511(12) Uani 0.50 1 d PD A 1 H2SA H 0.0344 0.7388 0.1222 0.061 Uiso 0.50 1 calc PR A 1 C3SA C 0.0742(7) 0.7947(13) 0.1974(5) 0.0511(12) Uani 0.50 1 d PD A 1 H3SA H 0.0415 0.7564 0.2138 0.061 Uiso 0.50 1 calc PR A 1 C4SA C 0.1251(8) 0.8687(15) 0.2256(6) 0.0511(12) Uani 0.50 1 d PD A 1 H4SA H 0.1275 0.8795 0.2621 0.061 Uiso 0.50 1 calc PR A 1 C5SA C 0.1727(9) 0.9274(16) 0.2022(8) 0.0511(12) Uani 0.50 1 d PD A 1 H5SA H 0.1985 0.9900 0.2193 0.061 Uiso 0.50 1 calc PR A 1 C6SA C 0.1815(10) 0.8921(16) 0.1533(6) 0.0511(12) Uani 0.50 1 d PD A 1 H6SA H 0.2220 0.9149 0.1403 0.061 Uiso 0.50 1 calc PR A 1 C1SB C 0.1299(9) 0.8055(14) 0.1325(6) 0.0511(12) Uani 0.50 1 d PGD B 2 H1SB H 0.1245 0.7741 0.0984 0.061 Uiso 0.50 1 calc PR B 2 C2SB C 0.0948(9) 0.7545(12) 0.1680(5) 0.0511(12) Uani 0.50 1 d PD B 2 H2SB H 0.0684 0.6877 0.1577 0.061 Uiso 0.50 1 calc PR B 2 C3SB C 0.0969(8) 0.7982(12) 0.2182(5) 0.0511(12) Uani 0.50 1 d PD B 2 H3SB H 0.0687 0.7700 0.2410 0.061 Uiso 0.50 1 calc PR B 2 C4SB C 0.1451(9) 0.8878(14) 0.2313(7) 0.0511(12) Uani 0.50 1 d PD B 2 H4SB H 0.1490 0.9219 0.2647 0.061 Uiso 0.50 1 calc PR B 2 C5SB C 0.1880(10) 0.9309(16) 0.1989(7) 0.0511(12) Uani 0.50 1 d PD B 2 H5SB H 0.2269 0.9798 0.2129 0.061 Uiso 0.50 1 calc PR B 2 C6SB C 0.1728(10) 0.9010(16) 0.1455(6) 0.0511(12) Uani 0.50 1 d PD B 2 H6SB H 0.1903 0.9425 0.1199 0.061 Uiso 0.50 1 calc PR B 2 Cl1 Cl 0.2949(2) 0.0569(4) 0.30884(17) 0.0563(10) Uani 0.50 1 d P C 1 C7S C 0.3750(9) 0.0068(12) 0.2979(6) 0.052(4) Uani 0.50 1 d P C 1 H7S1 H 0.3816 -0.0712 0.3105 0.063 Uiso 0.50 1 calc PR C 1 H7S2 H 0.4154 0.0513 0.3189 0.063 Uiso 0.50 1 calc PR C 1 Cl2 Cl 0.3791(2) 0.0111(4) 0.23113(18) 0.0563(11) Uani 0.50 1 d P C 1 Cl3 Cl 0.5309(2) 0.1903(4) 0.1943(2) 0.0729(15) Uani 0.50 1 d P D 1 C8S C 0.5659(9) 0.0803(14) 0.2338(5) 0.047(4) Uani 0.50 1 d P D 1 H8S1 H 0.5345 0.0644 0.2583 0.056 Uiso 0.50 1 calc PR D 1 H8S2 H 0.6143 0.1009 0.2551 0.056 Uiso 0.50 1 calc PR D 1 Cl4 Cl 0.5733(3) -0.0374(4) 0.1983(3) 0.0794(17) Uani 0.50 1 d P D 1 Cl5 Cl 0.5293(4) 0.0833(8) 0.1717(3) 0.136(3) Uani 0.50 1 d PDU E 2 C9S C 0.5273(15) 0.024(3) 0.2309(11) 0.134(11) Uani 0.50 1 d PDU E 2 H9S1 H 0.5501 0.0748 0.2598 0.160 Uiso 0.50 1 calc PR E 2 H9S2 H 0.5554 -0.0463 0.2352 0.160 Uiso 0.50 1 calc PR E 2 Cl6 Cl 0.4406(6) -0.0037(7) 0.2351(4) 0.140(3) Uani 0.50 1 d PDU E 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02095(11) 0.01276(10) 0.01720(10) 0.00011(7) 0.01105(8) 0.00040(7) Au2 0.02062(11) 0.01348(10) 0.01830(10) -0.00068(7) 0.01170(8) 0.00025(7) Au3 0.02377(12) 0.01732(11) 0.02467(12) -0.00360(8) 0.01253(9) 0.00013(8) Br1 0.0267(3) 0.0177(3) 0.0275(3) 0.0013(2) 0.0155(2) 0.0046(2) Br2 0.0347(3) 0.0178(3) 0.0375(3) -0.0011(2) 0.0184(3) 0.0006(2) P1 0.0246(7) 0.0164(6) 0.0182(7) 0.0014(5) 0.0120(6) 0.0008(6) P2 0.0214(7) 0.0128(6) 0.0181(7) -0.0014(5) 0.0104(6) -0.0007(5) P3 0.0231(7) 0.0175(7) 0.0240(7) -0.0020(6) 0.0130(6) 0.0012(6) F1 0.0264(18) 0.0278(18) 0.037(2) 0.0068(15) 0.0182(16) 0.0041(15) F2 0.0378(19) 0.0100(14) 0.0239(17) -0.0027(12) 0.0145(15) -0.0036(13) F3 0.031(2) 0.0318(19) 0.031(2) -0.0093(15) 0.0111(16) 0.0000(15) C1 0.024(3) 0.017(3) 0.023(3) -0.001(2) 0.010(2) 0.000(2) C2 0.039(4) 0.028(3) 0.033(3) 0.013(3) 0.020(3) 0.005(3) C3 0.044(4) 0.032(3) 0.047(4) 0.017(3) 0.033(3) 0.005(3) C4 0.027(3) 0.032(3) 0.034(3) 0.004(3) 0.020(3) -0.006(3) C5 0.024(3) 0.017(3) 0.025(3) 0.000(2) 0.010(2) 0.002(2) C6 0.027(3) 0.013(2) 0.022(3) -0.001(2) 0.016(2) -0.007(2) C7 0.029(3) 0.018(3) 0.024(3) 0.001(2) 0.018(2) -0.002(2) C8 0.043(4) 0.025(3) 0.024(3) -0.001(2) 0.021(3) -0.006(3) C9 0.046(4) 0.019(3) 0.038(4) 0.002(3) 0.024(3) 0.003(3) C10 0.043(4) 0.023(3) 0.041(4) 0.007(3) 0.027(3) 0.012(3) C11 0.039(4) 0.033(3) 0.036(4) 0.011(3) 0.022(3) 0.003(3) C12 0.028(3) 0.028(3) 0.027(3) 0.003(2) 0.013(3) 0.003(3) C13 0.033(3) 0.022(3) 0.014(3) 0.002(2) 0.009(2) 0.005(2) C14 0.029(3) 0.029(3) 0.028(3) -0.003(3) 0.017(3) 0.002(3) C15 0.035(4) 0.038(4) 0.029(3) -0.014(3) 0.015(3) 0.000(3) C16 0.029(3) 0.046(4) 0.023(3) -0.006(3) 0.003(3) -0.001(3) C17 0.024(3) 0.042(4) 0.024(3) 0.001(3) 0.004(3) -0.001(3) C18 0.028(3) 0.020(3) 0.024(3) 0.002(2) 0.014(2) 0.005(2) C19 0.021(3) 0.013(2) 0.020(3) -0.001(2) 0.009(2) 0.001(2) C20 0.025(3) 0.017(3) 0.020(3) -0.001(2) 0.010(2) -0.001(2) C21 0.038(3) 0.016(3) 0.016(3) 0.003(2) 0.010(2) 0.003(2) C22 0.028(3) 0.023(3) 0.015(3) -0.001(2) 0.010(2) 0.000(2) C23 0.025(3) 0.014(3) 0.024(3) -0.001(2) 0.011(2) -0.002(2) C24 0.022(3) 0.018(2) 0.014(2) 0.000(2) 0.008(2) -0.003(2) C25 0.027(3) 0.014(2) 0.022(3) 0.003(2) 0.008(2) -0.001(2) C26 0.027(3) 0.019(3) 0.030(3) 0.003(2) 0.013(3) 0.001(2) C27 0.024(3) 0.033(3) 0.038(4) 0.006(3) 0.009(3) 0.005(3) C28 0.029(3) 0.032(4) 0.042(4) 0.011(3) -0.004(3) -0.005(3) C29 0.046(4) 0.026(3) 0.031(4) 0.001(3) 0.000(3) -0.002(3) C30 0.035(3) 0.024(3) 0.020(3) -0.001(2) 0.005(3) 0.006(3) C31 0.027(3) 0.017(3) 0.019(3) 0.000(2) 0.013(2) -0.003(2) C32 0.029(3) 0.022(3) 0.030(3) 0.004(2) 0.007(3) -0.001(2) C33 0.042(4) 0.018(3) 0.029(3) 0.006(2) 0.002(3) -0.007(3) C34 0.053(4) 0.013(2) 0.013(3) -0.001(2) 0.011(3) -0.001(3) C35 0.038(4) 0.021(3) 0.030(3) 0.006(2) 0.020(3) 0.009(3) C36 0.026(3) 0.020(3) 0.036(3) 0.005(2) 0.019(3) 0.004(2) C37 0.022(3) 0.018(3) 0.027(3) -0.001(2) 0.015(2) -0.003(2) C38 0.024(3) 0.023(3) 0.032(3) -0.001(2) 0.014(3) 0.002(2) C39 0.038(4) 0.022(3) 0.042(4) -0.004(3) 0.024(3) 0.005(3) C40 0.035(3) 0.022(3) 0.032(3) -0.013(2) 0.018(3) 0.001(3) C41 0.024(3) 0.023(3) 0.029(3) -0.003(2) 0.014(3) -0.002(2) C42 0.020(3) 0.013(2) 0.029(3) -0.001(2) 0.015(2) 0.001(2) C43 0.031(3) 0.026(3) 0.022(3) 0.000(2) 0.015(3) -0.002(2) C44 0.021(3) 0.038(3) 0.027(3) 0.001(3) 0.011(2) 0.002(3) C45 0.025(3) 0.058(4) 0.023(3) 0.002(3) 0.014(3) 0.005(3) C46 0.033(4) 0.046(4) 0.022(3) 0.003(3) 0.011(3) -0.008(3) C47 0.059(5) 0.033(4) 0.042(4) 0.006(3) 0.027(4) 0.000(3) C48 0.052(4) 0.032(3) 0.037(4) 0.003(3) 0.031(3) 0.010(3) C49 0.021(3) 0.018(3) 0.029(3) -0.003(2) 0.011(2) 0.000(2) C50 0.032(4) 0.051(4) 0.029(3) -0.002(3) 0.016(3) -0.001(3) C51 0.032(4) 0.075(6) 0.038(4) -0.002(4) 0.007(3) -0.007(4) C52 0.027(3) 0.047(4) 0.037(4) 0.001(3) 0.011(3) 0.001(3) C53 0.030(3) 0.028(3) 0.031(3) 0.003(3) 0.019(3) 0.003(3) C54 0.024(3) 0.024(3) 0.028(3) -0.002(2) 0.016(2) 0.000(2) C1SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C2SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C3SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C4SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C5SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C6SA 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C1SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C2SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C3SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C4SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C5SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) C6SB 0.048(3) 0.048(2) 0.060(3) -0.001(2) 0.016(2) 0.018(2) Cl1 0.061(3) 0.061(3) 0.045(2) -0.0002(19) 0.009(2) 0.007(2) C7S 0.068(11) 0.030(8) 0.051(10) -0.012(7) -0.004(8) 0.010(7) Cl2 0.049(2) 0.057(3) 0.064(3) -0.009(2) 0.015(2) -0.009(2) Cl3 0.049(3) 0.046(2) 0.127(5) 0.019(3) 0.027(3) 0.008(2) C8S 0.047(9) 0.074(11) 0.018(6) -0.002(7) 0.006(6) -0.012(8) Cl4 0.072(3) 0.036(2) 0.146(5) -0.014(3) 0.057(4) -0.003(2) Cl5 0.100(5) 0.201(7) 0.114(5) 0.011(5) 0.038(4) 0.001(5) C9S 0.139(14) 0.132(14) 0.125(14) 0.016(9) 0.020(9) -0.003(9) Cl6 0.182(7) 0.111(5) 0.148(6) -0.045(5) 0.079(6) -0.052(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.075(5) . ? Au1 P1 2.3040(14) . ? Au1 Br1 2.5613(6) . ? Au1 Au2 2.6065(3) . ? Au2 C42 2.081(5) . ? Au2 C6 2.106(5) . ? Au2 P2 2.3615(13) . ? Au2 Au3 3.0432(3) . ? Au3 P3 2.2464(14) . ? Au3 Br2 2.4181(6) . ? P1 C13 1.802(6) . ? P1 C1 1.804(6) . ? P1 C7 1.826(6) . ? P2 C19 1.805(5) . ? P2 C31 1.814(5) . ? P2 C25 1.817(6) . ? P3 C43 1.822(5) . ? P3 C49 1.829(6) . ? P3 C37 1.832(6) . ? F1 C5 1.353(6) . ? F2 C23 1.360(6) . ? F3 C41 1.373(7) . ? C1 C6 1.404(8) . ? C1 C2 1.408(7) . ? C2 C3 1.373(8) . ? C2 H2 0.9500 . ? C3 C4 1.391(9) . ? C3 H3 0.9500 . ? C4 C5 1.372(8) . ? C4 H4 0.9500 . ? C5 C6 1.393(7) . ? C7 C8 1.374(8) . ? C7 C12 1.409(8) . ? C8 C9 1.396(8) . ? C8 H8 0.9500 . ? C9 C10 1.377(10) . ? C9 H9 0.9500 . ? C10 C11 1.377(9) . ? C10 H10 0.9500 . ? C11 C12 1.385(8) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.396(7) . ? C13 C18 1.410(8) . ? C14 C15 1.376(9) . ? C14 H14 0.9500 . ? C15 C16 1.396(9) . ? C15 H15 0.9500 . ? C16 C17 1.379(9) . ? C16 H16 0.9500 . ? C17 C18 1.379(8) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.380(7) . ? C19 C24 1.419(7) . ? C20 C21 1.367(7) . ? C20 H20 0.9500 . ? C21 C22 1.410(7) . ? C21 H21 0.9500 . ? C22 C23 1.383(7) . ? C22 H22 0.9500 . ? C23 C24 1.377(7) . ? C25 C30 1.393(8) . ? C25 C26 1.394(8) . ? C26 C27 1.410(9) . ? C26 H26 0.9500 . ? C27 C28 1.360(9) . ? C27 H27 0.9500 . ? C28 C29 1.398(10) . ? C28 H28 0.9500 . ? C29 C30 1.379(9) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.396(8) . ? C31 C36 1.406(8) . ? C32 C33 1.378(8) . ? C32 H32 0.9500 . ? C33 C34 1.384(9) . ? C33 H33 0.9500 . ? C34 C35 1.370(9) . ? C34 H34 0.9500 . ? C35 C36 1.382(8) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C37 C42 1.391(8) . ? C37 C38 1.392(8) . ? C38 C39 1.390(8) . ? C38 H38 0.9500 . ? C39 C40 1.384(9) . ? C39 H39 0.9500 . ? C40 C41 1.387(8) . ? C40 H40 0.9500 . ? C41 C42 1.380(8) . ? C43 C48 1.388(9) . ? C43 C44 1.394(8) . ? C44 C45 1.404(8) . ? C44 H44 0.9500 . ? C45 C46 1.368(9) . ? C45 H45 0.9500 . ? C46 C47 1.380(9) . ? C46 H46 0.9500 . ? C47 C48 1.391(9) . ? C47 H47 0.9500 . ? C48 H48 0.9500 . ? C49 C50 1.367(9) . ? C49 C54 1.399(7) . ? C50 C51 1.393(10) . ? C50 H50 0.9500 . ? C51 C52 1.394(9) . ? C51 H51 0.9500 . ? C52 C53 1.356(9) . ? C52 H52 0.9500 . ? C53 C54 1.390(8) . ? C53 H53 0.9500 . ? C54 H54 0.9500 . ? C1SA C6SA 1.393(5) . ? C1SA C2SA 1.393(5) . ? C1SA H1SA 0.9500 . ? C2SA C3SA 1.393(5) . ? C2SA H2SA 0.9500 . ? C3SA C4SA 1.393(5) . ? C3SA H3SA 0.9500 . ? C4SA C5SA 1.393(5) . ? C4SA H4SA 0.9500 . ? C5SA C6SA 1.393(5) . ? C5SA H5SA 0.9500 . ? C6SA H6SA 0.9500 . ? C1SB C6SB 1.402(5) . ? C1SB C2SB 1.403(5) . ? C1SB H1SB 0.9500 . ? C2SB C3SB 1.403(5) . ? C2SB H2SB 0.9500 . ? C3SB C4SB 1.403(5) . ? C3SB H3SB 0.9500 . ? C4SB C5SB 1.402(5) . ? C4SB H4SB 0.9500 . ? C5SB C6SB 1.402(5) . ? C5SB H5SB 0.9500 . ? C6SB H6SB 0.9500 . ? Cl1 C7S 1.721(17) . ? C7S Cl2 1.763(17) . ? C7S H7S1 0.9900 . ? C7S H7S2 0.9900 . ? Cl3 C8S 1.712(17) . ? C8S Cl4 1.712(16) . ? C8S H8S1 0.9900 . ? C8S H8S2 0.9900 . ? Cl5 C9S 1.71(2) . ? C9S Cl6 1.71(2) . ? C9S H9S1 0.9900 . ? C9S H9S2 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 P1 169.88(15) . . ? C24 Au1 Br1 93.81(14) . . ? P1 Au1 Br1 95.79(4) . . ? C24 Au1 Au2 88.09(14) . . ? P1 Au1 Au2 81.86(4) . . ? Br1 Au1 Au2 168.079(17) . . ? C42 Au2 C6 94.3(2) . . ? C42 Au2 P2 95.19(14) . . ? C6 Au2 P2 165.63(17) . . ? C42 Au2 Au1 170.75(15) . . ? C6 Au2 Au1 93.24(14) . . ? P2 Au2 Au1 78.45(3) . . ? C42 Au2 Au3 90.51(16) . . ? C6 Au2 Au3 77.59(16) . . ? P2 Au2 Au3 113.05(4) . . ? Au1 Au2 Au3 85.916(8) . . ? P3 Au3 Br2 172.98(4) . . ? P3 Au3 Au2 80.91(4) . . ? Br2 Au3 Au2 105.812(18) . . ? C13 P1 C1 106.8(3) . . ? C13 P1 C7 105.7(3) . . ? C1 P1 C7 105.9(2) . . ? C13 P1 Au1 113.50(18) . . ? C1 P1 Au1 108.83(19) . . ? C7 P1 Au1 115.45(18) . . ? C19 P2 C31 108.5(2) . . ? C19 P2 C25 106.8(3) . . ? C31 P2 C25 102.5(3) . . ? C19 P2 Au2 104.91(17) . . ? C31 P2 Au2 122.87(18) . . ? C25 P2 Au2 110.36(17) . . ? C43 P3 C49 103.3(3) . . ? C43 P3 C37 106.2(3) . . ? C49 P3 C37 106.1(2) . . ? C43 P3 Au3 112.98(19) . . ? C49 P3 Au3 110.26(18) . . ? C37 P3 Au3 116.98(19) . . ? C6 C1 C2 122.3(5) . . ? C6 C1 P1 117.4(4) . . ? C2 C1 P1 120.4(4) . . ? C3 C2 C1 119.8(6) . . ? C3 C2 H2 120.1 . . ? C1 C2 H2 120.1 . . ? C2 C3 C4 119.7(5) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C5 C4 C3 119.1(6) . . ? C5 C4 H4 120.5 . . ? C3 C4 H4 120.5 . . ? F1 C5 C4 115.2(5) . . ? F1 C5 C6 120.2(5) . . ? C4 C5 C6 124.6(6) . . ? C5 C6 C1 114.6(5) . . ? C5 C6 Au2 127.6(4) . . ? C1 C6 Au2 117.7(4) . . ? C8 C7 C12 119.6(5) . . ? C8 C7 P1 118.5(5) . . ? C12 C7 P1 121.9(4) . . ? C7 C8 C9 120.6(6) . . ? C7 C8 H8 119.7 . . ? C9 C8 H8 119.7 . . ? C10 C9 C8 119.8(6) . . ? C10 C9 H9 120.1 . . ? C8 C9 H9 120.1 . . ? C9 C10 C11 120.0(6) . . ? C9 C10 H10 120.0 . . ? C11 C10 H10 120.0 . . ? C10 C11 C12 121.1(7) . . ? C10 C11 H11 119.5 . . ? C12 C11 H11 119.5 . . ? C11 C12 C7 119.0(6) . . ? C11 C12 H12 120.5 . . ? C7 C12 H12 120.5 . . ? C14 C13 C18 119.1(6) . . ? C14 C13 P1 122.3(5) . . ? C18 C13 P1 118.6(4) . . ? C15 C14 C13 120.3(6) . . ? C15 C14 H14 119.9 . . ? C13 C14 H14 119.9 . . ? C14 C15 C16 120.7(6) . . ? C14 C15 H15 119.6 . . ? C16 C15 H15 119.6 . . ? C17 C16 C15 119.0(6) . . ? C17 C16 H16 120.5 . . ? C15 C16 H16 120.5 . . ? C16 C17 C18 121.5(6) . . ? C16 C17 H17 119.3 . . ? C18 C17 H17 119.3 . . ? C17 C18 C13 119.5(5) . . ? C17 C18 H18 120.3 . . ? C13 C18 H18 120.3 . . ? C20 C19 C24 123.7(5) . . ? C20 C19 P2 123.6(4) . . ? C24 C19 P2 112.7(4) . . ? C21 C20 C19 119.3(5) . . ? C21 C20 H20 120.4 . . ? C19 C20 H20 120.4 . . ? C20 C21 C22 119.8(5) . . ? C20 C21 H21 120.1 . . ? C22 C21 H21 120.1 . . ? C23 C22 C21 118.7(5) . . ? C23 C22 H22 120.7 . . ? C21 C22 H22 120.7 . . ? F2 C23 C24 119.4(5) . . ? F2 C23 C22 116.3(5) . . ? C24 C23 C22 124.3(5) . . ? C23 C24 C19 114.2(5) . . ? C23 C24 Au1 126.3(4) . . ? C19 C24 Au1 119.0(4) . . ? C30 C25 C26 120.1(5) . . ? C30 C25 P2 119.2(4) . . ? C26 C25 P2 120.7(4) . . ? C25 C26 C27 118.5(6) . . ? C25 C26 H26 120.7 . . ? C27 C26 H26 120.7 . . ? C28 C27 C26 120.7(6) . . ? C28 C27 H27 119.7 . . ? C26 C27 H27 119.7 . . ? C27 C28 C29 120.9(6) . . ? C27 C28 H28 119.6 . . ? C29 C28 H28 119.6 . . ? C30 C29 C28 119.1(6) . . ? C30 C29 H29 120.5 . . ? C28 C29 H29 120.5 . . ? C29 C30 C25 120.7(6) . . ? C29 C30 H30 119.6 . . ? C25 C30 H30 119.6 . . ? C32 C31 C36 118.1(5) . . ? C32 C31 P2 120.5(4) . . ? C36 C31 P2 121.5(4) . . ? C33 C32 C31 119.9(6) . . ? C33 C32 H32 120.0 . . ? C31 C32 H32 120.0 . . ? C32 C33 C34 121.5(6) . . ? C32 C33 H33 119.2 . . ? C34 C33 H33 119.2 . . ? C35 C34 C33 118.9(5) . . ? C35 C34 H34 120.6 . . ? C33 C34 H34 120.6 . . ? C34 C35 C36 120.8(6) . . ? C34 C35 H35 119.6 . . ? C36 C35 H35 119.6 . . ? C35 C36 C31 120.5(6) . . ? C35 C36 H36 119.8 . . ? C31 C36 H36 119.8 . . ? C42 C37 C38 120.1(5) . . ? C42 C37 P3 120.5(4) . . ? C38 C37 P3 119.3(5) . . ? C39 C38 C37 121.1(6) . . ? C39 C38 H38 119.5 . . ? C37 C38 H38 119.5 . . ? C40 C39 C38 119.7(5) . . ? C40 C39 H39 120.2 . . ? C38 C39 H39 120.2 . . ? C39 C40 C41 117.8(6) . . ? C39 C40 H40 121.1 . . ? C41 C40 H40 121.1 . . ? F3 C41 C42 118.6(5) . . ? F3 C41 C40 117.3(5) . . ? C42 C41 C40 124.1(6) . . ? C41 C42 C37 117.2(5) . . ? C41 C42 Au2 118.7(4) . . ? C37 C42 Au2 124.0(4) . . ? C48 C43 C44 119.5(5) . . ? C48 C43 P3 120.7(4) . . ? C44 C43 P3 119.7(5) . . ? C43 C44 C45 119.1(6) . . ? C43 C44 H44 120.4 . . ? C45 C44 H44 120.4 . . ? C46 C45 C44 121.1(6) . . ? C46 C45 H45 119.5 . . ? C44 C45 H45 119.5 . . ? C45 C46 C47 119.5(6) . . ? C45 C46 H46 120.2 . . ? C47 C46 H46 120.2 . . ? C46 C47 C48 120.5(7) . . ? C46 C47 H47 119.7 . . ? C48 C47 H47 119.7 . . ? C43 C48 C47 120.2(6) . . ? C43 C48 H48 119.9 . . ? C47 C48 H48 119.9 . . ? C50 C49 C54 120.0(6) . . ? C50 C49 P3 119.8(4) . . ? C54 C49 P3 120.1(5) . . ? C49 C50 C51 119.2(6) . . ? C49 C50 H50 120.4 . . ? C51 C50 H50 120.4 . . ? C50 C51 C52 121.1(7) . . ? C50 C51 H51 119.5 . . ? C52 C51 H51 119.5 . . ? C53 C52 C51 119.2(6) . . ? C53 C52 H52 120.4 . . ? C51 C52 H52 120.4 . . ? C52 C53 C54 120.7(6) . . ? C52 C53 H53 119.7 . . ? C54 C53 H53 119.7 . . ? C53 C54 C49 119.9(6) . . ? C53 C54 H54 120.1 . . ? C49 C54 H54 120.1 . . ? C6SA C1SA C2SA 122.3(13) . . ? C6SA C1SA H1SA 118.8 . . ? C2SA C1SA H1SA 118.8 . . ? C1SA C2SA C3SA 119.1(13) . . ? C1SA C2SA H2SA 120.5 . . ? C3SA C2SA H2SA 120.5 . . ? C4SA C3SA C2SA 117.6(13) . . ? C4SA C3SA H3SA 121.2 . . ? C2SA C3SA H3SA 121.2 . . ? C3SA C4SA C5SA 122.3(13) . . ? C3SA C4SA H4SA 118.9 . . ? C5SA C4SA H4SA 118.9 . . ? C6SA C5SA C4SA 118.4(13) . . ? C6SA C5SA H5SA 120.8 . . ? C4SA C5SA H5SA 120.8 . . ? C1SA C6SA C5SA 117.4(14) . . ? C1SA C6SA H6SA 121.3 . . ? C5SA C6SA H6SA 121.3 . . ? C6SB C1SB C2SB 122.5(13) . . ? C6SB C1SB H1SB 118.8 . . ? C2SB C1SB H1SB 118.8 . . ? C1SB C2SB C3SB 122.6(13) . . ? C1SB C2SB H2SB 118.7 . . ? C3SB C2SB H2SB 118.7 . . ? C4SB C3SB C2SB 113.0(12) . . ? C4SB C3SB H3SB 123.5 . . ? C2SB C3SB H3SB 123.5 . . ? C5SB C4SB C3SB 125.0(13) . . ? C5SB C4SB H4SB 117.5 . . ? C3SB C4SB H4SB 117.5 . . ? C6SB C5SB C4SB 119.4(13) . . ? C6SB C5SB H5SB 120.3 . . ? C4SB C5SB H5SB 120.3 . . ? C1SB C6SB C5SB 115.0(13) . . ? C1SB C6SB H6SB 122.5 . . ? C5SB C6SB H6SB 122.5 . . ? Cl1 C7S Cl2 113.3(9) . . ? Cl1 C7S H7S1 108.9 . . ? Cl2 C7S H7S1 108.9 . . ? Cl1 C7S H7S2 108.9 . . ? Cl2 C7S H7S2 108.9 . . ? H7S1 C7S H7S2 107.7 . . ? Cl3 C8S Cl4 112.3(8) . . ? Cl3 C8S H8S1 109.1 . . ? Cl4 C8S H8S1 109.1 . . ? Cl3 C8S H8S2 109.1 . . ? Cl4 C8S H8S2 109.1 . . ? H8S1 C8S H8S2 107.9 . . ? Cl5 C9S Cl6 111.2(19) . . ? Cl5 C9S H9S1 109.4 . . ? Cl6 C9S H9S1 109.4 . . ? Cl5 C9S H9S2 109.4 . . ? Cl6 C9S H9S2 109.4 . . ? H9S1 C9S H9S2 108.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -145.8(2) . . . . ? P1 Au1 Au2 C6 35.33(16) . . . . ? Br1 Au1 Au2 C6 114.72(17) . . . . ? C24 Au1 Au2 P2 45.98(15) . . . . ? P1 Au1 Au2 P2 -132.84(5) . . . . ? Br1 Au1 Au2 P2 -53.44(8) . . . . ? C24 Au1 Au2 Au3 -68.55(15) . . . . ? P1 Au1 Au2 Au3 112.63(4) . . . . ? Br1 Au1 Au2 Au3 -167.98(7) . . . . ? C42 Au2 Au3 P3 -19.49(15) . . . . ? C6 Au2 Au3 P3 -113.79(15) . . . . ? P2 Au2 Au3 P3 76.37(5) . . . . ? Au1 Au2 Au3 P3 151.98(4) . . . . ? C42 Au2 Au3 Br2 158.45(14) . . . . ? C6 Au2 Au3 Br2 64.14(15) . . . . ? P2 Au2 Au3 Br2 -105.69(4) . . . . ? Au1 Au2 Au3 Br2 -30.085(17) . . . . ? C24 Au1 P1 C13 72.2(9) . . . . ? Br1 Au1 P1 C13 -89.3(2) . . . . ? Au2 Au1 P1 C13 78.9(2) . . . . ? C24 Au1 P1 C1 -46.6(9) . . . . ? Br1 Au1 P1 C1 151.84(18) . . . . ? Au2 Au1 P1 C1 -39.94(18) . . . . ? C24 Au1 P1 C7 -165.6(9) . . . . ? Br1 Au1 P1 C7 32.9(2) . . . . ? Au2 Au1 P1 C7 -158.9(2) . . . . ? C42 Au2 P2 C19 123.0(2) . . . . ? C6 Au2 P2 C19 -105.8(6) . . . . ? Au1 Au2 P2 C19 -50.25(18) . . . . ? Au3 Au2 P2 C19 30.19(19) . . . . ? C42 Au2 P2 C31 -1.3(3) . . . . ? C6 Au2 P2 C31 129.9(6) . . . . ? Au1 Au2 P2 C31 -174.5(2) . . . . ? Au3 Au2 P2 C31 -94.1(2) . . . . ? C42 Au2 P2 C25 -122.3(2) . . . . ? C6 Au2 P2 C25 8.9(6) . . . . ? Au1 Au2 P2 C25 64.50(19) . . . . ? Au3 Au2 P2 C25 144.95(19) . . . . ? Au2 Au3 P3 C43 -99.5(2) . . . . ? Au2 Au3 P3 C49 145.6(2) . . . . ? Au2 Au3 P3 C37 24.32(19) . . . . ? C13 P1 C1 C6 -91.8(5) . . . . ? C7 P1 C1 C6 155.8(4) . . . . ? Au1 P1 C1 C6 31.1(5) . . . . ? C13 P1 C1 C2 87.1(5) . . . . ? C7 P1 C1 C2 -25.2(6) . . . . ? Au1 P1 C1 C2 -150.0(5) . . . . ? C6 C1 C2 C3 -0.9(10) . . . . ? P1 C1 C2 C3 -179.8(5) . . . . ? C1 C2 C3 C4 0.1(10) . . . . ? C2 C3 C4 C5 0.1(10) . . . . ? C3 C4 C5 F1 -179.0(6) . . . . ? C3 C4 C5 C6 0.4(10) . . . . ? F1 C5 C6 C1 178.3(5) . . . . ? C4 C5 C6 C1 -1.1(8) . . . . ? F1 C5 C6 Au2 -6.3(8) . . . . ? C4 C5 C6 Au2 174.2(5) . . . . ? C2 C1 C6 C5 1.3(8) . . . . ? P1 C1 C6 C5 -179.8(4) . . . . ? C2 C1 C6 Au2 -174.5(5) . . . . ? P1 C1 C6 Au2 4.4(6) . . . . ? C42 Au2 C6 C5 -21.4(5) . . . . ? P2 Au2 C6 C5 -152.7(4) . . . . ? Au1 Au2 C6 C5 153.3(5) . . . . ? Au3 Au2 C6 C5 68.2(5) . . . . ? C42 Au2 C6 C1 153.8(4) . . . . ? P2 Au2 C6 C1 22.5(9) . . . . ? Au1 Au2 C6 C1 -31.6(4) . . . . ? Au3 Au2 C6 C1 -116.7(4) . . . . ? C13 P1 C7 C8 166.7(4) . . . . ? C1 P1 C7 C8 -80.1(5) . . . . ? Au1 P1 C7 C8 40.4(5) . . . . ? C13 P1 C7 C12 -12.3(5) . . . . ? C1 P1 C7 C12 100.9(5) . . . . ? Au1 P1 C7 C12 -138.6(4) . . . . ? C12 C7 C8 C9 -0.9(8) . . . . ? P1 C7 C8 C9 -179.9(4) . . . . ? C7 C8 C9 C10 0.6(9) . . . . ? C8 C9 C10 C11 -0.5(9) . . . . ? C9 C10 C11 C12 0.6(9) . . . . ? C10 C11 C12 C7 -0.9(9) . . . . ? C8 C7 C12 C11 1.0(8) . . . . ? P1 C7 C12 C11 180.0(4) . . . . ? C1 P1 C13 C14 3.1(5) . . . . ? C7 P1 C13 C14 115.6(5) . . . . ? Au1 P1 C13 C14 -116.8(4) . . . . ? C1 P1 C13 C18 -176.4(4) . . . . ? C7 P1 C13 C18 -63.9(5) . . . . ? Au1 P1 C13 C18 63.6(5) . . . . ? C18 C13 C14 C15 0.9(9) . . . . ? P1 C13 C14 C15 -178.6(5) . . . . ? C13 C14 C15 C16 1.3(10) . . . . ? C14 C15 C16 C17 -2.4(10) . . . . ? C15 C16 C17 C18 1.3(10) . . . . ? C16 C17 C18 C13 0.9(9) . . . . ? C14 C13 C18 C17 -2.0(8) . . . . ? P1 C13 C18 C17 177.5(4) . . . . ? C31 P2 C19 C20 -11.2(6) . . . . ? C25 P2 C19 C20 98.6(5) . . . . ? Au2 P2 C19 C20 -144.2(5) . . . . ? C31 P2 C19 C24 167.1(4) . . . . ? C25 P2 C19 C24 -83.0(4) . . . . ? Au2 P2 C19 C24 34.2(4) . . . . ? C24 C19 C20 C21 -3.0(9) . . . . ? P2 C19 C20 C21 175.1(4) . . . . ? C19 C20 C21 C22 0.9(9) . . . . ? C20 C21 C22 C23 0.4(9) . . . . ? C21 C22 C23 F2 -179.3(5) . . . . ? C21 C22 C23 C24 0.3(9) . . . . ? F2 C23 C24 C19 177.4(5) . . . . ? C22 C23 C24 C19 -2.2(8) . . . . ? F2 C23 C24 Au1 -10.4(8) . . . . ? C22 C23 C24 Au1 170.0(5) . . . . ? C20 C19 C24 C23 3.6(8) . . . . ? P2 C19 C24 C23 -174.8(4) . . . . ? C20 C19 C24 Au1 -169.3(4) . . . . ? P2 C19 C24 Au1 12.4(6) . . . . ? P1 Au1 C24 C23 148.4(6) . . . . ? Br1 Au1 C24 C23 -50.0(5) . . . . ? Au2 Au1 C24 C23 141.7(5) . . . . ? P1 Au1 C24 C19 -39.7(12) . . . . ? Br1 Au1 C24 C19 121.8(4) . . . . ? Au2 Au1 C24 C19 -46.4(4) . . . . ? C19 P2 C25 C30 -174.7(4) . . . . ? C31 P2 C25 C30 -60.7(5) . . . . ? Au2 P2 C25 C30 71.8(5) . . . . ? C19 P2 C25 C26 1.7(5) . . . . ? C31 P2 C25 C26 115.7(4) . . . . ? Au2 P2 C25 C26 -111.8(4) . . . . ? C30 C25 C26 C27 1.8(8) . . . . ? P2 C25 C26 C27 -174.5(4) . . . . ? C25 C26 C27 C28 0.3(9) . . . . ? C26 C27 C28 C29 -1.0(10) . . . . ? C27 C28 C29 C30 -0.5(10) . . . . ? C28 C29 C30 C25 2.7(9) . . . . ? C26 C25 C30 C29 -3.3(8) . . . . ? P2 C25 C30 C29 173.1(5) . . . . ? C19 P2 C31 C32 90.4(5) . . . . ? C25 P2 C31 C32 -22.4(5) . . . . ? Au2 P2 C31 C32 -147.0(4) . . . . ? C19 P2 C31 C36 -88.2(5) . . . . ? C25 P2 C31 C36 159.0(5) . . . . ? Au2 P2 C31 C36 34.5(5) . . . . ? C36 C31 C32 C33 -3.4(8) . . . . ? P2 C31 C32 C33 178.0(5) . . . . ? C31 C32 C33 C34 -1.0(9) . . . . ? C32 C33 C34 C35 3.6(9) . . . . ? C33 C34 C35 C36 -1.6(9) . . . . ? C34 C35 C36 C31 -2.8(9) . . . . ? C32 C31 C36 C35 5.3(8) . . . . ? P2 C31 C36 C35 -176.1(4) . . . . ? C43 P3 C37 C42 103.3(5) . . . . ? C49 P3 C37 C42 -147.3(4) . . . . ? Au3 P3 C37 C42 -23.9(5) . . . . ? C43 P3 C37 C38 -73.2(5) . . . . ? C49 P3 C37 C38 36.2(5) . . . . ? Au3 P3 C37 C38 159.6(4) . . . . ? C42 C37 C38 C39 -1.6(8) . . . . ? P3 C37 C38 C39 174.9(4) . . . . ? C37 C38 C39 C40 0.2(9) . . . . ? C38 C39 C40 C41 1.4(9) . . . . ? C39 C40 C41 F3 179.6(5) . . . . ? C39 C40 C41 C42 -1.7(9) . . . . ? F3 C41 C42 C37 179.0(5) . . . . ? C40 C41 C42 C37 0.3(8) . . . . ? F3 C41 C42 Au2 3.4(7) . . . . ? C40 C41 C42 Au2 -175.3(4) . . . . ? C38 C37 C42 C41 1.4(8) . . . . ? P3 C37 C42 C41 -175.1(4) . . . . ? C38 C37 C42 Au2 176.7(4) . . . . ? P3 C37 C42 Au2 0.3(6) . . . . ? C6 Au2 C42 C41 -91.9(4) . . . . ? P2 Au2 C42 C41 77.3(4) . . . . ? Au3 Au2 C42 C41 -169.5(4) . . . . ? C6 Au2 C42 C37 92.7(5) . . . . ? P2 Au2 C42 C37 -98.1(4) . . . . ? Au3 Au2 C42 C37 15.1(4) . . . . ? C49 P3 C43 C48 -55.8(6) . . . . ? C37 P3 C43 C48 55.6(6) . . . . ? Au3 P3 C43 C48 -174.9(5) . . . . ? C49 P3 C43 C44 123.1(5) . . . . ? C37 P3 C43 C44 -125.5(5) . . . . ? Au3 P3 C43 C44 4.0(6) . . . . ? C48 C43 C44 C45 1.9(10) . . . . ? P3 C43 C44 C45 -177.0(5) . . . . ? C43 C44 C45 C46 -1.2(10) . . . . ? C44 C45 C46 C47 0.1(10) . . . . ? C45 C46 C47 C48 0.4(11) . . . . ? C44 C43 C48 C47 -1.4(11) . . . . ? P3 C43 C48 C47 177.5(6) . . . . ? C46 C47 C48 C43 0.3(12) . . . . ? C43 P3 C49 C50 -32.0(6) . . . . ? C37 P3 C49 C50 -143.5(5) . . . . ? Au3 P3 C49 C50 89.0(5) . . . . ? C43 P3 C49 C54 153.2(5) . . . . ? C37 P3 C49 C54 41.7(5) . . . . ? Au3 P3 C49 C54 -85.8(4) . . . . ? C54 C49 C50 C51 0.1(10) . . . . ? P3 C49 C50 C51 -174.7(5) . . . . ? C49 C50 C51 C52 -1.2(11) . . . . ? C50 C51 C52 C53 1.6(11) . . . . ? C51 C52 C53 C54 -0.8(10) . . . . ? C52 C53 C54 C49 -0.3(9) . . . . ? C50 C49 C54 C53 0.7(9) . . . . ? P3 C49 C54 C53 175.5(4) . . . . ? C6SA C1SA C2SA C3SA -8(3) . . . . ? C1SA C2SA C3SA C4SA 10(2) . . . . ? C2SA C3SA C4SA C5SA 1(3) . . . . ? C3SA C4SA C5SA C6SA -16(3) . . . . ? C2SA C1SA C6SA C5SA -7(3) . . . . ? C4SA C5SA C6SA C1SA 18(3) . . . . ? C6SB C1SB C2SB C3SB 3(3) . . . . ? C1SB C2SB C3SB C4SB -8(2) . . . . ? C2SB C3SB C4SB C5SB -1(3) . . . . ? C3SB C4SB C5SB C6SB 14(3) . . . . ? C2SB C1SB C6SB C5SB 10(3) . . . . ? C4SB C5SB C6SB C1SB -18(3) . . . . ? _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 29.00 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 3.753 _refine_diff_density_min -3.555 _refine_diff_density_rms 0.229 # Attachment 'neda01601.cif.txt' data_neda01601 _database_code_depnum_ccdc_archive 'CCDC 726000' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 Cl2 F2 P2, C H2 Cl2' _chemical_formula_sum 'C37 H28 Au2 Cl4 F2 P2' _chemical_formula_weight 1108.27 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.84910(10) _cell_length_b 11.4657(2) _cell_length_c 18.1948(3) _cell_angle_alpha 87.2030(10) _cell_angle_beta 77.6010(10) _cell_angle_gamma 86.2500(10) _cell_volume 1798.00(5) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 111885 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.41 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.047 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1048 _exptl_absorpt_coefficient_mu 8.574 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.340 _exptl_absorpt_correction_T_max 0.661 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 67525 _diffrn_reflns_av_R_equivalents 0.0700 _diffrn_reflns_av_sigmaI/netI 0.0429 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 35.00 _reflns_number_total 15839 _reflns_number_gt 13335 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0449P)^2^+2.7142P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 15839 _refine_ls_number_parameters 434 _refine_ls_number_restraints 27 _refine_ls_R_factor_all 0.0447 _refine_ls_R_factor_gt 0.0340 _refine_ls_wR_factor_ref 0.0864 _refine_ls_wR_factor_gt 0.0827 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.054 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.789396(12) 0.640022(9) 0.281581(6) 0.01137(3) Uani 1 1 d . . . Au2 Au 0.898578(12) 0.926429(9) 0.209043(6) 0.01267(3) Uani 1 1 d . . . P1 P 0.67933(9) 0.56793(7) 0.18610(5) 0.01357(13) Uani 1 1 d . . . P2 P 0.72860(9) 0.93367(7) 0.31857(4) 0.01130(12) Uani 1 1 d . . . Cl1 Cl 1.04698(8) 0.66121(7) 0.21781(5) 0.01813(13) Uani 1 1 d . . . Cl2 Cl 1.08695(9) 0.94632(7) 0.10104(4) 0.02018(14) Uani 1 1 d . . . F1 F 0.5195(3) 0.6206(2) 0.45355(12) 0.0228(4) Uani 1 1 d . . . F2 F 0.9039(2) 0.53393(16) 0.42318(12) 0.0181(4) Uani 1 1 d . . . C1 C 0.5138(4) 0.5537(3) 0.26141(18) 0.0148(5) Uani 1 1 d . . . C2 C 0.3673(4) 0.5105(3) 0.2698(2) 0.0190(6) Uani 1 1 d . . . H2 H 0.3334 0.4833 0.2279 0.023 Uiso 1 1 calc R . . C3 C 0.2732(4) 0.5085(3) 0.3406(2) 0.0209(6) Uani 1 1 d . . . H3 H 0.1719 0.4810 0.3476 0.025 Uiso 1 1 calc R . . C4 C 0.3245(4) 0.5462(3) 0.4021(2) 0.0192(6) Uani 1 1 d . . . H4 H 0.2589 0.5434 0.4508 0.023 Uiso 1 1 calc R . . C5 C 0.4719(4) 0.5880(3) 0.39236(18) 0.0163(5) Uani 1 1 d . . . C6 C 0.5680(3) 0.5956(3) 0.32182(17) 0.0130(5) Uani 1 1 d . . . C7 C 0.7314(4) 0.4321(3) 0.13953(19) 0.0188(6) Uani 1 1 d . . . C8 C 0.7074(6) 0.3272(3) 0.1812(2) 0.0293(8) Uani 1 1 d . . . H8 H 0.6623 0.3282 0.2335 0.035 Uiso 1 1 calc R . . C9 C 0.7494(6) 0.2212(4) 0.1465(3) 0.0375(11) Uani 1 1 d . . . H9 H 0.7330 0.1498 0.1750 0.045 Uiso 1 1 calc R . . C10 C 0.8149(6) 0.2195(4) 0.0706(3) 0.0343(10) Uani 1 1 d . . . H10 H 0.8459 0.1469 0.0473 0.041 Uiso 1 1 calc R . . C11 C 0.8359(5) 0.3239(4) 0.0277(2) 0.0311(8) Uani 1 1 d . . . H11 H 0.8790 0.3222 -0.0248 0.037 Uiso 1 1 calc R . . C12 C 0.7935(4) 0.4307(3) 0.0622(2) 0.0246(7) Uani 1 1 d . . . H12 H 0.8068 0.5020 0.0333 0.030 Uiso 1 1 calc R . . C13 C 0.6492(4) 0.6815(3) 0.11804(18) 0.0160(5) Uani 1 1 d . . . C14 C 0.5058(4) 0.7036(3) 0.0980(2) 0.0255(7) Uani 1 1 d . . . H14 H 0.4212 0.6571 0.1192 0.031 Uiso 1 1 calc R . . C15 C 0.4888(5) 0.7947(4) 0.0467(3) 0.0319(9) Uani 1 1 d . . . H15 H 0.3914 0.8115 0.0333 0.038 Uiso 1 1 calc R . . C16 C 0.6135(5) 0.8613(4) 0.0148(2) 0.0298(8) Uani 1 1 d . . . H16 H 0.6017 0.9218 -0.0215 0.036 Uiso 1 1 calc R . . C17 C 0.7542(5) 0.8401(3) 0.0353(2) 0.0258(7) Uani 1 1 d . . . H17 H 0.8384 0.8870 0.0141 0.031 Uiso 1 1 calc R . . C18 C 0.7725(4) 0.7498(3) 0.08718(19) 0.0187(6) Uani 1 1 d . . . H18 H 0.8694 0.7349 0.1014 0.022 Uiso 1 1 calc R . . C19 C 0.7917(3) 0.8385(2) 0.39057(17) 0.0118(5) Uani 1 1 d . . . C20 C 0.8144(4) 0.8847(3) 0.45701(18) 0.0153(5) Uani 1 1 d . . . H20 H 0.7926 0.9658 0.4653 0.018 Uiso 1 1 calc R . . C21 C 0.8685(4) 0.8135(3) 0.51095(19) 0.0184(6) Uani 1 1 d . . . H21 H 0.8829 0.8455 0.5560 0.022 Uiso 1 1 calc R . . C22 C 0.9014(4) 0.6946(3) 0.49842(19) 0.0174(5) Uani 1 1 d . . . H22 H 0.9412 0.6447 0.5339 0.021 Uiso 1 1 calc R . . C23 C 0.8746(3) 0.6514(3) 0.43298(18) 0.0139(5) Uani 1 1 d . . . C24 C 0.8217(3) 0.7176(3) 0.37725(17) 0.0130(5) Uani 1 1 d . . . C25 C 0.5313(3) 0.8986(3) 0.32190(18) 0.0141(5) Uani 1 1 d . . . C26 C 0.4770(4) 0.8951(3) 0.2551(2) 0.0198(6) Uani 1 1 d . . . H26 H 0.5441 0.9094 0.2077 0.024 Uiso 1 1 calc R . . C27 C 0.3233(4) 0.8706(4) 0.2592(3) 0.0277(8) Uani 1 1 d . . . H27 H 0.2857 0.8679 0.2142 0.033 Uiso 1 1 calc R . . C28 C 0.2243(4) 0.8500(3) 0.3283(3) 0.0276(8) Uani 1 1 d . . . H28 H 0.1197 0.8332 0.3305 0.033 Uiso 1 1 calc R . . C29 C 0.2787(4) 0.8542(3) 0.3942(2) 0.0244(7) Uani 1 1 d . . . H29 H 0.2107 0.8408 0.4414 0.029 Uiso 1 1 calc R . . C30 C 0.4315(4) 0.8777(3) 0.3915(2) 0.0185(6) Uani 1 1 d . . . H30 H 0.4684 0.8796 0.4368 0.022 Uiso 1 1 calc R . . C31 C 0.7156(3) 1.0824(3) 0.35096(17) 0.0139(5) Uani 1 1 d . . . C32 C 0.5739(4) 1.1418(3) 0.37924(18) 0.0163(5) Uani 1 1 d . . . H32 H 0.4802 1.1033 0.3842 0.020 Uiso 1 1 calc R . . C33 C 0.5696(4) 1.2578(3) 0.4002(2) 0.0198(6) Uani 1 1 d . . . H33 H 0.4732 1.2980 0.4199 0.024 Uiso 1 1 calc R . . C34 C 0.7065(4) 1.3142(3) 0.3923(2) 0.0204(6) Uani 1 1 d . . . H34 H 0.7033 1.3933 0.4061 0.025 Uiso 1 1 calc R . . C35 C 0.8480(4) 1.2559(3) 0.3642(2) 0.0194(6) Uani 1 1 d . . . H35 H 0.9413 1.2948 0.3595 0.023 Uiso 1 1 calc R . . C36 C 0.8533(4) 1.1405(3) 0.3427(2) 0.0181(6) Uani 1 1 d . . . H36 H 0.9501 1.1011 0.3225 0.022 Uiso 1 1 calc R . . Cl3A Cl 0.2580(11) 0.1894(8) 0.2276(6) 0.0547(6) Uani 0.218(4) 1 d PDU A 1 C1S C 0.138(3) 0.253(3) 0.1689(18) 0.089(3) Uani 0.218(4) 1 d PDU A 1 H1S1 H 0.0374 0.2805 0.2003 0.106 Uiso 0.218(4) 1 calc PR A 1 H1S2 H 0.1171 0.1927 0.1355 0.106 Uiso 0.218(4) 1 calc PR A 1 Cl4A Cl 0.2244(13) 0.3709(8) 0.1135(7) 0.0816(9) Uani 0.218(4) 1 d PDU A 1 Cl3B Cl 0.2689(3) 0.19851(19) 0.26090(16) 0.0547(6) Uani 0.782(4) 1 d PD A 2 C1T C 0.2127(14) 0.2167(7) 0.1736(5) 0.089(3) Uani 0.782(4) 1 d PD A 2 H1T1 H 0.3046 0.2040 0.1323 0.106 Uiso 0.782(4) 1 calc PR A 2 H1T2 H 0.1378 0.1578 0.1703 0.106 Uiso 0.782(4) 1 calc PR A 2 Cl4B Cl 0.1274(3) 0.3582(2) 0.16282(19) 0.0816(9) Uani 0.782(4) 1 d PD A 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01092(5) 0.01017(5) 0.01265(5) -0.00146(3) -0.00163(3) -0.00015(3) Au2 0.01232(5) 0.01269(5) 0.01239(5) -0.00068(4) -0.00157(4) 0.00033(4) P1 0.0125(3) 0.0141(3) 0.0143(3) -0.0023(3) -0.0031(3) -0.0008(3) P2 0.0103(3) 0.0106(3) 0.0131(3) -0.0013(2) -0.0027(2) -0.0001(2) Cl1 0.0119(3) 0.0194(3) 0.0220(3) -0.0015(3) -0.0011(2) -0.0006(2) Cl2 0.0196(3) 0.0222(3) 0.0160(3) 0.0004(3) 0.0025(3) -0.0023(3) F1 0.0241(10) 0.0295(11) 0.0143(9) -0.0044(8) -0.0001(7) -0.0079(8) F2 0.0217(9) 0.0106(8) 0.0224(9) 0.0010(7) -0.0065(8) 0.0014(7) C1 0.0139(12) 0.0128(12) 0.0171(13) -0.0010(10) -0.0021(10) -0.0005(9) C2 0.0134(12) 0.0188(14) 0.0251(15) -0.0019(12) -0.0035(11) -0.0041(10) C3 0.0128(13) 0.0185(14) 0.0307(17) 0.0007(13) -0.0023(12) -0.0040(11) C4 0.0149(13) 0.0193(14) 0.0215(14) 0.0009(12) 0.0000(11) -0.0019(11) C5 0.0174(13) 0.0149(12) 0.0157(13) -0.0027(10) -0.0004(10) -0.0019(10) C6 0.0104(11) 0.0123(11) 0.0154(12) -0.0025(9) -0.0003(9) -0.0003(9) C7 0.0197(14) 0.0183(14) 0.0196(14) -0.0068(11) -0.0071(11) 0.0041(11) C8 0.050(2) 0.0178(15) 0.0220(16) -0.0037(13) -0.0140(16) 0.0057(15) C9 0.065(3) 0.0193(17) 0.033(2) -0.0067(15) -0.022(2) 0.0113(18) C10 0.043(2) 0.0287(19) 0.035(2) -0.0184(17) -0.0188(19) 0.0166(17) C11 0.0304(19) 0.036(2) 0.0257(18) -0.0127(16) -0.0038(15) 0.0070(16) C12 0.0227(16) 0.0276(17) 0.0215(16) -0.0064(13) 0.0002(13) 0.0013(13) C13 0.0158(13) 0.0167(13) 0.0158(13) -0.0009(10) -0.0040(10) -0.0002(10) C14 0.0169(14) 0.0275(17) 0.0332(19) 0.0041(15) -0.0087(13) -0.0019(13) C15 0.0226(17) 0.038(2) 0.037(2) 0.0084(18) -0.0144(16) 0.0041(15) C16 0.0313(19) 0.0277(18) 0.0294(19) 0.0095(15) -0.0079(16) 0.0018(15) C17 0.0243(16) 0.0249(17) 0.0264(17) 0.0084(14) -0.0028(13) -0.0045(13) C18 0.0166(13) 0.0193(14) 0.0203(14) 0.0015(11) -0.0040(11) -0.0024(11) C19 0.0104(11) 0.0110(11) 0.0138(11) -0.0012(9) -0.0022(9) 0.0003(9) C20 0.0169(13) 0.0139(12) 0.0156(12) -0.0021(10) -0.0044(10) -0.0008(10) C21 0.0229(15) 0.0191(14) 0.0151(13) -0.0011(11) -0.0079(11) -0.0027(11) C22 0.0175(13) 0.0174(13) 0.0183(13) 0.0029(11) -0.0070(11) -0.0013(11) C23 0.0126(12) 0.0123(11) 0.0170(12) 0.0010(10) -0.0041(10) -0.0004(9) C24 0.0094(11) 0.0139(12) 0.0154(12) -0.0013(10) -0.0020(9) -0.0011(9) C25 0.0099(11) 0.0122(11) 0.0208(13) -0.0029(10) -0.0039(10) -0.0001(9) C26 0.0159(13) 0.0225(15) 0.0219(15) -0.0029(12) -0.0063(11) 0.0001(11) C27 0.0172(15) 0.0319(19) 0.038(2) -0.0088(16) -0.0146(14) 0.0004(13) C28 0.0124(13) 0.0259(17) 0.046(2) -0.0067(16) -0.0075(14) -0.0015(12) C29 0.0142(13) 0.0210(15) 0.0359(19) -0.0024(14) 0.0005(13) -0.0039(11) C30 0.0143(13) 0.0173(13) 0.0232(15) 0.0003(11) -0.0021(11) -0.0034(10) C31 0.0150(12) 0.0123(11) 0.0153(12) -0.0013(10) -0.0048(10) -0.0018(9) C32 0.0155(13) 0.0139(12) 0.0191(13) -0.0021(10) -0.0024(10) -0.0006(10) C33 0.0203(14) 0.0137(13) 0.0252(16) -0.0064(11) -0.0042(12) 0.0033(11) C34 0.0255(16) 0.0131(13) 0.0248(16) -0.0021(11) -0.0094(13) -0.0015(11) C35 0.0226(15) 0.0154(13) 0.0226(15) -0.0025(11) -0.0085(12) -0.0064(11) C36 0.0156(13) 0.0158(13) 0.0240(15) -0.0033(11) -0.0060(11) -0.0019(10) Cl3A 0.0450(8) 0.0429(8) 0.0712(16) -0.0032(11) -0.0004(11) -0.0049(6) C1S 0.118(6) 0.069(5) 0.080(5) -0.017(4) -0.019(4) -0.011(4) Cl4A 0.0862(17) 0.0730(13) 0.110(2) 0.0139(14) -0.0717(16) -0.0302(13) Cl3B 0.0450(8) 0.0429(8) 0.0712(16) -0.0032(11) -0.0004(11) -0.0049(6) C1T 0.118(6) 0.069(5) 0.080(5) -0.017(4) -0.019(4) -0.011(4) Cl4B 0.0862(17) 0.0730(13) 0.110(2) 0.0139(14) -0.0717(16) -0.0302(13) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C6 2.027(3) . ? Au1 C24 2.074(3) . ? Au1 Cl1 2.3473(7) . ? Au1 P1 2.3710(8) . ? Au2 P2 2.2256(8) . ? Au2 Cl2 2.3004(8) . ? P1 C1 1.788(3) . ? P1 C7 1.795(3) . ? P1 C13 1.800(3) . ? P2 C25 1.805(3) . ? P2 C31 1.820(3) . ? P2 C19 1.821(3) . ? F1 C5 1.349(4) . ? F2 C23 1.367(3) . ? C1 C2 1.394(4) . ? C1 C6 1.406(4) . ? C2 C3 1.376(5) . ? C2 H2 0.9500 . ? C3 C4 1.392(5) . ? C3 H3 0.9500 . ? C4 C5 1.391(4) . ? C4 H4 0.9500 . ? C5 C6 1.382(4) . ? C7 C8 1.393(5) . ? C7 C12 1.397(5) . ? C8 C9 1.390(5) . ? C8 H8 0.9500 . ? C9 C10 1.378(7) . ? C9 H9 0.9500 . ? C10 C11 1.397(7) . ? C10 H10 0.9500 . ? C11 C12 1.396(5) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.388(4) . ? C13 C14 1.398(5) . ? C14 C15 1.389(6) . ? C14 H14 0.9500 . ? C15 C16 1.389(6) . ? C15 H15 0.9500 . ? C16 C17 1.378(6) . ? C16 H16 0.9500 . ? C17 C18 1.392(5) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.401(4) . ? C19 C24 1.416(4) . ? C20 C21 1.390(4) . ? C20 H20 0.9500 . ? C21 C22 1.394(5) . ? C21 H21 0.9500 . ? C22 C23 1.384(4) . ? C22 H22 0.9500 . ? C23 C24 1.381(4) . ? C25 C30 1.400(5) . ? C25 C26 1.403(5) . ? C26 C27 1.392(5) . ? C26 H26 0.9500 . ? C27 C28 1.389(6) . ? C27 H27 0.9500 . ? C28 C29 1.388(6) . ? C28 H28 0.9500 . ? C29 C30 1.386(5) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.395(4) . ? C31 C36 1.403(4) . ? C32 C33 1.398(4) . ? C32 H32 0.9500 . ? C33 C34 1.387(5) . ? C33 H33 0.9500 . ? C34 C35 1.387(5) . ? C34 H34 0.9500 . ? C35 C36 1.393(4) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? Cl3A C1S 1.764(6) . ? C1S Cl4A 1.764(6) . ? C1S H1S1 0.9900 . ? C1S H1S2 0.9900 . ? Cl3B C1T 1.764(6) . ? C1T Cl4B 1.764(6) . ? C1T H1T1 0.9900 . ? C1T H1T2 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C6 Au1 C24 97.66(12) . . ? C6 Au1 Cl1 168.36(9) . . ? C24 Au1 Cl1 93.11(8) . . ? C6 Au1 P1 68.18(9) . . ? C24 Au1 P1 163.96(8) . . ? Cl1 Au1 P1 101.67(3) . . ? P2 Au2 Cl2 170.94(3) . . ? C1 P1 C7 110.67(16) . . ? C1 P1 C13 112.51(15) . . ? C7 P1 C13 109.32(16) . . ? C1 P1 Au1 83.07(11) . . ? C7 P1 Au1 126.92(11) . . ? C13 P1 Au1 111.50(11) . . ? C25 P2 C31 105.37(14) . . ? C25 P2 C19 105.16(14) . . ? C31 P2 C19 106.98(14) . . ? C25 P2 Au2 118.84(11) . . ? C31 P2 Au2 107.96(10) . . ? C19 P2 Au2 111.81(10) . . ? C2 C1 C6 122.8(3) . . ? C2 C1 P1 135.8(3) . . ? C6 C1 P1 101.3(2) . . ? C3 C2 C1 117.9(3) . . ? C3 C2 H2 121.0 . . ? C1 C2 H2 121.0 . . ? C2 C3 C4 120.8(3) . . ? C2 C3 H3 119.6 . . ? C4 C3 H3 119.6 . . ? C5 C4 C3 120.1(3) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? F1 C5 C6 120.5(3) . . ? F1 C5 C4 118.5(3) . . ? C6 C5 C4 121.0(3) . . ? C5 C6 C1 117.2(3) . . ? C5 C6 Au1 135.0(2) . . ? C1 C6 Au1 107.4(2) . . ? C8 C7 C12 120.0(3) . . ? C8 C7 P1 119.3(3) . . ? C12 C7 P1 120.7(3) . . ? C9 C8 C7 120.1(4) . . ? C9 C8 H8 119.9 . . ? C7 C8 H8 119.9 . . ? C10 C9 C8 120.1(4) . . ? C10 C9 H9 120.0 . . ? C8 C9 H9 120.0 . . ? C9 C10 C11 120.4(4) . . ? C9 C10 H10 119.8 . . ? C11 C10 H10 119.8 . . ? C12 C11 C10 119.9(4) . . ? C12 C11 H11 120.1 . . ? C10 C11 H11 120.1 . . ? C11 C12 C7 119.5(4) . . ? C11 C12 H12 120.2 . . ? C7 C12 H12 120.2 . . ? C18 C13 C14 120.4(3) . . ? C18 C13 P1 117.7(2) . . ? C14 C13 P1 121.8(3) . . ? C15 C14 C13 119.0(3) . . ? C15 C14 H14 120.5 . . ? C13 C14 H14 120.5 . . ? C16 C15 C14 120.3(4) . . ? C16 C15 H15 119.8 . . ? C14 C15 H15 119.8 . . ? C17 C16 C15 120.4(4) . . ? C17 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? C16 C17 C18 119.8(3) . . ? C16 C17 H17 120.1 . . ? C18 C17 H17 120.1 . . ? C13 C18 C17 119.9(3) . . ? C13 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? C20 C19 C24 120.7(3) . . ? C20 C19 P2 120.5(2) . . ? C24 C19 P2 118.8(2) . . ? C21 C20 C19 120.9(3) . . ? C21 C20 H20 119.6 . . ? C19 C20 H20 119.6 . . ? C20 C21 C22 119.4(3) . . ? C20 C21 H21 120.3 . . ? C22 C21 H21 120.3 . . ? C23 C22 C21 118.2(3) . . ? C23 C22 H22 120.9 . . ? C21 C22 H22 120.9 . . ? F2 C23 C24 118.1(3) . . ? F2 C23 C22 116.9(3) . . ? C24 C23 C22 125.0(3) . . ? C23 C24 C19 115.7(3) . . ? C23 C24 Au1 120.5(2) . . ? C19 C24 Au1 123.8(2) . . ? C30 C25 C26 120.1(3) . . ? C30 C25 P2 119.7(2) . . ? C26 C25 P2 120.2(2) . . ? C27 C26 C25 119.1(3) . . ? C27 C26 H26 120.5 . . ? C25 C26 H26 120.5 . . ? C28 C27 C26 120.8(4) . . ? C28 C27 H27 119.6 . . ? C26 C27 H27 119.6 . . ? C29 C28 C27 119.8(3) . . ? C29 C28 H28 120.1 . . ? C27 C28 H28 120.1 . . ? C30 C29 C28 120.5(4) . . ? C30 C29 H29 119.7 . . ? C28 C29 H29 119.7 . . ? C29 C30 C25 119.7(3) . . ? C29 C30 H30 120.1 . . ? C25 C30 H30 120.1 . . ? C32 C31 C36 119.6(3) . . ? C32 C31 P2 122.2(2) . . ? C36 C31 P2 118.1(2) . . ? C31 C32 C33 120.1(3) . . ? C31 C32 H32 120.0 . . ? C33 C32 H32 120.0 . . ? C34 C33 C32 119.9(3) . . ? C34 C33 H33 120.1 . . ? C32 C33 H33 120.1 . . ? C33 C34 C35 120.5(3) . . ? C33 C34 H34 119.8 . . ? C35 C34 H34 119.8 . . ? C34 C35 C36 120.1(3) . . ? C34 C35 H35 120.0 . . ? C36 C35 H35 120.0 . . ? C35 C36 C31 119.9(3) . . ? C35 C36 H36 120.0 . . ? C31 C36 H36 120.0 . . ? Cl3A C1S Cl4A 111.4(9) . . ? Cl3A C1S H1S1 109.3 . . ? Cl4A C1S H1S1 109.3 . . ? Cl3A C1S H1S2 109.3 . . ? Cl4A C1S H1S2 109.3 . . ? H1S1 C1S H1S2 108.0 . . ? Cl4B C1T Cl3B 111.0(6) . . ? Cl4B C1T H1T1 109.4 . . ? Cl3B C1T H1T1 109.4 . . ? Cl4B C1T H1T2 109.4 . . ? Cl3B C1T H1T2 109.4 . . ? H1T1 C1T H1T2 108.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 Au1 P1 C1 -0.19(13) . . . . ? C24 Au1 P1 C1 -29.4(3) . . . . ? Cl1 Au1 P1 C1 173.86(10) . . . . ? C6 Au1 P1 C7 -110.90(18) . . . . ? C24 Au1 P1 C7 -140.1(3) . . . . ? Cl1 Au1 P1 C7 63.15(15) . . . . ? C6 Au1 P1 C13 111.32(15) . . . . ? C24 Au1 P1 C13 82.1(3) . . . . ? Cl1 Au1 P1 C13 -74.63(12) . . . . ? C7 P1 C1 C2 -49.7(4) . . . . ? C13 P1 C1 C2 72.9(4) . . . . ? Au1 P1 C1 C2 -176.6(4) . . . . ? C7 P1 C1 C6 127.2(2) . . . . ? C13 P1 C1 C6 -110.2(2) . . . . ? Au1 P1 C1 C6 0.26(18) . . . . ? C6 C1 C2 C3 -0.5(5) . . . . ? P1 C1 C2 C3 175.9(3) . . . . ? C1 C2 C3 C4 -1.3(5) . . . . ? C2 C3 C4 C5 0.8(5) . . . . ? C3 C4 C5 F1 -178.1(3) . . . . ? C3 C4 C5 C6 1.6(5) . . . . ? F1 C5 C6 C1 176.4(3) . . . . ? C4 C5 C6 C1 -3.2(5) . . . . ? F1 C5 C6 Au1 4.0(5) . . . . ? C4 C5 C6 Au1 -175.6(3) . . . . ? C2 C1 C6 C5 2.7(5) . . . . ? P1 C1 C6 C5 -174.7(2) . . . . ? C2 C1 C6 Au1 177.1(3) . . . . ? P1 C1 C6 Au1 -0.3(2) . . . . ? C24 Au1 C6 C5 -14.6(3) . . . . ? Cl1 Au1 C6 C5 142.9(3) . . . . ? P1 Au1 C6 C5 173.2(3) . . . . ? C24 Au1 C6 C1 172.4(2) . . . . ? Cl1 Au1 C6 C1 -30.0(6) . . . . ? P1 Au1 C6 C1 0.25(18) . . . . ? C1 P1 C7 C8 -33.0(4) . . . . ? C13 P1 C7 C8 -157.4(3) . . . . ? Au1 P1 C7 C8 64.0(3) . . . . ? C1 P1 C7 C12 146.3(3) . . . . ? C13 P1 C7 C12 21.8(3) . . . . ? Au1 P1 C7 C12 -116.7(3) . . . . ? C12 C7 C8 C9 1.9(6) . . . . ? P1 C7 C8 C9 -178.9(4) . . . . ? C7 C8 C9 C10 0.0(7) . . . . ? C8 C9 C10 C11 -1.6(7) . . . . ? C9 C10 C11 C12 1.4(7) . . . . ? C10 C11 C12 C7 0.5(6) . . . . ? C8 C7 C12 C11 -2.1(6) . . . . ? P1 C7 C12 C11 178.7(3) . . . . ? C1 P1 C13 C18 141.4(3) . . . . ? C7 P1 C13 C18 -95.2(3) . . . . ? Au1 P1 C13 C18 50.1(3) . . . . ? C1 P1 C13 C14 -36.7(3) . . . . ? C7 P1 C13 C14 86.7(3) . . . . ? Au1 P1 C13 C14 -128.0(3) . . . . ? C18 C13 C14 C15 0.2(6) . . . . ? P1 C13 C14 C15 178.2(3) . . . . ? C13 C14 C15 C16 1.1(7) . . . . ? C14 C15 C16 C17 -1.9(7) . . . . ? C15 C16 C17 C18 1.4(7) . . . . ? C14 C13 C18 C17 -0.7(5) . . . . ? P1 C13 C18 C17 -178.9(3) . . . . ? C16 C17 C18 C13 0.0(6) . . . . ? C25 P2 C19 C20 -109.3(3) . . . . ? C31 P2 C19 C20 2.4(3) . . . . ? Au2 P2 C19 C20 120.4(2) . . . . ? C25 P2 C19 C24 72.5(3) . . . . ? C31 P2 C19 C24 -175.7(2) . . . . ? Au2 P2 C19 C24 -57.8(2) . . . . ? C24 C19 C20 C21 0.7(5) . . . . ? P2 C19 C20 C21 -177.4(3) . . . . ? C19 C20 C21 C22 0.4(5) . . . . ? C20 C21 C22 C23 -1.8(5) . . . . ? C21 C22 C23 F2 -178.3(3) . . . . ? C21 C22 C23 C24 2.1(5) . . . . ? F2 C23 C24 C19 179.4(2) . . . . ? C22 C23 C24 C19 -1.0(5) . . . . ? F2 C23 C24 Au1 -0.3(4) . . . . ? C22 C23 C24 Au1 179.3(2) . . . . ? C20 C19 C24 C23 -0.5(4) . . . . ? P2 C19 C24 C23 177.7(2) . . . . ? C20 C19 C24 Au1 179.2(2) . . . . ? P2 C19 C24 Au1 -2.6(3) . . . . ? C6 Au1 C24 C23 88.1(2) . . . . ? Cl1 Au1 C24 C23 -87.4(2) . . . . ? P1 Au1 C24 C23 115.3(3) . . . . ? C6 Au1 C24 C19 -91.6(2) . . . . ? Cl1 Au1 C24 C19 92.9(2) . . . . ? P1 Au1 C24 C19 -64.4(4) . . . . ? C31 P2 C25 C30 -72.7(3) . . . . ? C19 P2 C25 C30 40.1(3) . . . . ? Au2 P2 C25 C30 166.2(2) . . . . ? C31 P2 C25 C26 105.7(3) . . . . ? C19 P2 C25 C26 -141.5(3) . . . . ? Au2 P2 C25 C26 -15.4(3) . . . . ? C30 C25 C26 C27 -0.1(5) . . . . ? P2 C25 C26 C27 -178.5(3) . . . . ? C25 C26 C27 C28 0.2(6) . . . . ? C26 C27 C28 C29 0.2(6) . . . . ? C27 C28 C29 C30 -0.6(6) . . . . ? C28 C29 C30 C25 0.7(5) . . . . ? C26 C25 C30 C29 -0.3(5) . . . . ? P2 C25 C30 C29 178.1(3) . . . . ? C25 P2 C31 C32 6.5(3) . . . . ? C19 P2 C31 C32 -105.1(3) . . . . ? Au2 P2 C31 C32 134.4(2) . . . . ? C25 P2 C31 C36 -169.7(3) . . . . ? C19 P2 C31 C36 78.7(3) . . . . ? Au2 P2 C31 C36 -41.7(3) . . . . ? C36 C31 C32 C33 -1.0(5) . . . . ? P2 C31 C32 C33 -177.1(3) . . . . ? C31 C32 C33 C34 0.6(5) . . . . ? C32 C33 C34 C35 -0.6(5) . . . . ? C33 C34 C35 C36 0.9(5) . . . . ? C34 C35 C36 C31 -1.3(5) . . . . ? C32 C31 C36 C35 1.3(5) . . . . ? P2 C31 C36 C35 177.6(3) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 4.081 _refine_diff_density_min -3.527 _refine_diff_density_rms 0.224 # Attachment 'neda02001.cif.txt' data_neda02001 _database_code_depnum_ccdc_archive 'CCDC 726001' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 Cl2 F2 P2, 0.85(C6 H14), 0.3(C H2 Cl2)' _chemical_formula_sum 'C41.40 H38.50 Au2 Cl2.60 F2 P2' _chemical_formula_weight 1122.07 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 16.6877(2) _cell_length_b 20.0851(3) _cell_length_c 11.64580(10) _cell_angle_alpha 90.00 _cell_angle_beta 95.7130(10) _cell_angle_gamma 90.00 _cell_volume 3883.98(8) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 73771 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 33.142 _exptl_crystal_description polyhedron _exptl_crystal_colour yellow _exptl_crystal_size_max 0.34 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.919 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2148.4 _exptl_absorpt_coefficient_mu 7.846 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.102 _exptl_absorpt_correction_T_max 0.263 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 80609 _diffrn_reflns_av_R_equivalents 0.0834 _diffrn_reflns_av_sigmaI/netI 0.0447 _diffrn_reflns_limit_h_min -25 _diffrn_reflns_limit_h_max 25 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 30 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.65 _diffrn_reflns_theta_max 33.00 _reflns_number_total 14619 _reflns_number_gt 12010 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0694P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 14619 _refine_ls_number_parameters 466 _refine_ls_number_restraints 42 _refine_ls_R_factor_all 0.0542 _refine_ls_R_factor_gt 0.0402 _refine_ls_wR_factor_ref 0.1100 _refine_ls_wR_factor_gt 0.1046 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.046 _refine_ls_shift/su_max 0.026 _refine_ls_shift/su_mean 0.001 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.181836(8) 0.459272(7) 0.191048(11) 0.01376(4) Uani 1 1 d . . . Au2 Au 0.307243(8) 0.533554(7) 0.204356(11) 0.01465(4) Uani 1 1 d . . . Cl1 Cl 0.06381(5) 0.39345(5) 0.19983(8) 0.01914(17) Uani 1 1 d . . . Cl2 Cl 0.41599(6) 0.60952(5) 0.21566(9) 0.0250(2) Uani 1 1 d . . . P1 P 0.22110(6) 0.44241(5) 0.38679(8) 0.01548(17) Uani 1 1 d . . . P2 P 0.23036(6) 0.59987(5) 0.07082(8) 0.01647(18) Uani 1 1 d . . . F1 F 0.57312(14) 0.41980(15) 0.4198(2) 0.0325(6) Uani 1 1 d . . . F2 F 0.04270(17) 0.41341(15) -0.23802(19) 0.0312(6) Uani 1 1 d . . . C1 C 0.3290(2) 0.43777(19) 0.4069(3) 0.0168(7) Uani 1 1 d . . . C2 C 0.3710(2) 0.4002(2) 0.4953(3) 0.0246(8) Uani 1 1 d . . . H2 H 0.3423 0.3785 0.5512 0.029 Uiso 1 1 calc R . . C3 C 0.4533(3) 0.3948(2) 0.5011(4) 0.0268(9) Uani 1 1 d . . . H3 H 0.4826 0.3699 0.5607 0.032 Uiso 1 1 calc R . . C4 C 0.4922(2) 0.4270(2) 0.4165(3) 0.0217(8) Uani 1 1 d . . . C5 C 0.4528(2) 0.4655(2) 0.3302(3) 0.0203(8) Uani 1 1 d . . . H5 H 0.4823 0.4875 0.2758 0.024 Uiso 1 1 calc R . . C6 C 0.3691(2) 0.47150(19) 0.3238(3) 0.0165(7) Uani 1 1 d . . . C7 C 0.1873(2) 0.3680(2) 0.4542(3) 0.0191(7) Uani 1 1 d . . . C8 C 0.1986(3) 0.3068(2) 0.4014(4) 0.0266(9) Uani 1 1 d . . . H8 H 0.2183 0.3058 0.3276 0.032 Uiso 1 1 calc R . . C9 C 0.1818(3) 0.2481(2) 0.4543(4) 0.0317(10) Uani 1 1 d . . . H9 H 0.1904 0.2067 0.4180 0.038 Uiso 1 1 calc R . . C10 C 0.1519(3) 0.2498(3) 0.5624(4) 0.0333(10) Uani 1 1 d . . . H10 H 0.1406 0.2094 0.5999 0.040 Uiso 1 1 calc R . . C11 C 0.1386(3) 0.3094(3) 0.6146(4) 0.0314(10) Uani 1 1 d . . . H11 H 0.1172 0.3102 0.6871 0.038 Uiso 1 1 calc R . . C12 C 0.1566(3) 0.3689(2) 0.5613(4) 0.0256(8) Uani 1 1 d . . . H12 H 0.1479 0.4101 0.5979 0.031 Uiso 1 1 calc R . . C13 C 0.1866(2) 0.5137(2) 0.4629(3) 0.0182(7) Uani 1 1 d . . . C14 C 0.2408(3) 0.5508(2) 0.5372(3) 0.0233(8) Uani 1 1 d . . . H14 H 0.2949 0.5365 0.5540 0.028 Uiso 1 1 calc R . . C15 C 0.2138(3) 0.6091(2) 0.5861(4) 0.0289(9) Uani 1 1 d . . . H15 H 0.2499 0.6348 0.6366 0.035 Uiso 1 1 calc R . . C16 C 0.1357(3) 0.6294(2) 0.5617(4) 0.0344(11) Uani 1 1 d . . . H16 H 0.1184 0.6695 0.5948 0.041 Uiso 1 1 calc R . . C17 C 0.0811(3) 0.5923(3) 0.4892(4) 0.0328(11) Uani 1 1 d . . . H17 H 0.0266 0.6060 0.4748 0.039 Uiso 1 1 calc R . . C18 C 0.1082(3) 0.5347(2) 0.4383(4) 0.0247(9) Uani 1 1 d . . . H18 H 0.0724 0.5098 0.3863 0.030 Uiso 1 1 calc R . . C19 C 0.1736(2) 0.54478(19) -0.0273(3) 0.0179(7) Uani 1 1 d . . . C20 C 0.1500(2) 0.5620(2) -0.1422(3) 0.0202(7) Uani 1 1 d . . . H20 H 0.1634 0.6045 -0.1707 0.024 Uiso 1 1 calc R . . C21 C 0.1065(2) 0.5163(2) -0.2151(3) 0.0222(8) Uani 1 1 d . . . H21 H 0.0917 0.5261 -0.2942 0.027 Uiso 1 1 calc R . . C22 C 0.0864(2) 0.4573(2) -0.1677(3) 0.0212(8) Uani 1 1 d . . . C23 C 0.1077(2) 0.4386(2) -0.0546(3) 0.0214(7) Uani 1 1 d . . . H23 H 0.0925 0.3964 -0.0271 0.026 Uiso 1 1 calc R . . C24 C 0.1524(2) 0.4836(2) 0.0191(3) 0.0168(7) Uani 1 1 d . . . C25 C 0.2886(2) 0.6546(2) -0.0129(3) 0.0207(7) Uani 1 1 d . . . C26 C 0.3301(3) 0.6268(3) -0.1006(4) 0.0312(10) Uani 1 1 d . . . H26 H 0.3259 0.5805 -0.1170 0.037 Uiso 1 1 calc R . . C27 C 0.3774(3) 0.6674(3) -0.1631(4) 0.0372(11) Uani 1 1 d . . . H27 H 0.4046 0.6489 -0.2236 0.045 Uiso 1 1 calc R . . C28 C 0.3851(3) 0.7335(3) -0.1381(4) 0.0374(11) Uani 1 1 d . . . H28 H 0.4172 0.7608 -0.1818 0.045 Uiso 1 1 calc R . . C29 C 0.3462(3) 0.7616(3) -0.0488(4) 0.0347(10) Uani 1 1 d . . . H29 H 0.3525 0.8075 -0.0310 0.042 Uiso 1 1 calc R . . C30 C 0.2978(3) 0.7211(2) 0.0140(4) 0.0266(8) Uani 1 1 d . . . H30 H 0.2713 0.7396 0.0751 0.032 Uiso 1 1 calc R . . C31 C 0.1613(2) 0.6532(2) 0.1378(3) 0.0192(7) Uani 1 1 d . . . C32 C 0.1837(3) 0.6786(2) 0.2486(4) 0.0285(9) Uani 1 1 d . . . H32 H 0.2337 0.6660 0.2890 0.034 Uiso 1 1 calc R . . C33 C 0.1331(3) 0.7221(3) 0.2996(4) 0.0318(10) Uani 1 1 d . . . H33 H 0.1490 0.7403 0.3737 0.038 Uiso 1 1 calc R . . C34 C 0.0596(3) 0.7387(2) 0.2421(4) 0.0299(9) Uani 1 1 d . . . H34 H 0.0245 0.7679 0.2774 0.036 Uiso 1 1 calc R . . C35 C 0.0365(3) 0.7134(2) 0.1338(4) 0.0309(9) Uani 1 1 d . . . H35 H -0.0144 0.7252 0.0952 0.037 Uiso 1 1 calc R . . C36 C 0.0872(2) 0.6705(2) 0.0803(4) 0.0230(8) Uani 1 1 d . . . H36 H 0.0712 0.6533 0.0055 0.028 Uiso 1 1 calc R . . C1S C 0.3373(2) 0.4409(2) -0.1826(4) 0.141(3) Uani 0.25 1 d PRDU A 1 H1S1 H 0.3790 0.4452 -0.2457 0.212 Uiso 0.25 1 d PR B 1 H1S2 H 0.3035 0.4809 -0.1973 0.212 Uiso 0.25 1 d PR C 1 H1S3 H 0.3039 0.4018 -0.2139 0.212 Uiso 0.25 1 d PR D 1 C2S C 0.395(2) 0.426(2) -0.080(3) 0.141(3) Uani 0.25 1 d PD A 1 H2S1 H 0.4472 0.4091 -0.1016 0.170 Uiso 0.25 1 calc PR A 1 H2S2 H 0.4036 0.4643 -0.0274 0.170 Uiso 0.25 1 calc PR A 1 C3S C 0.346(2) 0.372(2) -0.032(4) 0.141(3) Uani 0.25 1 d PD A 1 H3S1 H 0.3006 0.3924 0.0044 0.170 Uiso 0.25 1 calc PR A 1 H3S2 H 0.3242 0.3421 -0.0940 0.170 Uiso 0.25 1 calc PR A 1 C4S C 0.399(2) 0.335(3) 0.056(3) 0.141(3) Uani 0.25 1 d PD A 1 H4S1 H 0.4473 0.3618 0.0779 0.170 Uiso 0.25 1 calc PR A 1 H4S2 H 0.4168 0.2938 0.0186 0.170 Uiso 0.25 1 calc PR A 1 C5S C 0.365(3) 0.314(3) 0.164(3) 0.141(3) Uani 0.25 1 d PD A 1 H5S1 H 0.3349 0.3530 0.1897 0.170 Uiso 0.25 1 calc PR A 1 H5S2 H 0.3248 0.2791 0.1425 0.170 Uiso 0.25 1 calc PR A 1 C6S C 0.415(4) 0.289(3) 0.269(3) 0.141(3) Uani 0.25 1 d PD A 1 H6S1 H 0.3927 0.3120 0.3231 0.212 Uiso 0.25 1 d PR A 1 H6S2 H 0.4736 0.2935 0.2671 0.212 Uiso 0.25 1 d PR A 1 H6S3 H 0.4000 0.2420 0.2593 0.212 Uiso 0.25 1 d PR A 1 C1T C 0.3400(15) 0.4333(14) -0.193(2) 0.141(3) Uani 0.60 1 d PD E 2 H1T1 H 0.3817 0.4376 -0.2459 0.212 Uiso 0.60 1 d PR E 2 H1T2 H 0.3062 0.4734 -0.1974 0.212 Uiso 0.60 1 d PR E 2 H1T3 H 0.3065 0.3943 -0.2140 0.212 Uiso 0.60 1 d PR E 2 C2T C 0.3715(15) 0.4357(10) -0.0686(19) 0.141(3) Uani 0.60 1 d PD E 2 H2T1 H 0.3325 0.4559 -0.0201 0.170 Uiso 0.60 1 calc PR E 2 H2T2 H 0.4237 0.4594 -0.0562 0.170 Uiso 0.60 1 calc PR E 2 C3T C 0.3804(15) 0.3627(10) -0.0494(16) 0.141(3) Uani 0.60 1 d PD E 2 H3T1 H 0.3365 0.3385 -0.0952 0.170 Uiso 0.60 1 calc PR E 2 H3T2 H 0.4326 0.3471 -0.0733 0.170 Uiso 0.60 1 calc PR E 2 C4T C 0.3768(15) 0.3503(11) 0.0761(16) 0.141(3) Uani 0.60 1 d PD E 2 H4T1 H 0.3235 0.3658 0.0956 0.170 Uiso 0.60 1 calc PR E 2 H4T2 H 0.4177 0.3792 0.1185 0.170 Uiso 0.60 1 calc PR E 2 C5T C 0.3888(15) 0.2817(10) 0.1235(16) 0.141(3) Uani 0.60 1 d PD E 2 H5T1 H 0.4326 0.2622 0.0829 0.170 Uiso 0.60 1 calc PR E 2 H5T2 H 0.3393 0.2569 0.0959 0.170 Uiso 0.60 1 calc PR E 2 C6T C 0.4071(18) 0.2627(12) 0.2469(16) 0.141(3) Uani 0.60 1 d PD E 2 H6T1 H 0.3850 0.2854 0.3112 0.212 Uiso 0.60 1 d PR E 2 H6T2 H 0.4659 0.2669 0.2552 0.212 Uiso 0.60 1 d PR E 2 H6T3 H 0.3924 0.2155 0.2473 0.212 Uiso 0.60 1 d PR E 2 Cl3 Cl 0.3101(9) 0.4392(10) -0.1991(13) 0.082(4) Uani 0.15 1 d PD F 3 C7S C 0.392(3) 0.4043(18) -0.107(4) 0.082(4) Uani 0.15 1 d PD F 3 H7S1 H 0.4353 0.3897 -0.1531 0.099 Uiso 0.15 1 calc PR F 3 H7S2 H 0.3730 0.3652 -0.0653 0.099 Uiso 0.15 1 calc PR F 3 Cl4 Cl 0.4285(8) 0.4673(8) -0.0060(10) 0.082(4) Uani 0.15 1 d PD F 3 Cl5 Cl 0.3402(9) 0.2390(8) 0.2061(14) 0.083(3) Uani 0.15 1 d PD G 4 C8S C 0.3782(16) 0.276(3) 0.341(3) 0.083(3) Uani 0.15 1 d PD G 4 H8S1 H 0.3736 0.3249 0.3367 0.100 Uiso 0.15 1 calc PR G 4 H8S2 H 0.3477 0.2597 0.4039 0.100 Uiso 0.15 1 calc PR G 4 Cl6 Cl 0.4818(9) 0.2513(8) 0.3657(14) 0.083(3) Uani 0.15 1 d PD G 4 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01313(7) 0.01564(7) 0.01239(7) 0.00004(4) 0.00073(5) -0.00032(4) Au2 0.01356(7) 0.01631(7) 0.01393(7) 0.00044(4) 0.00057(5) -0.00085(4) Cl1 0.0162(4) 0.0217(4) 0.0196(4) -0.0017(3) 0.0022(3) -0.0040(3) Cl2 0.0207(4) 0.0239(5) 0.0289(5) 0.0046(4) -0.0049(3) -0.0075(4) P1 0.0145(4) 0.0186(5) 0.0134(4) 0.0015(3) 0.0015(3) -0.0004(3) P2 0.0176(4) 0.0173(4) 0.0144(4) 0.0007(3) 0.0009(3) -0.0009(3) F1 0.0121(11) 0.0424(17) 0.0422(15) 0.0037(13) -0.0017(10) 0.0036(10) F2 0.0386(15) 0.0370(16) 0.0168(11) -0.0045(10) -0.0032(10) -0.0139(12) C1 0.0126(15) 0.0178(17) 0.0195(16) 0.0000(13) -0.0008(12) 0.0016(13) C2 0.0191(18) 0.034(2) 0.0203(18) 0.0078(16) 0.0000(14) 0.0025(16) C3 0.0201(18) 0.032(2) 0.026(2) 0.0103(17) -0.0056(15) 0.0015(17) C4 0.0112(15) 0.026(2) 0.0270(19) -0.0005(16) -0.0023(13) 0.0044(14) C5 0.0156(17) 0.024(2) 0.0212(18) 0.0041(14) 0.0007(14) -0.0010(13) C6 0.0149(16) 0.0175(17) 0.0168(16) -0.0004(13) -0.0005(12) 0.0008(12) C7 0.0172(16) 0.0231(19) 0.0170(16) 0.0064(14) 0.0012(13) -0.0005(14) C8 0.029(2) 0.027(2) 0.0233(19) 0.0021(16) -0.0004(15) -0.0049(17) C9 0.034(2) 0.021(2) 0.038(2) 0.0037(18) -0.0060(19) -0.0033(18) C10 0.030(2) 0.032(3) 0.036(2) 0.014(2) -0.0058(18) -0.0087(19) C11 0.036(2) 0.035(3) 0.024(2) 0.0072(18) 0.0043(17) -0.007(2) C12 0.024(2) 0.028(2) 0.0249(19) 0.0043(16) 0.0036(15) -0.0010(16) C13 0.0214(17) 0.0211(18) 0.0123(15) 0.0026(13) 0.0031(12) 0.0012(14) C14 0.025(2) 0.025(2) 0.0198(18) -0.0014(15) 0.0009(15) -0.0044(16) C15 0.039(2) 0.027(2) 0.0205(19) -0.0023(16) 0.0039(17) -0.0062(19) C16 0.056(3) 0.026(2) 0.022(2) -0.0011(17) 0.011(2) 0.010(2) C17 0.034(2) 0.045(3) 0.0203(19) 0.0020(18) 0.0047(17) 0.019(2) C18 0.0213(19) 0.033(2) 0.0187(18) 0.0002(15) -0.0019(14) 0.0067(16) C19 0.0195(17) 0.0201(18) 0.0138(16) -0.0001(13) 0.0001(13) 0.0005(13) C20 0.0244(18) 0.0222(19) 0.0136(16) 0.0000(14) 0.0003(13) -0.0010(15) C21 0.0235(19) 0.031(2) 0.0119(15) -0.0002(15) 0.0002(13) -0.0013(16) C22 0.0181(17) 0.028(2) 0.0168(17) -0.0051(14) -0.0014(13) -0.0045(14) C23 0.0223(18) 0.025(2) 0.0166(17) -0.0029(14) 0.0009(13) -0.0032(15) C24 0.0136(15) 0.0215(18) 0.0151(15) -0.0013(13) 0.0004(12) 0.0005(13) C25 0.0212(17) 0.0219(19) 0.0184(17) 0.0052(14) -0.0011(13) -0.0017(14) C26 0.032(2) 0.033(2) 0.030(2) -0.0018(18) 0.0097(18) -0.0060(19) C27 0.042(3) 0.040(3) 0.032(2) 0.000(2) 0.014(2) -0.009(2) C28 0.037(3) 0.039(3) 0.037(3) 0.015(2) 0.004(2) -0.011(2) C29 0.031(2) 0.025(2) 0.048(3) 0.011(2) 0.004(2) -0.0034(18) C30 0.024(2) 0.022(2) 0.034(2) 0.0008(17) 0.0045(16) -0.0010(16) C31 0.0187(17) 0.0203(18) 0.0187(16) 0.0012(14) 0.0026(13) -0.0002(14) C32 0.032(2) 0.031(2) 0.0216(19) -0.0013(17) 0.0006(16) 0.0090(18) C33 0.042(3) 0.031(2) 0.023(2) -0.0006(17) 0.0090(18) 0.009(2) C34 0.033(2) 0.023(2) 0.036(2) -0.0006(18) 0.0174(19) 0.0007(17) C35 0.0196(19) 0.026(2) 0.047(3) 0.0015(19) 0.0040(18) 0.0024(16) C36 0.0172(17) 0.023(2) 0.028(2) -0.0010(15) 0.0002(14) -0.0013(15) C1S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C2S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C3S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C4S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C5S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C6S 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C1T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C2T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C3T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C4T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C5T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) C6T 0.132(5) 0.144(5) 0.153(5) -0.012(4) 0.033(4) 0.007(4) Cl3 0.068(6) 0.107(9) 0.067(5) -0.052(5) -0.019(5) 0.033(6) C7S 0.068(6) 0.107(9) 0.067(5) -0.052(5) -0.019(5) 0.033(6) Cl4 0.068(6) 0.107(9) 0.067(5) -0.052(5) -0.019(5) 0.033(6) Cl5 0.072(6) 0.070(7) 0.110(8) -0.029(6) 0.021(5) 0.011(5) C8S 0.072(6) 0.070(7) 0.110(8) -0.029(6) 0.021(5) 0.011(5) Cl6 0.072(6) 0.070(7) 0.110(8) -0.029(6) 0.021(5) 0.011(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.073(4) . ? Au1 P1 2.3331(9) . ? Au1 Cl1 2.3828(9) . ? Au1 Au2 2.56223(19) . ? Au2 C6 2.066(4) . ? Au2 P2 2.3327(10) . ? Au2 Cl2 2.3646(10) . ? P1 C1 1.795(4) . ? P1 C7 1.805(4) . ? P1 C13 1.808(4) . ? P2 C19 1.792(4) . ? P2 C31 1.806(4) . ? P2 C25 1.813(4) . ? F1 C4 1.355(4) . ? F2 C22 1.364(4) . ? C1 C6 1.404(5) . ? C1 C2 1.406(5) . ? C2 C3 1.373(5) . ? C2 H2 0.9500 . ? C3 C4 1.392(6) . ? C3 H3 0.9500 . ? C4 C5 1.381(5) . ? C5 C6 1.396(5) . ? C5 H5 0.9500 . ? C7 C8 1.395(6) . ? C7 C12 1.395(5) . ? C8 C9 1.373(6) . ? C8 H8 0.9500 . ? C9 C10 1.400(7) . ? C9 H9 0.9500 . ? C10 C11 1.370(7) . ? C10 H10 0.9500 . ? C11 C12 1.392(6) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.376(6) . ? C13 C14 1.402(5) . ? C14 C15 1.396(6) . ? C14 H14 0.9500 . ? C15 C16 1.369(7) . ? C15 H15 0.9500 . ? C16 C17 1.395(7) . ? C16 H16 0.9500 . ? C17 C18 1.396(6) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.400(5) . ? C19 C24 1.401(5) . ? C20 C21 1.402(6) . ? C20 H20 0.9500 . ? C21 C22 1.364(6) . ? C21 H21 0.9500 . ? C22 C23 1.382(5) . ? C23 C24 1.408(5) . ? C23 H23 0.9500 . ? C25 C30 1.379(6) . ? C25 C26 1.406(6) . ? C26 C27 1.391(6) . ? C26 H26 0.9500 . ? C27 C28 1.362(8) . ? C27 H27 0.9500 . ? C28 C29 1.398(7) . ? C28 H28 0.9500 . ? C29 C30 1.402(6) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.391(5) . ? C31 C32 1.404(6) . ? C32 C33 1.389(6) . ? C32 H32 0.9500 . ? C33 C34 1.378(7) . ? C33 H33 0.9500 . ? C34 C35 1.380(7) . ? C34 H34 0.9500 . ? C35 C36 1.397(6) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C1S C2S 1.488(11) . ? C1S H1S1 1.0650 . ? C1S H1S2 0.9867 . ? C1S H1S3 1.0093 . ? C2S C3S 1.488(11) . ? C2S H2S1 0.9900 . ? C2S H2S2 0.9900 . ? C3S C4S 1.488(11) . ? C3S H3S1 0.9900 . ? C3S H3S2 0.9900 . ? C4S C5S 1.488(11) . ? C4S H4S1 0.9900 . ? C4S H4S2 0.9900 . ? C5S C6S 1.488(11) . ? C5S H5S1 0.9900 . ? C5S H5S2 0.9900 . ? C6S H6S1 0.8894 . ? C6S H6S2 0.9870 . ? C6S H6S3 0.9834 . ? C1T C2T 1.489(10) . ? C1T H1S1 0.9703 . ? C1T H1S2 1.1307 . ? C1T H1S3 0.8915 . ? C1T H1T1 0.9800 . ? C1T H1T2 0.9800 . ? C1T H1T3 0.9800 . ? C2T C3T 1.489(9) . ? C2T H2T1 0.9900 . ? C2T H2T2 0.9900 . ? C3T C4T 1.489(9) . ? C3T H3T1 0.9900 . ? C3T H3T2 0.9900 . ? C4T C5T 1.489(9) . ? C4T H4T1 0.9900 . ? C4T H4T2 0.9900 . ? C5T C6T 1.489(9) . ? C5T H5T1 0.9900 . ? C5T H5T2 0.9900 . ? C6T H6T1 0.9800 . ? C6T H6T2 0.9800 . ? C6T H6T3 0.9800 . ? Cl3 C7S 1.793(16) . ? C7S Cl4 1.793(16) . ? C7S H7S1 0.9900 . ? C7S H7S2 0.9900 . ? Cl5 C8S 1.793(16) . ? C8S Cl6 1.793(16) . ? C8S H6S1 0.7989 . ? C8S H6S3 1.2502 . ? C8S H8S1 0.9900 . ? C8S H8S2 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 P1 174.20(11) . . ? C24 Au1 Cl1 93.17(11) . . ? P1 Au1 Cl1 91.75(3) . . ? C24 Au1 Au2 91.97(10) . . ? P1 Au1 Au2 82.95(2) . . ? Cl1 Au1 Au2 173.79(2) . . ? C6 Au2 P2 176.53(11) . . ? C6 Au2 Cl2 91.28(11) . . ? P2 Au2 Cl2 92.11(3) . . ? C6 Au2 Au1 92.29(10) . . ? P2 Au2 Au1 84.29(2) . . ? Cl2 Au2 Au1 175.42(3) . . ? C1 P1 C7 104.68(18) . . ? C1 P1 C13 109.97(18) . . ? C7 P1 C13 108.31(18) . . ? C1 P1 Au1 108.39(12) . . ? C7 P1 Au1 118.39(13) . . ? C13 P1 Au1 106.97(12) . . ? C19 P2 C31 108.79(18) . . ? C19 P2 C25 107.97(18) . . ? C31 P2 C25 105.78(19) . . ? C19 P2 Au2 107.05(13) . . ? C31 P2 Au2 112.50(13) . . ? C25 P2 Au2 114.56(13) . . ? C6 C1 C2 121.8(3) . . ? C6 C1 P1 115.2(3) . . ? C2 C1 P1 122.9(3) . . ? C3 C2 C1 120.1(4) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C2 C3 C4 117.6(4) . . ? C2 C3 H3 121.2 . . ? C4 C3 H3 121.2 . . ? F1 C4 C5 118.7(4) . . ? F1 C4 C3 117.7(3) . . ? C5 C4 C3 123.6(4) . . ? C4 C5 C6 119.2(4) . . ? C4 C5 H5 120.4 . . ? C6 C5 H5 120.4 . . ? C5 C6 C1 117.7(3) . . ? C5 C6 Au2 121.2(3) . . ? C1 C6 Au2 120.9(3) . . ? C8 C7 C12 118.9(4) . . ? C8 C7 P1 118.4(3) . . ? C12 C7 P1 122.4(3) . . ? C9 C8 C7 121.1(4) . . ? C9 C8 H8 119.4 . . ? C7 C8 H8 119.4 . . ? C8 C9 C10 119.2(4) . . ? C8 C9 H9 120.4 . . ? C10 C9 H9 120.4 . . ? C11 C10 C9 120.6(4) . . ? C11 C10 H10 119.7 . . ? C9 C10 H10 119.7 . . ? C10 C11 C12 120.0(4) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C11 C12 C7 120.2(4) . . ? C11 C12 H12 119.9 . . ? C7 C12 H12 119.9 . . ? C18 C13 C14 120.5(4) . . ? C18 C13 P1 118.9(3) . . ? C14 C13 P1 120.4(3) . . ? C15 C14 C13 118.9(4) . . ? C15 C14 H14 120.6 . . ? C13 C14 H14 120.6 . . ? C16 C15 C14 120.3(4) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C15 C16 C17 121.2(4) . . ? C15 C16 H16 119.4 . . ? C17 C16 H16 119.4 . . ? C16 C17 C18 118.7(4) . . ? C16 C17 H17 120.6 . . ? C18 C17 H17 120.6 . . ? C13 C18 C17 120.4(4) . . ? C13 C18 H18 119.8 . . ? C17 C18 H18 119.8 . . ? C20 C19 C24 121.8(4) . . ? C20 C19 P2 122.5(3) . . ? C24 C19 P2 115.6(3) . . ? C19 C20 C21 119.8(4) . . ? C19 C20 H20 120.1 . . ? C21 C20 H20 120.1 . . ? C22 C21 C20 117.2(3) . . ? C22 C21 H21 121.4 . . ? C20 C21 H21 121.4 . . ? F2 C22 C21 117.2(3) . . ? F2 C22 C23 117.9(4) . . ? C21 C22 C23 124.9(4) . . ? C22 C23 C24 118.5(4) . . ? C22 C23 H23 120.8 . . ? C24 C23 H23 120.8 . . ? C19 C24 C23 117.8(3) . . ? C19 C24 Au1 122.4(3) . . ? C23 C24 Au1 119.8(3) . . ? C30 C25 C26 119.9(4) . . ? C30 C25 P2 121.3(3) . . ? C26 C25 P2 118.6(3) . . ? C27 C26 C25 119.7(5) . . ? C27 C26 H26 120.2 . . ? C25 C26 H26 120.2 . . ? C28 C27 C26 120.3(5) . . ? C28 C27 H27 119.8 . . ? C26 C27 H27 119.8 . . ? C27 C28 C29 120.8(4) . . ? C27 C28 H28 119.6 . . ? C29 C28 H28 119.6 . . ? C28 C29 C30 119.2(5) . . ? C28 C29 H29 120.4 . . ? C30 C29 H29 120.4 . . ? C25 C30 C29 120.0(4) . . ? C25 C30 H30 120.0 . . ? C29 C30 H30 120.0 . . ? C36 C31 C32 119.6(4) . . ? C36 C31 P2 121.0(3) . . ? C32 C31 P2 119.3(3) . . ? C33 C32 C31 120.3(4) . . ? C33 C32 H32 119.9 . . ? C31 C32 H32 119.9 . . ? C34 C33 C32 119.6(4) . . ? C34 C33 H33 120.2 . . ? C32 C33 H33 120.2 . . ? C33 C34 C35 120.6(4) . . ? C33 C34 H34 119.7 . . ? C35 C34 H34 119.7 . . ? C34 C35 C36 120.6(4) . . ? C34 C35 H35 119.7 . . ? C36 C35 H35 119.7 . . ? C31 C36 C35 119.3(4) . . ? C31 C36 H36 120.4 . . ? C35 C36 H36 120.4 . . ? C2S C1S H1S1 99.0 . . ? C2S C1S H1S2 128.1 . . ? H1S1 C1S H1S2 102.5 . . ? C2S C1S H1S3 114.8 . . ? H1S1 C1S H1S3 100.9 . . ? H1S2 C1S H1S3 106.6 . . ? C3S C2S C1S 97(2) . . ? C3S C2S H2S1 112.4 . . ? C1S C2S H2S1 112.4 . . ? C3S C2S H2S2 112.4 . . ? C1S C2S H2S2 112.4 . . ? H2S1 C2S H2S2 110.0 . . ? C4S C3S C2S 109(3) . . ? C4S C3S H3S1 109.9 . . ? C2S C3S H3S1 109.9 . . ? C4S C3S H3S2 111.0 . . ? C2S C3S H3S2 109.9 . . ? H3S1 C3S H3S2 108.3 . . ? C3S C4S C5S 119(3) . . ? C3S C4S H4S1 109.0 . . ? C5S C4S H4S1 107.7 . . ? C3S C4S H4S2 107.7 . . ? C5S C4S H4S2 107.7 . . ? H4S1 C4S H4S2 107.1 . . ? C6S C5S C4S 124(3) . . ? C6S C5S H5S1 106.3 . . ? C4S C5S H5S1 106.3 . . ? C6S C5S H5S2 106.3 . . ? C4S C5S H5S2 106.3 . . ? H5S1 C5S H5S2 106.4 . . ? C5S C6S H6S1 99.9 . . ? C5S C6S H6S2 115.3 . . ? H6S1 C6S H6S2 117.0 . . ? C5S C6S H6S3 96.9 . . ? H6S1 C6S H6S3 117.3 . . ? H6S2 C6S H6S3 108.6 . . ? C2T C1T H1T1 113.9 . . ? C2T C1T H1T2 100.0 . . ? H1T1 C1T H1T2 109.5 . . ? C2T C1T H1T3 114.1 . . ? H1T1 C1T H1T3 109.5 . . ? H1T2 C1T H1T3 109.5 . . ? C1T C2T C3T 97.8(18) . . ? C1T C2T H2T1 112.2 . . ? C3T C2T H2T1 112.2 . . ? C1T C2T H2T2 112.2 . . ? C3T C2T H2T2 112.2 . . ? H2T1 C2T H2T2 109.8 . . ? C4T C3T C2T 107.4(18) . . ? C4T C3T H3T1 110.2 . . ? C2T C3T H3T1 110.2 . . ? C4T C3T H3T2 110.2 . . ? C2T C3T H3T2 110.2 . . ? H3T1 C3T H3T2 108.5 . . ? C3T C4T C5T 120.1(19) . . ? C3T C4T H4T1 107.3 . . ? C5T C4T H4T1 107.3 . . ? C3T C4T H4T2 107.3 . . ? C5T C4T H4T2 107.3 . . ? H4T1 C4T H4T2 106.9 . . ? C4T C5T C6T 127.1(19) . . ? C4T C5T H5T1 105.5 . . ? C6T C5T H5T1 105.5 . . ? C4T C5T H5T2 105.6 . . ? C6T C5T H5T2 105.5 . . ? H5T1 C5T H5T2 106.1 . . ? C5T C6T H6T1 124.1 . . ? C5T C6T H6T2 100.4 . . ? H6T1 C6T H6T2 109.5 . . ? C5T C6T H6T3 103.1 . . ? H6T1 C6T H6T3 109.5 . . ? H6T2 C6T H6T3 109.5 . . ? Cl3 C7S Cl4 107.8(16) . . ? Cl3 C7S H7S1 110.1 . . ? Cl4 C7S H7S1 110.1 . . ? Cl3 C7S H7S2 110.1 . . ? Cl4 C7S H7S2 110.1 . . ? H7S1 C7S H7S2 108.5 . . ? Cl6 C8S Cl5 106.2(17) . . ? Cl6 C8S H8S1 110.4 . . ? Cl5 C8S H8S1 110.4 . . ? Cl6 C8S H8S2 110.5 . . ? Cl5 C8S H8S2 110.5 . . ? H8S1 C8S H8S2 108.7 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -147.90(15) . . . . ? P1 Au1 Au2 C6 34.88(11) . . . . ? C24 Au1 Au2 P2 32.67(11) . . . . ? P1 Au1 Au2 P2 -144.55(3) . . . . ? Cl1 Au1 P1 C1 145.20(14) . . . . ? Au2 Au1 P1 C1 -38.04(14) . . . . ? Cl1 Au1 P1 C7 26.30(15) . . . . ? Au2 Au1 P1 C7 -156.94(15) . . . . ? Cl1 Au1 P1 C13 -96.27(14) . . . . ? Au2 Au1 P1 C13 80.49(14) . . . . ? Cl2 Au2 P2 C19 144.42(14) . . . . ? Au1 Au2 P2 C19 -38.41(13) . . . . ? Cl2 Au2 P2 C31 -96.12(14) . . . . ? Au1 Au2 P2 C31 81.05(14) . . . . ? Cl2 Au2 P2 C25 24.74(15) . . . . ? Au1 Au2 P2 C25 -158.08(15) . . . . ? C7 P1 C1 C6 153.4(3) . . . . ? C13 P1 C1 C6 -90.5(3) . . . . ? Au1 P1 C1 C6 26.1(3) . . . . ? C7 P1 C1 C2 -23.2(4) . . . . ? C13 P1 C1 C2 92.9(4) . . . . ? Au1 P1 C1 C2 -150.5(3) . . . . ? C6 C1 C2 C3 -1.1(6) . . . . ? P1 C1 C2 C3 175.3(4) . . . . ? C1 C2 C3 C4 -0.6(7) . . . . ? C2 C3 C4 F1 -177.8(4) . . . . ? C2 C3 C4 C5 2.1(7) . . . . ? F1 C4 C5 C6 178.0(4) . . . . ? C3 C4 C5 C6 -1.9(7) . . . . ? C4 C5 C6 C1 0.1(6) . . . . ? C4 C5 C6 Au2 175.5(3) . . . . ? C2 C1 C6 C5 1.3(6) . . . . ? P1 C1 C6 C5 -175.3(3) . . . . ? C2 C1 C6 Au2 -174.1(3) . . . . ? P1 C1 C6 Au2 9.3(4) . . . . ? Cl2 Au2 C6 C5 -33.1(3) . . . . ? Au1 Au2 C6 C5 149.8(3) . . . . ? Cl2 Au2 C6 C1 142.2(3) . . . . ? Au1 Au2 C6 C1 -35.0(3) . . . . ? C1 P1 C7 C8 -70.3(3) . . . . ? C13 P1 C7 C8 172.4(3) . . . . ? Au1 P1 C7 C8 50.5(4) . . . . ? C1 P1 C7 C12 104.3(4) . . . . ? C13 P1 C7 C12 -13.0(4) . . . . ? Au1 P1 C7 C12 -134.9(3) . . . . ? C12 C7 C8 C9 -1.5(6) . . . . ? P1 C7 C8 C9 173.2(3) . . . . ? C7 C8 C9 C10 0.8(7) . . . . ? C8 C9 C10 C11 0.6(7) . . . . ? C9 C10 C11 C12 -1.4(7) . . . . ? C10 C11 C12 C7 0.7(7) . . . . ? C8 C7 C12 C11 0.8(6) . . . . ? P1 C7 C12 C11 -173.8(3) . . . . ? C1 P1 C13 C18 165.8(3) . . . . ? C7 P1 C13 C18 -80.4(3) . . . . ? Au1 P1 C13 C18 48.3(3) . . . . ? C1 P1 C13 C14 -8.0(4) . . . . ? C7 P1 C13 C14 105.8(3) . . . . ? Au1 P1 C13 C14 -125.5(3) . . . . ? C18 C13 C14 C15 0.3(6) . . . . ? P1 C13 C14 C15 174.0(3) . . . . ? C13 C14 C15 C16 0.1(6) . . . . ? C14 C15 C16 C17 0.9(7) . . . . ? C15 C16 C17 C18 -2.1(7) . . . . ? C14 C13 C18 C17 -1.6(6) . . . . ? P1 C13 C18 C17 -175.4(3) . . . . ? C16 C17 C18 C13 2.5(7) . . . . ? C31 P2 C19 C20 87.3(4) . . . . ? C25 P2 C19 C20 -27.0(4) . . . . ? Au2 P2 C19 C20 -150.9(3) . . . . ? C31 P2 C19 C24 -91.2(3) . . . . ? C25 P2 C19 C24 154.5(3) . . . . ? Au2 P2 C19 C24 30.6(3) . . . . ? C24 C19 C20 C21 -2.4(6) . . . . ? P2 C19 C20 C21 179.2(3) . . . . ? C19 C20 C21 C22 2.6(6) . . . . ? C20 C21 C22 F2 178.7(4) . . . . ? C20 C21 C22 C23 -2.0(6) . . . . ? F2 C22 C23 C24 -179.6(4) . . . . ? C21 C22 C23 C24 1.0(6) . . . . ? C20 C19 C24 C23 1.4(6) . . . . ? P2 C19 C24 C23 179.9(3) . . . . ? C20 C19 C24 Au1 -176.8(3) . . . . ? P2 C19 C24 Au1 1.7(4) . . . . ? C22 C23 C24 C19 -0.7(6) . . . . ? C22 C23 C24 Au1 177.6(3) . . . . ? Cl1 Au1 C24 C19 147.9(3) . . . . ? Au2 Au1 C24 C19 -28.6(3) . . . . ? Cl1 Au1 C24 C23 -30.3(3) . . . . ? Au2 Au1 C24 C23 153.2(3) . . . . ? C19 P2 C25 C30 140.1(3) . . . . ? C31 P2 C25 C30 23.7(4) . . . . ? Au2 P2 C25 C30 -100.8(3) . . . . ? C19 P2 C25 C26 -45.1(4) . . . . ? C31 P2 C25 C26 -161.5(3) . . . . ? Au2 P2 C25 C26 74.0(3) . . . . ? C30 C25 C26 C27 -2.8(7) . . . . ? P2 C25 C26 C27 -177.7(4) . . . . ? C25 C26 C27 C28 1.5(8) . . . . ? C26 C27 C28 C29 0.5(8) . . . . ? C27 C28 C29 C30 -1.1(8) . . . . ? C26 C25 C30 C29 2.3(6) . . . . ? P2 C25 C30 C29 177.0(3) . . . . ? C28 C29 C30 C25 -0.4(7) . . . . ? C19 P2 C31 C36 -29.4(4) . . . . ? C25 P2 C31 C36 86.4(4) . . . . ? Au2 P2 C31 C36 -147.8(3) . . . . ? C19 P2 C31 C32 152.0(3) . . . . ? C25 P2 C31 C32 -92.2(4) . . . . ? Au2 P2 C31 C32 33.5(4) . . . . ? C36 C31 C32 C33 -1.6(7) . . . . ? P2 C31 C32 C33 177.0(4) . . . . ? C31 C32 C33 C34 1.9(7) . . . . ? C32 C33 C34 C35 -1.0(7) . . . . ? C33 C34 C35 C36 -0.1(7) . . . . ? C32 C31 C36 C35 0.5(6) . . . . ? P2 C31 C36 C35 -178.2(3) . . . . ? C34 C35 C36 C31 0.4(7) . . . . ? C1S C2S C3S C4S 165(4) . . . . ? C2S C3S C4S C5S 139(5) . . . . ? C3S C4S C5S C6S -166(5) . . . . ? C1T C2T C3T C4T -156(2) . . . . ? C2T C3T C4T C5T -176(2) . . . . ? C3T C4T C5T C6T 164(2) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 33.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 4.666 _refine_diff_density_min -4.155 _refine_diff_density_rms 0.236 # Attachment 'neda02101.cif.txt' data_neda02101 _database_code_depnum_ccdc_archive 'CCDC 726002' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 Cl2 F2 P2' _chemical_formula_sum 'C36 H26 Au2 Cl2 F2 P2' _chemical_formula_weight 1023.34 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.01700(10) _cell_length_b 15.97300(10) _cell_length_c 18.1351(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.4610(10) _cell_angle_gamma 90.00 _cell_volume 3191.21(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 72345 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description polyhedron _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.130 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1928 _exptl_absorpt_coefficient_mu 9.490 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.067 _exptl_absorpt_correction_T_max 0.124 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 76037 _diffrn_reflns_av_R_equivalents 0.0554 _diffrn_reflns_av_sigmaI/netI 0.0322 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 2.79 _diffrn_reflns_theta_max 35.00 _reflns_number_total 14036 _reflns_number_gt 11981 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0251P)^2^+3.8101P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 14036 _refine_ls_number_parameters 397 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0367 _refine_ls_R_factor_gt 0.0266 _refine_ls_wR_factor_ref 0.0599 _refine_ls_wR_factor_gt 0.0576 _refine_ls_goodness_of_fit_ref 1.038 _refine_ls_restrained_S_all 1.038 _refine_ls_shift/su_max 0.007 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.098851(8) 0.770863(6) 0.423771(5) 0.01522(2) Uani 1 1 d . . . Au2 Au 0.413666(9) 0.745981(6) 0.473056(5) 0.01688(2) Uani 1 1 d . . . P1 P 0.16388(5) 0.89148(4) 0.37651(3) 0.01344(10) Uani 1 1 d . . . P2 P 0.42227(6) 0.66002(4) 0.37657(3) 0.01480(10) Uani 1 1 d . . . Cl1 Cl 0.01769(6) 0.65112(4) 0.47238(4) 0.02455(12) Uani 1 1 d . . . Cl2 Cl 0.41739(7) 0.82735(5) 0.57702(4) 0.02774(14) Uani 1 1 d . . . F1 F 0.67485(14) 0.91382(11) 0.27801(10) 0.0251(3) Uani 1 1 d . . . F2 F 0.06632(16) 0.71684(11) 0.13475(10) 0.0282(4) Uani 1 1 d . . . C1 C 0.1504(2) 0.97838(15) 0.44043(13) 0.0151(4) Uani 1 1 d . . . C2 C 0.1736(2) 0.96279(16) 0.51514(14) 0.0180(4) Uani 1 1 d . . . H2 H 0.1841 0.9070 0.5321 0.022 Uiso 1 1 calc R . . C3 C 0.1812(2) 1.02922(17) 0.56434(14) 0.0204(5) Uani 1 1 d . . . H3 H 0.1974 1.0188 0.6150 0.024 Uiso 1 1 calc R . . C4 C 0.1651(2) 1.11108(17) 0.53974(15) 0.0206(5) Uani 1 1 d . . . H4 H 0.1736 1.1565 0.5733 0.025 Uiso 1 1 calc R . . C5 C 0.1367(2) 1.12639(16) 0.46622(15) 0.0197(4) Uani 1 1 d . . . H5 H 0.1220 1.1820 0.4499 0.024 Uiso 1 1 calc R . . C6 C 0.1298(2) 1.06014(15) 0.41660(14) 0.0169(4) Uani 1 1 d . . . H6 H 0.1110 1.0707 0.3662 0.020 Uiso 1 1 calc R . . C7 C 0.0889(2) 0.92304(15) 0.29100(13) 0.0149(4) Uani 1 1 d . . . C8 C 0.1469(2) 0.97796(15) 0.24256(14) 0.0173(4) Uani 1 1 d . . . H8 H 0.2223 1.0025 0.2563 0.021 Uiso 1 1 calc R . . C9 C 0.0949(2) 0.99682(16) 0.17448(14) 0.0205(5) Uani 1 1 d . . . H9 H 0.1341 1.0347 0.1420 0.025 Uiso 1 1 calc R . . C10 C -0.0150(2) 0.96005(17) 0.15400(14) 0.0220(5) Uani 1 1 d . . . H10 H -0.0500 0.9720 0.1071 0.026 Uiso 1 1 calc R . . C11 C -0.0733(2) 0.90597(18) 0.20196(14) 0.0209(5) Uani 1 1 d . . . H11 H -0.1486 0.8815 0.1881 0.025 Uiso 1 1 calc R . . C12 C -0.0217(2) 0.88741(16) 0.27044(14) 0.0179(4) Uani 1 1 d . . . H12 H -0.0621 0.8504 0.3031 0.021 Uiso 1 1 calc R . . C13 C 0.3238(2) 0.89274(14) 0.35097(13) 0.0143(4) Uani 1 1 d . . . C14 C 0.4002(2) 0.95615(15) 0.37754(14) 0.0172(4) Uani 1 1 d . . . H14 H 0.3694 0.9953 0.4121 0.021 Uiso 1 1 calc R . . C15 C 0.5200(2) 0.96350(15) 0.35486(14) 0.0184(4) Uani 1 1 d . . . H15 H 0.5722 1.0056 0.3742 0.022 Uiso 1 1 calc R . . C16 C 0.5596(2) 0.90698(16) 0.30313(14) 0.0179(4) Uani 1 1 d . . . C17 C 0.4883(2) 0.84278(15) 0.27550(13) 0.0163(4) Uani 1 1 d . . . H17 H 0.5200 0.8053 0.2398 0.020 Uiso 1 1 calc R . . C18 C 0.3697(2) 0.83341(14) 0.30039(13) 0.0141(4) Uani 1 1 d . . . C19 C 0.2958(2) 0.76022(14) 0.27332(13) 0.0141(4) Uani 1 1 d . . . C20 C 0.2159(2) 0.77105(15) 0.21431(14) 0.0174(4) Uani 1 1 d . . . H20 H 0.2099 0.8237 0.1902 0.021 Uiso 1 1 calc R . . C21 C 0.1453(2) 0.70427(16) 0.19121(14) 0.0197(4) Uani 1 1 d . . . C22 C 0.1510(2) 0.62593(16) 0.22294(15) 0.0207(5) Uani 1 1 d . . . H22 H 0.0996 0.5818 0.2068 0.025 Uiso 1 1 calc R . . C23 C 0.2352(2) 0.61413(15) 0.27957(14) 0.0177(4) Uani 1 1 d . . . H23 H 0.2431 0.5603 0.3014 0.021 Uiso 1 1 calc R . . C24 C 0.3082(2) 0.67957(14) 0.30509(13) 0.0150(4) Uani 1 1 d . . . C25 C 0.4026(2) 0.55140(15) 0.40333(14) 0.0180(4) Uani 1 1 d . . . C26 C 0.3033(2) 0.53055(18) 0.44734(16) 0.0237(5) Uani 1 1 d . . . H26 H 0.2504 0.5731 0.4645 0.028 Uiso 1 1 calc R . . C27 C 0.2822(3) 0.44742(19) 0.46580(17) 0.0275(6) Uani 1 1 d . . . H27 H 0.2138 0.4331 0.4948 0.033 Uiso 1 1 calc R . . C28 C 0.3609(3) 0.38531(18) 0.44202(16) 0.0272(6) Uani 1 1 d . . . H28 H 0.3452 0.3284 0.4540 0.033 Uiso 1 1 calc R . . C29 C 0.4620(3) 0.40584(17) 0.40102(16) 0.0276(6) Uani 1 1 d . . . H29 H 0.5172 0.3634 0.3864 0.033 Uiso 1 1 calc R . . C30 C 0.4826(3) 0.48867(16) 0.38117(15) 0.0229(5) Uani 1 1 d . . . H30 H 0.5514 0.5026 0.3524 0.028 Uiso 1 1 calc R . . C31 C 0.5646(2) 0.66477(15) 0.32657(13) 0.0163(4) Uani 1 1 d . . . C32 C 0.6706(2) 0.69122(16) 0.36233(15) 0.0199(4) Uani 1 1 d . . . H32 H 0.6702 0.7024 0.4138 0.024 Uiso 1 1 calc R . . C33 C 0.7769(2) 0.70114(17) 0.32220(16) 0.0227(5) Uani 1 1 d . . . H33 H 0.8497 0.7173 0.3468 0.027 Uiso 1 1 calc R . . C34 C 0.7776(2) 0.68777(17) 0.24692(16) 0.0228(5) Uani 1 1 d . . . H34 H 0.8497 0.6972 0.2197 0.027 Uiso 1 1 calc R . . C35 C 0.6727(2) 0.66047(17) 0.21094(15) 0.0219(5) Uani 1 1 d . . . H35 H 0.6732 0.6507 0.1593 0.026 Uiso 1 1 calc R . . C36 C 0.5671(2) 0.64756(15) 0.25109(14) 0.0183(4) Uani 1 1 d . . . H36 H 0.4963 0.6269 0.2270 0.022 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01606(4) 0.01384(4) 0.01576(4) 0.00042(3) 0.00072(3) -0.00132(3) Au2 0.02201(4) 0.01508(4) 0.01350(4) -0.00127(3) -0.00304(3) 0.00093(3) P1 0.0140(2) 0.0126(2) 0.0136(3) -0.00019(19) -0.00083(19) -0.00039(19) P2 0.0171(3) 0.0134(2) 0.0138(3) -0.00062(19) -0.0024(2) -0.0005(2) Cl1 0.0270(3) 0.0190(3) 0.0277(3) 0.0040(2) 0.0031(2) -0.0060(2) Cl2 0.0382(4) 0.0255(3) 0.0194(3) -0.0085(2) -0.0071(3) 0.0061(3) F1 0.0155(7) 0.0261(8) 0.0338(9) -0.0052(7) 0.0060(6) -0.0040(6) F2 0.0321(9) 0.0243(8) 0.0278(9) -0.0027(7) -0.0161(7) 0.0017(7) C1 0.0145(9) 0.0158(10) 0.0151(10) -0.0008(7) -0.0001(8) 0.0000(7) C2 0.0189(10) 0.0184(11) 0.0168(10) -0.0014(8) -0.0022(8) 0.0019(8) C3 0.0192(11) 0.0257(12) 0.0162(11) -0.0036(9) -0.0003(8) 0.0000(9) C4 0.0180(10) 0.0230(12) 0.0207(12) -0.0076(9) 0.0019(9) -0.0018(9) C5 0.0222(11) 0.0149(10) 0.0220(12) -0.0028(8) 0.0013(9) 0.0015(8) C6 0.0171(10) 0.0164(10) 0.0173(11) -0.0003(8) -0.0012(8) 0.0004(8) C7 0.0151(9) 0.0150(10) 0.0148(10) -0.0014(7) -0.0017(8) 0.0022(7) C8 0.0190(10) 0.0148(10) 0.0180(11) 0.0002(8) -0.0022(8) -0.0009(8) C9 0.0236(12) 0.0202(11) 0.0177(11) 0.0022(8) -0.0017(9) 0.0016(9) C10 0.0248(12) 0.0248(12) 0.0163(11) -0.0015(9) -0.0061(9) 0.0047(9) C11 0.0170(10) 0.0281(13) 0.0176(11) -0.0040(9) -0.0049(8) 0.0022(9) C12 0.0155(10) 0.0208(11) 0.0174(11) -0.0016(8) -0.0008(8) -0.0010(8) C13 0.0147(9) 0.0131(9) 0.0151(10) -0.0002(7) -0.0005(7) 0.0000(7) C14 0.0168(10) 0.0145(10) 0.0203(11) -0.0021(8) -0.0023(8) 0.0000(8) C15 0.0164(10) 0.0162(10) 0.0224(12) -0.0012(8) -0.0021(8) -0.0011(8) C16 0.0127(9) 0.0197(11) 0.0213(11) 0.0018(8) 0.0018(8) -0.0004(8) C17 0.0179(10) 0.0147(10) 0.0164(10) 0.0001(8) 0.0019(8) -0.0003(8) C18 0.0144(9) 0.0126(9) 0.0152(10) -0.0002(7) -0.0016(7) -0.0006(7) C19 0.0144(9) 0.0155(10) 0.0124(9) -0.0015(7) -0.0003(7) -0.0006(7) C20 0.0191(10) 0.0169(10) 0.0161(10) -0.0021(8) -0.0015(8) 0.0019(8) C21 0.0214(11) 0.0211(11) 0.0164(10) -0.0036(8) -0.0058(8) 0.0031(9) C22 0.0212(11) 0.0191(11) 0.0218(12) -0.0038(9) -0.0043(9) -0.0030(9) C23 0.0194(10) 0.0147(10) 0.0190(11) 0.0000(8) -0.0025(8) -0.0023(8) C24 0.0152(9) 0.0147(10) 0.0150(10) -0.0019(7) -0.0013(7) -0.0010(7) C25 0.0222(11) 0.0151(10) 0.0165(10) 0.0013(8) -0.0049(8) 0.0000(8) C26 0.0216(12) 0.0231(12) 0.0263(13) 0.0060(10) -0.0020(10) -0.0018(9) C27 0.0253(12) 0.0292(14) 0.0280(14) 0.0108(11) -0.0069(11) -0.0073(10) C28 0.0402(15) 0.0184(12) 0.0227(13) 0.0063(9) -0.0110(11) -0.0068(11) C29 0.0440(16) 0.0180(12) 0.0209(12) -0.0004(9) -0.0039(11) 0.0061(11) C30 0.0316(13) 0.0177(11) 0.0195(12) 0.0007(9) -0.0002(10) 0.0041(10) C31 0.0169(10) 0.0137(10) 0.0182(10) -0.0002(8) -0.0017(8) 0.0002(7) C32 0.0205(11) 0.0182(11) 0.0208(11) 0.0003(8) -0.0040(9) -0.0010(8) C33 0.0175(10) 0.0203(12) 0.0303(13) -0.0017(10) -0.0033(9) 0.0004(9) C34 0.0203(11) 0.0197(11) 0.0285(13) -0.0032(9) 0.0036(10) 0.0019(9) C35 0.0238(12) 0.0198(11) 0.0223(12) -0.0038(9) 0.0007(9) 0.0032(9) C36 0.0191(10) 0.0173(10) 0.0186(11) -0.0020(8) -0.0026(8) 0.0014(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 P1 2.2292(6) . ? Au1 Cl1 2.2908(6) . ? Au1 Au2 3.59669(13) . ? Au2 P2 2.2267(6) . ? Au2 Cl2 2.2900(6) . ? P1 C1 1.815(2) . ? P1 C7 1.822(2) . ? P1 C13 1.825(2) . ? P2 C25 1.815(2) . ? P2 C31 1.820(3) . ? P2 C24 1.825(2) . ? F1 C16 1.357(3) . ? F2 C21 1.353(3) . ? C1 C6 1.394(3) . ? C1 C2 1.399(3) . ? C2 C3 1.388(3) . ? C2 H2 0.9500 . ? C3 C4 1.392(4) . ? C3 H3 0.9500 . ? C4 C5 1.389(4) . ? C4 H4 0.9500 . ? C5 C6 1.391(3) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 C12 1.394(3) . ? C7 C8 1.399(3) . ? C8 C9 1.390(3) . ? C8 H8 0.9500 . ? C9 C10 1.393(4) . ? C9 H9 0.9500 . ? C10 C11 1.387(4) . ? C10 H10 0.9500 . ? C11 C12 1.393(3) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.400(3) . ? C13 C18 1.415(3) . ? C14 C15 1.390(3) . ? C14 H14 0.9500 . ? C15 C16 1.375(3) . ? C15 H15 0.9500 . ? C16 C17 1.383(3) . ? C17 C18 1.394(3) . ? C17 H17 0.9500 . ? C18 C19 1.504(3) . ? C19 C20 1.391(3) . ? C19 C24 1.417(3) . ? C20 C21 1.383(4) . ? C20 H20 0.9500 . ? C21 C22 1.379(4) . ? C22 C23 1.391(3) . ? C22 H22 0.9500 . ? C23 C24 1.396(3) . ? C23 H23 0.9500 . ? C25 C30 1.396(4) . ? C25 C26 1.400(4) . ? C26 C27 1.389(4) . ? C26 H26 0.9500 . ? C27 C28 1.388(4) . ? C27 H27 0.9500 . ? C28 C29 1.383(4) . ? C28 H28 0.9500 . ? C29 C30 1.390(4) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.396(3) . ? C31 C36 1.397(3) . ? C32 C33 1.393(4) . ? C32 H32 0.9500 . ? C33 C34 1.382(4) . ? C33 H33 0.9500 . ? C34 C35 1.393(4) . ? C34 H34 0.9500 . ? C35 C36 1.393(4) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag P1 Au1 Cl1 175.71(2) . . ? P2 Au2 Cl2 175.06(2) . . ? C1 P1 C7 107.04(11) . . ? C1 P1 C13 103.75(11) . . ? C7 P1 C13 102.27(11) . . ? C1 P1 Au1 112.78(8) . . ? C7 P1 Au1 114.93(8) . . ? C13 P1 Au1 114.90(8) . . ? C25 P2 C31 106.16(11) . . ? C25 P2 C24 105.68(11) . . ? C31 P2 C24 103.32(11) . . ? C25 P2 Au2 111.93(8) . . ? C31 P2 Au2 114.09(8) . . ? C24 P2 Au2 114.78(8) . . ? C6 C1 C2 119.7(2) . . ? C6 C1 P1 122.18(18) . . ? C2 C1 P1 117.84(18) . . ? C3 C2 C1 119.7(2) . . ? C3 C2 H2 120.1 . . ? C1 C2 H2 120.1 . . ? C2 C3 C4 120.3(2) . . ? C2 C3 H3 119.8 . . ? C4 C3 H3 119.8 . . ? C5 C4 C3 120.0(2) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? C4 C5 C6 119.9(2) . . ? C4 C5 H5 120.1 . . ? C6 C5 H5 120.1 . . ? C5 C6 C1 120.3(2) . . ? C5 C6 H6 119.9 . . ? C1 C6 H6 119.9 . . ? C12 C7 C8 119.4(2) . . ? C12 C7 P1 120.28(19) . . ? C8 C7 P1 120.10(17) . . ? C9 C8 C7 120.4(2) . . ? C9 C8 H8 119.8 . . ? C7 C8 H8 119.8 . . ? C8 C9 C10 119.8(2) . . ? C8 C9 H9 120.1 . . ? C10 C9 H9 120.1 . . ? C11 C10 C9 120.1(2) . . ? C11 C10 H10 120.0 . . ? C9 C10 H10 120.0 . . ? C10 C11 C12 120.3(2) . . ? C10 C11 H11 119.9 . . ? C12 C11 H11 119.9 . . ? C11 C12 C7 120.1(2) . . ? C11 C12 H12 120.0 . . ? C7 C12 H12 120.0 . . ? C14 C13 C18 119.4(2) . . ? C14 C13 P1 119.99(18) . . ? C18 C13 P1 120.50(17) . . ? C15 C14 C13 121.9(2) . . ? C15 C14 H14 119.0 . . ? C13 C14 H14 119.0 . . ? C16 C15 C14 116.9(2) . . ? C16 C15 H15 121.5 . . ? C14 C15 H15 121.5 . . ? F1 C16 C15 118.6(2) . . ? F1 C16 C17 117.9(2) . . ? C15 C16 C17 123.5(2) . . ? C16 C17 C18 119.6(2) . . ? C16 C17 H17 120.2 . . ? C18 C17 H17 120.2 . . ? C17 C18 C13 118.6(2) . . ? C17 C18 C19 118.9(2) . . ? C13 C18 C19 122.5(2) . . ? C20 C19 C24 118.9(2) . . ? C20 C19 C18 119.4(2) . . ? C24 C19 C18 121.6(2) . . ? C21 C20 C19 119.2(2) . . ? C21 C20 H20 120.4 . . ? C19 C20 H20 120.4 . . ? F2 C21 C22 118.5(2) . . ? F2 C21 C20 118.1(2) . . ? C22 C21 C20 123.4(2) . . ? C21 C22 C23 117.3(2) . . ? C21 C22 H22 121.3 . . ? C23 C22 H22 121.3 . . ? C22 C23 C24 121.5(2) . . ? C22 C23 H23 119.3 . . ? C24 C23 H23 119.3 . . ? C23 C24 C19 119.5(2) . . ? C23 C24 P2 119.94(18) . . ? C19 C24 P2 120.49(17) . . ? C30 C25 C26 119.5(2) . . ? C30 C25 P2 122.2(2) . . ? C26 C25 P2 118.4(2) . . ? C27 C26 C25 119.8(3) . . ? C27 C26 H26 120.1 . . ? C25 C26 H26 120.1 . . ? C28 C27 C26 120.1(3) . . ? C28 C27 H27 119.9 . . ? C26 C27 H27 119.9 . . ? C29 C28 C27 120.3(3) . . ? C29 C28 H28 119.8 . . ? C27 C28 H28 119.8 . . ? C28 C29 C30 119.9(3) . . ? C28 C29 H29 120.0 . . ? C30 C29 H29 120.0 . . ? C29 C30 C25 120.2(3) . . ? C29 C30 H30 119.9 . . ? C25 C30 H30 119.9 . . ? C32 C31 C36 119.5(2) . . ? C32 C31 P2 120.13(19) . . ? C36 C31 P2 120.24(18) . . ? C33 C32 C31 119.7(2) . . ? C33 C32 H32 120.2 . . ? C31 C32 H32 120.2 . . ? C34 C33 C32 120.7(2) . . ? C34 C33 H33 119.7 . . ? C32 C33 H33 119.7 . . ? C33 C34 C35 120.0(2) . . ? C33 C34 H34 120.0 . . ? C35 C34 H34 120.0 . . ? C34 C35 C36 119.7(2) . . ? C34 C35 H35 120.2 . . ? C36 C35 H35 120.2 . . ? C35 C36 C31 120.4(2) . . ? C35 C36 H36 119.8 . . ? C31 C36 H36 119.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C7 P1 C1 C6 -21.9(2) . . . . ? C13 P1 C1 C6 85.8(2) . . . . ? Au1 P1 C1 C6 -149.28(18) . . . . ? C7 P1 C1 C2 164.46(18) . . . . ? C13 P1 C1 C2 -87.8(2) . . . . ? Au1 P1 C1 C2 37.1(2) . . . . ? C6 C1 C2 C3 -2.8(4) . . . . ? P1 C1 C2 C3 170.97(19) . . . . ? C1 C2 C3 C4 0.4(4) . . . . ? C2 C3 C4 C5 2.5(4) . . . . ? C3 C4 C5 C6 -2.9(4) . . . . ? C4 C5 C6 C1 0.5(4) . . . . ? C2 C1 C6 C5 2.4(4) . . . . ? P1 C1 C6 C5 -171.10(19) . . . . ? C1 P1 C7 C12 -108.3(2) . . . . ? C13 P1 C7 C12 143.0(2) . . . . ? Au1 P1 C7 C12 17.8(2) . . . . ? C1 P1 C7 C8 77.0(2) . . . . ? C13 P1 C7 C8 -31.7(2) . . . . ? Au1 P1 C7 C8 -156.87(17) . . . . ? C12 C7 C8 C9 -0.1(4) . . . . ? P1 C7 C8 C9 174.60(19) . . . . ? C7 C8 C9 C10 -0.8(4) . . . . ? C8 C9 C10 C11 1.2(4) . . . . ? C9 C10 C11 C12 -0.7(4) . . . . ? C10 C11 C12 C7 -0.1(4) . . . . ? C8 C7 C12 C11 0.5(4) . . . . ? P1 C7 C12 C11 -174.15(19) . . . . ? C1 P1 C13 C14 -3.8(2) . . . . ? C7 P1 C13 C14 107.4(2) . . . . ? Au1 P1 C13 C14 -127.35(18) . . . . ? C1 P1 C13 C18 -179.44(19) . . . . ? C7 P1 C13 C18 -68.2(2) . . . . ? Au1 P1 C13 C18 57.0(2) . . . . ? C18 C13 C14 C15 1.0(4) . . . . ? P1 C13 C14 C15 -174.72(19) . . . . ? C13 C14 C15 C16 1.9(4) . . . . ? C14 C15 C16 F1 178.0(2) . . . . ? C14 C15 C16 C17 -2.5(4) . . . . ? F1 C16 C17 C18 179.5(2) . . . . ? C15 C16 C17 C18 0.1(4) . . . . ? C16 C17 C18 C13 2.9(3) . . . . ? C16 C17 C18 C19 -176.3(2) . . . . ? C14 C13 C18 C17 -3.4(3) . . . . ? P1 C13 C18 C17 172.27(18) . . . . ? C14 C13 C18 C19 175.8(2) . . . . ? P1 C13 C18 C19 -8.5(3) . . . . ? C17 C18 C19 C20 -96.7(3) . . . . ? C13 C18 C19 C20 84.1(3) . . . . ? C17 C18 C19 C24 81.4(3) . . . . ? C13 C18 C19 C24 -97.8(3) . . . . ? C24 C19 C20 C21 3.9(4) . . . . ? C18 C19 C20 C21 -177.9(2) . . . . ? C19 C20 C21 F2 178.6(2) . . . . ? C19 C20 C21 C22 -1.1(4) . . . . ? F2 C21 C22 C23 178.4(2) . . . . ? C20 C21 C22 C23 -1.9(4) . . . . ? C21 C22 C23 C24 2.1(4) . . . . ? C22 C23 C24 C19 0.7(4) . . . . ? C22 C23 C24 P2 -177.1(2) . . . . ? C20 C19 C24 C23 -3.7(3) . . . . ? C18 C19 C24 C23 178.1(2) . . . . ? C20 C19 C24 P2 174.07(18) . . . . ? C18 C19 C24 P2 -4.1(3) . . . . ? C25 P2 C24 C23 -4.2(2) . . . . ? C31 P2 C24 C23 107.1(2) . . . . ? Au2 P2 C24 C23 -128.08(18) . . . . ? C25 P2 C24 C19 178.00(19) . . . . ? C31 P2 C24 C19 -70.7(2) . . . . ? Au2 P2 C24 C19 54.2(2) . . . . ? C31 P2 C25 C30 -4.6(2) . . . . ? C24 P2 C25 C30 104.7(2) . . . . ? Au2 P2 C25 C30 -129.6(2) . . . . ? C31 P2 C25 C26 175.7(2) . . . . ? C24 P2 C25 C26 -75.0(2) . . . . ? Au2 P2 C25 C26 50.7(2) . . . . ? C30 C25 C26 C27 -2.8(4) . . . . ? P2 C25 C26 C27 176.9(2) . . . . ? C25 C26 C27 C28 1.4(4) . . . . ? C26 C27 C28 C29 1.2(4) . . . . ? C27 C28 C29 C30 -2.4(4) . . . . ? C28 C29 C30 C25 0.9(4) . . . . ? C26 C25 C30 C29 1.7(4) . . . . ? P2 C25 C30 C29 -178.0(2) . . . . ? C25 P2 C31 C32 -98.8(2) . . . . ? C24 P2 C31 C32 150.3(2) . . . . ? Au2 P2 C31 C32 25.0(2) . . . . ? C25 P2 C31 C36 85.6(2) . . . . ? C24 P2 C31 C36 -25.3(2) . . . . ? Au2 P2 C31 C36 -150.61(17) . . . . ? C36 C31 C32 C33 0.8(4) . . . . ? P2 C31 C32 C33 -174.8(2) . . . . ? C31 C32 C33 C34 2.2(4) . . . . ? C32 C33 C34 C35 -2.9(4) . . . . ? C33 C34 C35 C36 0.6(4) . . . . ? C34 C35 C36 C31 2.4(4) . . . . ? C32 C31 C36 C35 -3.1(4) . . . . ? P2 C31 C36 C35 172.55(19) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.100 _refine_diff_density_min -1.949 _refine_diff_density_rms 0.161 # Attachment 'neda02201.cif.txt' data_neda02201 _database_code_depnum_ccdc_archive 'CCDC 726003' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C72 H52 Au4 F4 P4, C H2 Cl2' _chemical_formula_sum 'C73 H54 Au4 Cl2 F4 P4' _chemical_formula_weight 1989.81 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 14.2878(2) _cell_length_b 16.7228(3) _cell_length_c 27.8198(4) _cell_angle_alpha 90.00 _cell_angle_beta 101.9280(10) _cell_angle_gamma 90.00 _cell_volume 6503.52(18) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 320599 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 28.283 _exptl_crystal_description piece _exptl_crystal_colour colorless _exptl_crystal_size_max 0.13 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.032 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3752 _exptl_absorpt_coefficient_mu 9.230 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.359 _exptl_absorpt_correction_T_max 0.640 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 80637 _diffrn_reflns_av_R_equivalents 0.0746 _diffrn_reflns_av_sigmaI/netI 0.0535 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -22 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 28.00 _reflns_number_total 15654 _reflns_number_gt 12060 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0285P)^2^+14.7218P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 15654 _refine_ls_number_parameters 805 _refine_ls_number_restraints 33 _refine_ls_R_factor_all 0.0606 _refine_ls_R_factor_gt 0.0355 _refine_ls_wR_factor_ref 0.0731 _refine_ls_wR_factor_gt 0.0674 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.032 _refine_ls_shift/su_max 0.003 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.123157(14) 0.316837(12) 0.452480(7) 0.01751(5) Uani 1 1 d . . . Au2 Au 0.128306(15) 0.135084(12) 0.429087(7) 0.01884(5) Uani 1 1 d . . . Au3 Au 0.290751(15) 0.197550(12) 0.379979(7) 0.01788(5) Uani 1 1 d . . . Au4 Au 0.165257(15) 0.340339(12) 0.341147(7) 0.01865(5) Uani 1 1 d . . . P1 P -0.01844(10) 0.34903(9) 0.39969(5) 0.0196(3) Uani 1 1 d . . . P2 P 0.19668(10) 0.14492(8) 0.51112(5) 0.0175(3) Uani 1 1 d . . . P3 P 0.21987(10) 0.09936(8) 0.32707(5) 0.0180(3) Uani 1 1 d . . . P4 P 0.31221(10) 0.39925(8) 0.36594(5) 0.0190(3) Uani 1 1 d . . . F1 F -0.1086(3) 0.2247(2) 0.19652(13) 0.0438(10) Uani 1 1 d . . . F2 F 0.4171(2) 0.4338(2) 0.58563(12) 0.0316(8) Uani 1 1 d . . . F3 F -0.1939(2) 0.0431(3) 0.30946(14) 0.0483(11) Uani 1 1 d . . . F4 F 0.5634(2) 0.2519(2) 0.53786(11) 0.0277(7) Uani 1 1 d . . . C1 C -0.0464(4) 0.3093(3) 0.3374(2) 0.0222(12) Uani 1 1 d . . . C2 C -0.1400(4) 0.2867(3) 0.3165(2) 0.0282(13) Uani 1 1 d . . . H2 H -0.1886 0.2912 0.3351 0.034 Uiso 1 1 calc R . . C3 C -0.1622(4) 0.2577(4) 0.2689(2) 0.0321(14) Uani 1 1 d . . . H3 H -0.2254 0.2417 0.2541 0.039 Uiso 1 1 calc R . . C4 C -0.0881(4) 0.2531(4) 0.2438(2) 0.0292(14) Uani 1 1 d . . . C5 C 0.0037(4) 0.2745(3) 0.2640(2) 0.0277(13) Uani 1 1 d . . . H5 H 0.0517 0.2697 0.2451 0.033 Uiso 1 1 calc R . . C6 C 0.0281(4) 0.3035(3) 0.31217(19) 0.0188(11) Uani 1 1 d . . . C7 C -0.0255(4) 0.4574(3) 0.39447(19) 0.0205(12) Uani 1 1 d . . . C8 C -0.0060(4) 0.4981(3) 0.35351(19) 0.0227(12) Uani 1 1 d . . . H8 H 0.0038 0.4686 0.3258 0.027 Uiso 1 1 calc R . . C9 C -0.0010(4) 0.5807(4) 0.3532(2) 0.0284(13) Uani 1 1 d . . . H9 H 0.0126 0.6077 0.3254 0.034 Uiso 1 1 calc R . . C10 C -0.0156(4) 0.6235(4) 0.3931(2) 0.0312(14) Uani 1 1 d . . . H10 H -0.0103 0.6801 0.3929 0.037 Uiso 1 1 calc R . . C11 C -0.0376(4) 0.5858(4) 0.4332(2) 0.0323(15) Uani 1 1 d . . . H11 H -0.0502 0.6164 0.4599 0.039 Uiso 1 1 calc R . . C12 C -0.0415(4) 0.5036(4) 0.4346(2) 0.0296(14) Uani 1 1 d . . . H12 H -0.0551 0.4776 0.4627 0.036 Uiso 1 1 calc R . . C13 C -0.1192(4) 0.3211(3) 0.4269(2) 0.0231(12) Uani 1 1 d . . . C14 C -0.2047(4) 0.3640(4) 0.4186(2) 0.0316(14) Uani 1 1 d . . . H14 H -0.2103 0.4124 0.4003 0.038 Uiso 1 1 calc R . . C15 C -0.2818(4) 0.3359(4) 0.4372(2) 0.0378(16) Uani 1 1 d . . . H15 H -0.3400 0.3652 0.4314 0.045 Uiso 1 1 calc R . . C16 C -0.2743(5) 0.2662(4) 0.4637(2) 0.0378(16) Uani 1 1 d . . . H16 H -0.3275 0.2473 0.4760 0.045 Uiso 1 1 calc R . . C17 C -0.1902(5) 0.2237(4) 0.4724(3) 0.0376(16) Uani 1 1 d . . . H17 H -0.1853 0.1757 0.4910 0.045 Uiso 1 1 calc R . . C18 C -0.1120(4) 0.2505(4) 0.4540(2) 0.0281(13) Uani 1 1 d . . . H18 H -0.0541 0.2208 0.4600 0.034 Uiso 1 1 calc R . . C19 C 0.2672(4) 0.2320(3) 0.53384(18) 0.0173(11) Uani 1 1 d . . . C20 C 0.3461(4) 0.2273(3) 0.57325(19) 0.0218(12) Uani 1 1 d . . . H20 H 0.3650 0.1770 0.5879 0.026 Uiso 1 1 calc R . . C21 C 0.3961(4) 0.2948(3) 0.59086(20) 0.0226(12) Uani 1 1 d . . . H21 H 0.4489 0.2920 0.6179 0.027 Uiso 1 1 calc R . . C22 C 0.3681(4) 0.3658(3) 0.5686(2) 0.0229(12) Uani 1 1 d . . . C23 C 0.2915(4) 0.3730(3) 0.5296(2) 0.0210(12) Uani 1 1 d . . . H23 H 0.2740 0.4243 0.5159 0.025 Uiso 1 1 calc R . . C24 C 0.2388(4) 0.3052(3) 0.5098(2) 0.0211(12) Uani 1 1 d . . . C25 C 0.2704(4) 0.0571(3) 0.5312(2) 0.0237(12) Uani 1 1 d . . . C26 C 0.2735(4) 0.0195(3) 0.5765(2) 0.0260(13) Uani 1 1 d . . . H26 H 0.2361 0.0400 0.5982 0.031 Uiso 1 1 calc R . . C27 C 0.3301(4) -0.0469(4) 0.5899(2) 0.0310(14) Uani 1 1 d . . . H27 H 0.3309 -0.0720 0.6206 0.037 Uiso 1 1 calc R . . C28 C 0.3860(4) -0.0775(4) 0.5588(2) 0.0289(14) Uani 1 1 d . . . H28 H 0.4254 -0.1230 0.5682 0.035 Uiso 1 1 calc R . . C29 C 0.3835(4) -0.0406(4) 0.5139(2) 0.0288(14) Uani 1 1 d . . . H29 H 0.4213 -0.0612 0.4924 0.035 Uiso 1 1 calc R . . C30 C 0.3266(4) 0.0258(3) 0.5000(2) 0.0259(13) Uani 1 1 d . . . H30 H 0.3257 0.0503 0.4691 0.031 Uiso 1 1 calc R . . C31 C 0.1047(4) 0.1376(3) 0.5482(2) 0.0194(11) Uani 1 1 d . . . C32 C 0.0228(4) 0.0946(3) 0.5294(2) 0.0301(14) Uani 1 1 d . . . H32 H 0.0128 0.0734 0.4970 0.036 Uiso 1 1 calc R . . C33 C -0.0454(4) 0.0821(4) 0.5583(3) 0.0365(16) Uani 1 1 d . . . H33 H -0.1016 0.0521 0.5457 0.044 Uiso 1 1 calc R . . C34 C -0.0308(5) 0.1137(4) 0.6053(3) 0.0430(18) Uani 1 1 d . . . H34 H -0.0760 0.1044 0.6253 0.052 Uiso 1 1 calc R . . C35 C 0.0494(5) 0.1585(4) 0.6226(2) 0.0347(16) Uani 1 1 d . . . H35 H 0.0582 0.1817 0.6544 0.042 Uiso 1 1 calc R . . C36 C 0.1178(4) 0.1707(3) 0.5947(2) 0.0266(13) Uani 1 1 d . . . H36 H 0.1733 0.2014 0.6074 0.032 Uiso 1 1 calc R . . C37 C 0.0928(4) 0.0806(3) 0.32113(18) 0.0182(11) Uani 1 1 d . . . C38 C 0.0384(4) 0.0483(3) 0.2780(2) 0.0265(13) Uani 1 1 d . . . H38 H 0.0681 0.0353 0.2515 0.032 Uiso 1 1 calc R . . C39 C -0.0587(4) 0.0351(4) 0.2737(2) 0.0283(13) Uani 1 1 d . . . H39 H -0.0964 0.0129 0.2446 0.034 Uiso 1 1 calc R . . C40 C -0.0988(4) 0.0553(4) 0.3130(2) 0.0310(14) Uani 1 1 d . . . C41 C -0.0466(4) 0.0869(3) 0.3559(2) 0.0258(13) Uani 1 1 d . . . H41 H -0.0777 0.0999 0.3819 0.031 Uiso 1 1 calc R . . C42 C 0.0513(4) 0.1001(3) 0.36168(19) 0.0200(12) Uani 1 1 d . . . C43 C 0.2363(4) 0.1163(3) 0.26466(19) 0.0207(12) Uani 1 1 d . . . C44 C 0.2476(4) 0.0548(4) 0.2326(2) 0.0288(14) Uani 1 1 d . . . H44 H 0.2513 0.0009 0.2436 0.035 Uiso 1 1 calc R . . C45 C 0.2533(4) 0.0728(4) 0.1844(2) 0.0321(15) Uani 1 1 d . . . H45 H 0.2588 0.0307 0.1622 0.039 Uiso 1 1 calc R . . C46 C 0.2511(4) 0.1502(4) 0.1686(2) 0.0312(14) Uani 1 1 d . . . H46 H 0.2537 0.1615 0.1355 0.037 Uiso 1 1 calc R . . C47 C 0.2451(4) 0.2120(4) 0.2006(2) 0.0299(14) Uani 1 1 d . . . H47 H 0.2467 0.2658 0.1899 0.036 Uiso 1 1 calc R . . C48 C 0.2368(4) 0.1955(3) 0.2486(2) 0.0252(13) Uani 1 1 d . . . H48 H 0.2313 0.2381 0.2705 0.030 Uiso 1 1 calc R . . C49 C 0.2813(4) 0.0047(3) 0.34472(19) 0.0175(11) Uani 1 1 d . . . C50 C 0.3769(4) 0.0064(3) 0.3693(2) 0.0234(12) Uani 1 1 d . . . H50 H 0.4080 0.0563 0.3772 0.028 Uiso 1 1 calc R . . C51 C 0.4267(4) -0.0640(3) 0.3823(2) 0.0245(13) Uani 1 1 d . . . H51 H 0.4916 -0.0623 0.3993 0.029 Uiso 1 1 calc R . . C52 C 0.3817(4) -0.1370(4) 0.3704(2) 0.0285(13) Uani 1 1 d . . . H52 H 0.4159 -0.1854 0.3790 0.034 Uiso 1 1 calc R . . C53 C 0.2873(4) -0.1393(3) 0.3462(2) 0.0279(13) Uani 1 1 d . . . H53 H 0.2561 -0.1892 0.3387 0.033 Uiso 1 1 calc R . . C54 C 0.2381(4) -0.0693(3) 0.3330(2) 0.0244(13) Uani 1 1 d . . . H54 H 0.1736 -0.0715 0.3155 0.029 Uiso 1 1 calc R . . C55 C 0.3897(4) 0.3549(3) 0.41850(18) 0.0158(11) Uani 1 1 d . . . C56 C 0.4572(4) 0.4020(3) 0.4509(2) 0.0208(12) Uani 1 1 d . . . H56 H 0.4616 0.4577 0.4449 0.025 Uiso 1 1 calc R . . C57 C 0.5168(4) 0.3680(3) 0.4912(2) 0.0223(12) Uani 1 1 d . . . H57 H 0.5631 0.3987 0.5130 0.027 Uiso 1 1 calc R . . C58 C 0.5058(4) 0.2874(3) 0.49816(19) 0.0197(12) Uani 1 1 d . . . C59 C 0.4419(4) 0.2401(3) 0.46750(19) 0.0188(11) Uani 1 1 d . . . H59 H 0.4390 0.1845 0.4740 0.023 Uiso 1 1 calc R . . C60 C 0.3806(4) 0.2732(3) 0.42650(18) 0.0186(11) Uani 1 1 d . . . C61 C 0.2952(4) 0.5027(3) 0.3824(2) 0.0223(12) Uani 1 1 d . . . C62 C 0.3306(5) 0.5678(4) 0.3611(2) 0.0329(15) Uani 1 1 d . . . H62 H 0.3688 0.5597 0.3373 0.039 Uiso 1 1 calc R . . C63 C 0.3106(5) 0.6453(4) 0.3744(2) 0.0359(15) Uani 1 1 d . . . H63 H 0.3339 0.6898 0.3592 0.043 Uiso 1 1 calc R . . C64 C 0.2572(4) 0.6572(4) 0.4094(2) 0.0352(15) Uani 1 1 d . . . H64 H 0.2440 0.7101 0.4185 0.042 Uiso 1 1 calc R . . C65 C 0.2225(4) 0.5936(4) 0.4316(2) 0.0314(14) Uani 1 1 d . . . H65 H 0.1867 0.6025 0.4563 0.038 Uiso 1 1 calc R . . C66 C 0.2400(4) 0.5163(3) 0.4178(2) 0.0272(13) Uani 1 1 d . . . H66 H 0.2145 0.4723 0.4325 0.033 Uiso 1 1 calc R . . C67 C 0.3800(4) 0.4065(3) 0.3166(2) 0.0247(13) Uani 1 1 d . . . C68 C 0.3312(5) 0.4153(4) 0.2688(2) 0.0342(15) Uani 1 1 d . . . H68 H 0.2633 0.4151 0.2613 0.041 Uiso 1 1 calc R . . C69 C 0.3816(6) 0.4243(4) 0.2317(2) 0.0456(18) Uani 1 1 d . . . H69 H 0.3478 0.4308 0.1987 0.055 Uiso 1 1 calc R . . C70 C 0.4799(6) 0.4242(5) 0.2420(3) 0.063(2) Uani 1 1 d . . . H70 H 0.5136 0.4306 0.2162 0.075 Uiso 1 1 calc R . . C71 C 0.5297(6) 0.4147(6) 0.2897(3) 0.073(3) Uani 1 1 d . . . H71 H 0.5976 0.4138 0.2968 0.088 Uiso 1 1 calc R . . C72 C 0.4796(5) 0.4064(5) 0.3275(2) 0.051(2) Uani 1 1 d . . . H72 H 0.5133 0.4007 0.3605 0.061 Uiso 1 1 calc R . . Cl1 Cl 0.4439(19) 0.6875(19) 0.2727(7) 0.117(5) Uani 0.57 1 d PD A 1 C1S C 0.5054(8) 0.7034(8) 0.2228(4) 0.053(3) Uani 0.57 1 d PDU A 1 H1S1 H 0.5460 0.6568 0.2192 0.063 Uiso 0.57 1 calc PR A 1 H1S2 H 0.5464 0.7515 0.2291 0.063 Uiso 0.57 1 calc PR A 1 Cl2 Cl 0.4138(4) 0.7166(3) 0.16774(16) 0.0822(13) Uani 0.57 1 d PDU A 1 Cl1A Cl 0.439(3) 0.709(3) 0.2770(9) 0.117(5) Uani 0.43 1 d PD B 2 C1T C 0.4972(16) 0.6389(13) 0.2430(5) 0.074(6) Uani 0.43 1 d PDU B 2 H1T1 H 0.4678 0.5854 0.2431 0.089 Uiso 0.43 1 calc PR B 2 H1T2 H 0.5661 0.6346 0.2581 0.089 Uiso 0.43 1 calc PR B 2 Cl2A Cl 0.4822(6) 0.6758(5) 0.1806(3) 0.102(2) Uani 0.43 1 d PDU B 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01801(10) 0.01874(11) 0.01520(10) 0.00140(8) 0.00206(8) 0.00055(8) Au2 0.02237(11) 0.01945(12) 0.01418(10) -0.00240(8) 0.00259(8) -0.00029(9) Au3 0.02260(11) 0.01420(11) 0.01644(10) -0.00089(8) 0.00308(8) -0.00133(8) Au4 0.01996(11) 0.01791(11) 0.01748(10) -0.00140(8) 0.00250(8) 0.00145(8) P1 0.0174(7) 0.0240(8) 0.0167(7) 0.0018(6) 0.0020(6) 0.0020(6) P2 0.0224(7) 0.0173(7) 0.0128(6) -0.0006(5) 0.0034(6) 0.0006(6) P3 0.0245(8) 0.0151(7) 0.0146(7) -0.0019(5) 0.0042(6) -0.0001(6) P4 0.0222(7) 0.0168(7) 0.0180(7) 0.0010(6) 0.0040(6) -0.0002(6) F1 0.037(2) 0.057(3) 0.030(2) -0.0238(18) -0.0076(17) 0.0100(19) F2 0.0286(19) 0.0288(19) 0.034(2) -0.0055(15) -0.0016(15) -0.0110(15) F3 0.023(2) 0.082(3) 0.039(2) -0.022(2) 0.0050(17) -0.010(2) F4 0.0239(18) 0.0336(19) 0.0230(17) 0.0053(15) -0.0012(14) 0.0017(15) C1 0.021(3) 0.022(3) 0.021(3) 0.005(2) 0.000(2) 0.009(2) C2 0.026(3) 0.030(4) 0.028(3) -0.006(3) 0.005(3) 0.003(3) C3 0.021(3) 0.038(4) 0.032(3) -0.007(3) -0.008(3) 0.003(3) C4 0.032(3) 0.028(3) 0.022(3) -0.010(3) -0.007(3) 0.009(3) C5 0.027(3) 0.029(3) 0.025(3) -0.005(3) 0.002(3) 0.008(3) C6 0.020(3) 0.016(3) 0.019(3) -0.001(2) 0.000(2) 0.006(2) C7 0.021(3) 0.018(3) 0.022(3) -0.001(2) 0.003(2) 0.009(2) C8 0.023(3) 0.026(3) 0.018(3) -0.002(2) 0.001(2) 0.000(2) C9 0.034(3) 0.027(3) 0.023(3) 0.001(2) 0.002(3) 0.001(3) C10 0.033(4) 0.021(3) 0.034(3) 0.004(3) -0.006(3) 0.007(3) C11 0.034(4) 0.034(4) 0.026(3) -0.010(3) -0.003(3) 0.014(3) C12 0.031(3) 0.035(4) 0.022(3) -0.006(3) 0.004(3) 0.002(3) C13 0.023(3) 0.029(3) 0.018(3) -0.003(2) 0.006(2) -0.002(2) C14 0.023(3) 0.045(4) 0.028(3) 0.001(3) 0.007(3) 0.002(3) C15 0.022(3) 0.056(5) 0.035(4) -0.011(3) 0.005(3) 0.004(3) C16 0.034(4) 0.044(4) 0.039(4) -0.003(3) 0.017(3) -0.009(3) C17 0.036(4) 0.031(4) 0.049(4) 0.000(3) 0.018(3) -0.007(3) C18 0.021(3) 0.034(4) 0.030(3) 0.001(3) 0.007(3) -0.002(3) C19 0.023(3) 0.018(3) 0.011(2) -0.003(2) 0.005(2) 0.004(2) C20 0.025(3) 0.019(3) 0.021(3) 0.001(2) 0.004(2) 0.004(2) C21 0.020(3) 0.029(3) 0.017(3) -0.002(2) -0.001(2) 0.002(2) C22 0.020(3) 0.024(3) 0.025(3) -0.005(2) 0.008(2) -0.009(2) C23 0.023(3) 0.015(3) 0.026(3) 0.004(2) 0.007(2) 0.003(2) C24 0.024(3) 0.019(3) 0.021(3) -0.001(2) 0.007(2) 0.000(2) C25 0.025(3) 0.021(3) 0.026(3) -0.005(2) 0.006(2) -0.001(2) C26 0.032(3) 0.027(3) 0.019(3) 0.005(2) 0.007(3) 0.003(3) C27 0.036(4) 0.029(4) 0.026(3) 0.009(3) 0.002(3) 0.003(3) C28 0.025(3) 0.021(3) 0.039(4) 0.000(3) 0.002(3) 0.000(3) C29 0.022(3) 0.031(4) 0.034(3) -0.008(3) 0.008(3) 0.002(3) C30 0.027(3) 0.025(3) 0.027(3) -0.001(2) 0.008(3) -0.002(3) C31 0.022(3) 0.016(3) 0.023(3) -0.001(2) 0.010(2) 0.002(2) C32 0.030(3) 0.024(3) 0.037(4) 0.001(3) 0.008(3) -0.004(3) C33 0.028(3) 0.026(4) 0.057(5) 0.003(3) 0.013(3) -0.010(3) C34 0.051(5) 0.032(4) 0.055(5) 0.004(3) 0.033(4) 0.001(3) C35 0.046(4) 0.033(4) 0.032(4) 0.002(3) 0.024(3) 0.007(3) C36 0.033(3) 0.018(3) 0.030(3) -0.004(2) 0.010(3) -0.005(3) C37 0.023(3) 0.015(3) 0.015(3) 0.002(2) 0.000(2) 0.002(2) C38 0.027(3) 0.028(3) 0.023(3) -0.006(2) 0.003(3) -0.003(3) C39 0.027(3) 0.037(4) 0.018(3) -0.007(3) -0.003(2) -0.004(3) C40 0.022(3) 0.040(4) 0.030(3) -0.006(3) 0.003(3) -0.003(3) C41 0.023(3) 0.031(3) 0.024(3) -0.008(2) 0.007(2) 0.001(3) C42 0.023(3) 0.018(3) 0.018(3) 0.003(2) 0.000(2) -0.001(2) C43 0.022(3) 0.022(3) 0.018(3) -0.001(2) 0.004(2) -0.001(2) C44 0.039(4) 0.023(3) 0.026(3) 0.000(2) 0.011(3) 0.001(3) C45 0.040(4) 0.035(4) 0.024(3) -0.004(3) 0.011(3) 0.002(3) C46 0.040(4) 0.036(4) 0.019(3) 0.003(3) 0.009(3) -0.006(3) C47 0.038(4) 0.024(3) 0.028(3) 0.011(3) 0.007(3) 0.002(3) C48 0.031(3) 0.026(3) 0.018(3) 0.000(2) 0.004(2) 0.003(3) C49 0.024(3) 0.008(3) 0.021(3) 0.001(2) 0.006(2) 0.000(2) C50 0.026(3) 0.021(3) 0.023(3) -0.005(2) 0.006(2) -0.004(2) C51 0.023(3) 0.021(3) 0.027(3) -0.005(2) 0.000(2) 0.000(2) C52 0.034(3) 0.024(3) 0.025(3) 0.006(2) 0.002(3) 0.005(3) C53 0.035(4) 0.016(3) 0.033(3) 0.003(2) 0.007(3) -0.003(3) C54 0.024(3) 0.023(3) 0.023(3) 0.005(2) -0.002(2) 0.000(2) C55 0.017(3) 0.019(3) 0.013(2) 0.000(2) 0.006(2) -0.002(2) C56 0.024(3) 0.013(3) 0.026(3) -0.003(2) 0.008(2) -0.003(2) C57 0.019(3) 0.023(3) 0.025(3) -0.003(2) 0.005(2) -0.001(2) C58 0.016(3) 0.027(3) 0.015(3) 0.004(2) 0.002(2) 0.002(2) C59 0.016(3) 0.019(3) 0.022(3) 0.002(2) 0.004(2) 0.001(2) C60 0.024(3) 0.020(3) 0.015(3) -0.002(2) 0.009(2) -0.004(2) C61 0.020(3) 0.021(3) 0.025(3) -0.002(2) 0.002(2) -0.003(2) C62 0.040(4) 0.023(3) 0.036(4) 0.006(3) 0.007(3) -0.002(3) C63 0.042(4) 0.018(3) 0.044(4) 0.003(3) 0.000(3) 0.001(3) C64 0.029(3) 0.022(3) 0.049(4) -0.005(3) -0.006(3) 0.004(3) C65 0.025(3) 0.026(3) 0.040(4) -0.008(3) 0.000(3) 0.007(3) C66 0.026(3) 0.022(3) 0.032(3) 0.002(3) 0.003(3) -0.003(3) C67 0.034(3) 0.020(3) 0.021(3) 0.001(2) 0.008(3) 0.000(3) C68 0.038(4) 0.042(4) 0.025(3) 0.012(3) 0.011(3) 0.010(3) C69 0.059(5) 0.055(5) 0.026(4) 0.006(3) 0.015(3) 0.004(4) C70 0.069(6) 0.086(7) 0.042(5) 0.002(4) 0.034(4) -0.008(5) C71 0.046(5) 0.140(9) 0.041(5) 0.003(5) 0.025(4) -0.009(5) C72 0.035(4) 0.092(6) 0.026(4) 0.003(4) 0.010(3) -0.015(4) Cl1 0.110(3) 0.173(16) 0.067(3) 0.027(5) 0.015(2) -0.005(6) C1S 0.042(6) 0.046(6) 0.071(7) -0.023(5) 0.015(5) -0.009(5) Cl2 0.089(3) 0.084(3) 0.065(3) -0.024(2) -0.003(2) -0.027(3) Cl1A 0.110(3) 0.173(16) 0.067(3) 0.027(5) 0.015(2) -0.005(6) C1T 0.062(8) 0.066(8) 0.088(9) 0.014(7) 0.004(7) 0.016(7) Cl2A 0.114(5) 0.122(5) 0.076(4) -0.030(4) 0.036(4) -0.008(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.055(6) . ? Au1 P1 2.3046(14) . ? Au1 Au2 3.1124(3) . ? Au1 Au4 3.2984(3) . ? Au2 C42 2.053(5) . ? Au2 P2 2.2952(14) . ? Au2 Au3 3.1073(3) . ? Au3 C60 2.059(5) . ? Au3 P3 2.2962(14) . ? Au3 Au4 3.0468(3) . ? Au4 C6 2.053(5) . ? Au4 P4 2.2926(15) . ? P1 C7 1.819(5) . ? P1 C13 1.820(5) . ? P1 C1 1.823(6) . ? P2 C19 1.808(5) . ? P2 C25 1.826(6) . ? P2 C31 1.834(5) . ? P3 C37 1.816(5) . ? P3 C43 1.822(5) . ? P3 C49 1.828(5) . ? P4 C55 1.801(5) . ? P4 C61 1.819(6) . ? P4 C67 1.839(6) . ? F1 C4 1.373(6) . ? F2 C22 1.367(6) . ? F3 C40 1.357(7) . ? F4 C58 1.369(6) . ? C1 C6 1.394(7) . ? C1 C2 1.395(8) . ? C2 C3 1.385(8) . ? C2 H2 0.9500 . ? C3 C4 1.385(8) . ? C3 H3 0.9500 . ? C4 C5 1.363(8) . ? C5 C6 1.401(7) . ? C5 H5 0.9500 . ? C7 C8 1.404(7) . ? C7 C12 1.414(7) . ? C8 C9 1.383(8) . ? C8 H8 0.9500 . ? C9 C10 1.372(8) . ? C9 H9 0.9500 . ? C10 C11 1.374(8) . ? C10 H10 0.9500 . ? C11 C12 1.377(9) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C18 1.394(8) . ? C13 C14 1.395(8) . ? C14 C15 1.391(8) . ? C14 H14 0.9500 . ? C15 C16 1.372(9) . ? C15 H15 0.9500 . ? C16 C17 1.374(9) . ? C16 H16 0.9500 . ? C17 C18 1.395(8) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.402(7) . ? C19 C24 1.413(7) . ? C20 C21 1.371(8) . ? C20 H20 0.9500 . ? C21 C22 1.361(8) . ? C21 H21 0.9500 . ? C22 C23 1.378(7) . ? C23 C24 1.409(7) . ? C23 H23 0.9500 . ? C25 C30 1.399(7) . ? C25 C26 1.401(7) . ? C26 C27 1.380(8) . ? C26 H26 0.9500 . ? C27 C28 1.389(8) . ? C27 H27 0.9500 . ? C28 C29 1.387(8) . ? C28 H28 0.9500 . ? C29 C30 1.383(8) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.381(8) . ? C31 C36 1.385(7) . ? C32 C33 1.402(8) . ? C32 H32 0.9500 . ? C33 C34 1.383(9) . ? C33 H33 0.9500 . ? C34 C35 1.371(9) . ? C34 H34 0.9500 . ? C35 C36 1.382(8) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C37 C38 1.396(7) . ? C37 C42 1.417(7) . ? C38 C39 1.385(8) . ? C38 H38 0.9500 . ? C39 C40 1.377(8) . ? C39 H39 0.9500 . ? C40 C41 1.376(8) . ? C41 C42 1.392(7) . ? C41 H41 0.9500 . ? C43 C44 1.391(7) . ? C43 C48 1.398(8) . ? C44 C45 1.395(8) . ? C44 H44 0.9500 . ? C45 C46 1.365(8) . ? C45 H45 0.9500 . ? C46 C47 1.377(8) . ? C46 H46 0.9500 . ? C47 C48 1.395(8) . ? C47 H47 0.9500 . ? C48 H48 0.9500 . ? C49 C54 1.390(7) . ? C49 C50 1.396(7) . ? C50 C51 1.385(8) . ? C50 H50 0.9500 . ? C51 C52 1.388(8) . ? C51 H51 0.9500 . ? C52 C53 1.378(8) . ? C52 H52 0.9500 . ? C53 C54 1.375(8) . ? C53 H53 0.9500 . ? C54 H54 0.9500 . ? C55 C60 1.394(7) . ? C55 C56 1.416(7) . ? C56 C57 1.383(7) . ? C56 H56 0.9500 . ? C57 C58 1.374(8) . ? C57 H57 0.9500 . ? C58 C59 1.366(7) . ? C59 C60 1.401(7) . ? C59 H59 0.9500 . ? C61 C62 1.384(8) . ? C61 C66 1.403(8) . ? C62 C63 1.393(8) . ? C62 H62 0.9500 . ? C63 C64 1.370(9) . ? C63 H63 0.9500 . ? C64 C65 1.373(9) . ? C64 H64 0.9500 . ? C65 C66 1.385(8) . ? C65 H65 0.9500 . ? C66 H66 0.9500 . ? C67 C68 1.376(8) . ? C67 C72 1.392(9) . ? C68 C69 1.383(8) . ? C68 H68 0.9500 . ? C69 C70 1.375(10) . ? C69 H69 0.9500 . ? C70 C71 1.379(11) . ? C70 H70 0.9500 . ? C71 C72 1.395(9) . ? C71 H71 0.9500 . ? C72 H72 0.9500 . ? Cl1 C1S 1.810(11) . ? C1S Cl2 1.811(11) . ? C1S H1S1 0.9900 . ? C1S H1S2 0.9900 . ? Cl1A C1T 1.810(11) . ? C1T Cl2A 1.810(11) . ? C1T H1T1 0.9900 . ? C1T H1T2 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 P1 167.40(15) . . ? C24 Au1 Au2 91.12(15) . . ? P1 Au1 Au2 98.65(4) . . ? C24 Au1 Au4 117.81(15) . . ? P1 Au1 Au4 71.35(3) . . ? Au2 Au1 Au4 84.447(7) . . ? C42 Au2 P2 165.04(15) . . ? C42 Au2 Au3 90.11(15) . . ? P2 Au2 Au3 102.12(4) . . ? C42 Au2 Au1 115.97(15) . . ? P2 Au2 Au1 75.27(3) . . ? Au3 Au2 Au1 79.381(7) . . ? C60 Au3 P3 167.89(15) . . ? C60 Au3 Au4 89.19(15) . . ? P3 Au3 Au4 100.60(4) . . ? C60 Au3 Au2 110.84(13) . . ? P3 Au3 Au2 76.76(3) . . ? Au4 Au3 Au2 88.914(8) . . ? C6 Au4 P4 170.88(15) . . ? C6 Au4 Au3 110.37(14) . . ? P4 Au4 Au3 78.16(4) . . ? C6 Au4 Au1 89.34(15) . . ? P4 Au4 Au1 95.86(3) . . ? Au3 Au4 Au1 77.399(7) . . ? C7 P1 C13 104.6(3) . . ? C7 P1 C1 106.8(2) . . ? C13 P1 C1 105.4(3) . . ? C7 P1 Au1 108.10(19) . . ? C13 P1 Au1 109.89(19) . . ? C1 P1 Au1 120.81(18) . . ? C19 P2 C25 107.2(3) . . ? C19 P2 C31 105.6(2) . . ? C25 P2 C31 102.1(2) . . ? C19 P2 Au2 119.81(17) . . ? C25 P2 Au2 110.28(18) . . ? C31 P2 Au2 110.28(19) . . ? C37 P3 C43 105.3(2) . . ? C37 P3 C49 106.8(2) . . ? C43 P3 C49 104.0(2) . . ? C37 P3 Au3 118.82(17) . . ? C43 P3 Au3 111.93(18) . . ? C49 P3 Au3 108.89(18) . . ? C55 P4 C61 106.2(2) . . ? C55 P4 C67 107.6(2) . . ? C61 P4 C67 104.1(3) . . ? C55 P4 Au4 115.98(17) . . ? C61 P4 Au4 108.85(18) . . ? C67 P4 Au4 113.2(2) . . ? C6 C1 C2 122.6(5) . . ? C6 C1 P1 117.6(4) . . ? C2 C1 P1 119.8(4) . . ? C3 C2 C1 120.2(5) . . ? C3 C2 H2 119.9 . . ? C1 C2 H2 119.9 . . ? C2 C3 C4 117.0(5) . . ? C2 C3 H3 121.5 . . ? C4 C3 H3 121.5 . . ? C5 C4 F1 118.7(5) . . ? C5 C4 C3 123.3(5) . . ? F1 C4 C3 117.9(5) . . ? C4 C5 C6 120.8(5) . . ? C4 C5 H5 119.6 . . ? C6 C5 H5 119.6 . . ? C1 C6 C5 116.1(5) . . ? C1 C6 Au4 123.3(4) . . ? C5 C6 Au4 120.5(4) . . ? C8 C7 C12 117.9(5) . . ? C8 C7 P1 122.0(4) . . ? C12 C7 P1 119.8(4) . . ? C9 C8 C7 120.6(5) . . ? C9 C8 H8 119.7 . . ? C7 C8 H8 119.7 . . ? C10 C9 C8 119.9(6) . . ? C10 C9 H9 120.0 . . ? C8 C9 H9 120.0 . . ? C9 C10 C11 121.1(6) . . ? C9 C10 H10 119.5 . . ? C11 C10 H10 119.5 . . ? C10 C11 C12 119.9(6) . . ? C10 C11 H11 120.0 . . ? C12 C11 H11 120.0 . . ? C11 C12 C7 120.6(6) . . ? C11 C12 H12 119.7 . . ? C7 C12 H12 119.7 . . ? C18 C13 C14 119.3(5) . . ? C18 C13 P1 117.8(4) . . ? C14 C13 P1 122.7(4) . . ? C15 C14 C13 119.9(6) . . ? C15 C14 H14 120.0 . . ? C13 C14 H14 120.0 . . ? C16 C15 C14 120.5(6) . . ? C16 C15 H15 119.8 . . ? C14 C15 H15 119.8 . . ? C15 C16 C17 120.1(6) . . ? C15 C16 H16 119.9 . . ? C17 C16 H16 119.9 . . ? C16 C17 C18 120.5(6) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C13 C18 C17 119.7(6) . . ? C13 C18 H18 120.2 . . ? C17 C18 H18 120.2 . . ? C20 C19 C24 121.5(5) . . ? C20 C19 P2 121.9(4) . . ? C24 C19 P2 116.6(4) . . ? C21 C20 C19 120.6(5) . . ? C21 C20 H20 119.7 . . ? C19 C20 H20 119.7 . . ? C22 C21 C20 118.2(5) . . ? C22 C21 H21 120.9 . . ? C20 C21 H21 120.9 . . ? C21 C22 F2 119.1(5) . . ? C21 C22 C23 123.0(5) . . ? F2 C22 C23 117.8(5) . . ? C22 C23 C24 120.7(5) . . ? C22 C23 H23 119.6 . . ? C24 C23 H23 119.6 . . ? C23 C24 C19 115.8(5) . . ? C23 C24 Au1 120.4(4) . . ? C19 C24 Au1 123.7(4) . . ? C30 C25 C26 118.3(5) . . ? C30 C25 P2 118.7(4) . . ? C26 C25 P2 123.0(4) . . ? C27 C26 C25 120.8(5) . . ? C27 C26 H26 119.6 . . ? C25 C26 H26 119.6 . . ? C26 C27 C28 120.6(5) . . ? C26 C27 H27 119.7 . . ? C28 C27 H27 119.7 . . ? C29 C28 C27 119.0(6) . . ? C29 C28 H28 120.5 . . ? C27 C28 H28 120.5 . . ? C30 C29 C28 120.9(5) . . ? C30 C29 H29 119.5 . . ? C28 C29 H29 119.5 . . ? C29 C30 C25 120.4(5) . . ? C29 C30 H30 119.8 . . ? C25 C30 H30 119.8 . . ? C32 C31 C36 120.1(5) . . ? C32 C31 P2 118.1(4) . . ? C36 C31 P2 121.7(4) . . ? C31 C32 C33 119.7(6) . . ? C31 C32 H32 120.2 . . ? C33 C32 H32 120.2 . . ? C34 C33 C32 119.8(6) . . ? C34 C33 H33 120.1 . . ? C32 C33 H33 120.1 . . ? C35 C34 C33 119.6(6) . . ? C35 C34 H34 120.2 . . ? C33 C34 H34 120.2 . . ? C34 C35 C36 121.2(6) . . ? C34 C35 H35 119.4 . . ? C36 C35 H35 119.4 . . ? C35 C36 C31 119.5(6) . . ? C35 C36 H36 120.3 . . ? C31 C36 H36 120.3 . . ? C38 C37 C42 121.5(5) . . ? C38 C37 P3 120.9(4) . . ? C42 C37 P3 117.6(4) . . ? C39 C38 C37 120.4(5) . . ? C39 C38 H38 119.8 . . ? C37 C38 H38 119.8 . . ? C40 C39 C38 117.8(5) . . ? C40 C39 H39 121.1 . . ? C38 C39 H39 121.1 . . ? F3 C40 C41 118.5(5) . . ? F3 C40 C39 118.7(5) . . ? C41 C40 C39 122.8(5) . . ? C40 C41 C42 120.9(5) . . ? C40 C41 H41 119.6 . . ? C42 C41 H41 119.6 . . ? C41 C42 C37 116.6(5) . . ? C41 C42 Au2 119.1(4) . . ? C37 C42 Au2 124.0(4) . . ? C44 C43 C48 119.1(5) . . ? C44 C43 P3 123.4(4) . . ? C48 C43 P3 117.4(4) . . ? C43 C44 C45 119.7(6) . . ? C43 C44 H44 120.1 . . ? C45 C44 H44 120.1 . . ? C46 C45 C44 120.7(6) . . ? C46 C45 H45 119.7 . . ? C44 C45 H45 119.7 . . ? C45 C46 C47 120.4(5) . . ? C45 C46 H46 119.8 . . ? C47 C46 H46 119.8 . . ? C46 C47 C48 119.9(5) . . ? C46 C47 H47 120.0 . . ? C48 C47 H47 120.0 . . ? C47 C48 C43 120.0(5) . . ? C47 C48 H48 120.0 . . ? C43 C48 H48 120.0 . . ? C54 C49 C50 118.4(5) . . ? C54 C49 P3 122.9(4) . . ? C50 C49 P3 118.7(4) . . ? C51 C50 C49 120.5(5) . . ? C51 C50 H50 119.7 . . ? C49 C50 H50 119.7 . . ? C50 C51 C52 119.9(5) . . ? C50 C51 H51 120.1 . . ? C52 C51 H51 120.1 . . ? C53 C52 C51 119.9(5) . . ? C53 C52 H52 120.0 . . ? C51 C52 H52 120.0 . . ? C54 C53 C52 120.1(5) . . ? C54 C53 H53 119.9 . . ? C52 C53 H53 119.9 . . ? C53 C54 C49 121.1(5) . . ? C53 C54 H54 119.4 . . ? C49 C54 H54 119.4 . . ? C60 C55 C56 121.1(5) . . ? C60 C55 P4 118.1(4) . . ? C56 C55 P4 120.7(4) . . ? C57 C56 C55 120.8(5) . . ? C57 C56 H56 119.6 . . ? C55 C56 H56 119.6 . . ? C58 C57 C56 116.6(5) . . ? C58 C57 H57 121.7 . . ? C56 C57 H57 121.7 . . ? C59 C58 F4 117.7(5) . . ? C59 C58 C57 124.2(5) . . ? F4 C58 C57 118.1(5) . . ? C58 C59 C60 120.2(5) . . ? C58 C59 H59 119.9 . . ? C60 C59 H59 119.9 . . ? C55 C60 C59 117.1(5) . . ? C55 C60 Au3 124.6(4) . . ? C59 C60 Au3 118.2(4) . . ? C62 C61 C66 118.8(5) . . ? C62 C61 P4 124.1(4) . . ? C66 C61 P4 117.0(4) . . ? C61 C62 C63 120.3(6) . . ? C61 C62 H62 119.8 . . ? C63 C62 H62 119.8 . . ? C64 C63 C62 119.9(6) . . ? C64 C63 H63 120.0 . . ? C62 C63 H63 120.0 . . ? C63 C64 C65 120.8(6) . . ? C63 C64 H64 119.6 . . ? C65 C64 H64 119.6 . . ? C64 C65 C66 119.7(6) . . ? C64 C65 H65 120.1 . . ? C66 C65 H65 120.1 . . ? C65 C66 C61 120.4(6) . . ? C65 C66 H66 119.8 . . ? C61 C66 H66 119.8 . . ? C68 C67 C72 120.0(5) . . ? C68 C67 P4 119.2(5) . . ? C72 C67 P4 120.7(5) . . ? C67 C68 C69 119.7(6) . . ? C67 C68 H68 120.1 . . ? C69 C68 H68 120.1 . . ? C70 C69 C68 120.7(7) . . ? C70 C69 H69 119.7 . . ? C68 C69 H69 119.7 . . ? C69 C70 C71 120.2(7) . . ? C69 C70 H70 119.9 . . ? C71 C70 H70 119.9 . . ? C70 C71 C72 119.5(8) . . ? C70 C71 H71 120.2 . . ? C72 C71 H71 120.2 . . ? C67 C72 C71 119.8(7) . . ? C67 C72 H72 120.1 . . ? C71 C72 H72 120.1 . . ? Cl1 C1S Cl2 106.6(10) . . ? Cl1 C1S H1S1 110.4 . . ? Cl2 C1S H1S1 110.4 . . ? Cl1 C1S H1S2 110.4 . . ? Cl2 C1S H1S2 110.4 . . ? H1S1 C1S H1S2 108.6 . . ? Cl1A C1T Cl2A 107.7(14) . . ? Cl1A C1T H1T1 110.2 . . ? Cl2A C1T H1T1 110.2 . . ? Cl1A C1T H1T2 110.2 . . ? Cl2A C1T H1T2 110.2 . . ? H1T1 C1T H1T2 108.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C42 -164.5(2) . . . . ? P1 Au1 Au2 C42 23.47(17) . . . . ? Au4 Au1 Au2 C42 -46.66(16) . . . . ? C24 Au1 Au2 P2 26.07(15) . . . . ? P1 Au1 Au2 P2 -145.96(5) . . . . ? Au4 Au1 Au2 P2 143.90(4) . . . . ? C24 Au1 Au2 Au3 -79.61(15) . . . . ? P1 Au1 Au2 Au3 108.36(3) . . . . ? Au4 Au1 Au2 Au3 38.226(7) . . . . ? C42 Au2 Au3 C60 163.3(2) . . . . ? P2 Au2 Au3 C60 -25.35(17) . . . . ? Au1 Au2 Au3 C60 46.90(16) . . . . ? C42 Au2 Au3 P3 -26.55(15) . . . . ? P2 Au2 Au3 P3 144.78(5) . . . . ? Au1 Au2 Au3 P3 -142.98(4) . . . . ? C42 Au2 Au3 Au4 74.61(15) . . . . ? P2 Au2 Au3 Au4 -114.07(4) . . . . ? Au1 Au2 Au3 Au4 -41.823(7) . . . . ? C60 Au3 Au4 C6 -156.0(2) . . . . ? P3 Au3 Au4 C6 31.12(16) . . . . ? Au2 Au3 Au4 C6 -45.19(15) . . . . ? C60 Au3 Au4 P4 27.31(14) . . . . ? P3 Au3 Au4 P4 -145.52(5) . . . . ? Au2 Au3 Au4 P4 138.17(4) . . . . ? C60 Au3 Au4 Au1 -71.54(13) . . . . ? P3 Au3 Au4 Au1 115.64(3) . . . . ? Au2 Au3 Au4 Au1 39.325(7) . . . . ? C24 Au1 Au4 C6 159.9(2) . . . . ? P1 Au1 Au4 C6 -29.49(15) . . . . ? Au2 Au1 Au4 C6 71.60(14) . . . . ? C24 Au1 Au4 P4 -27.58(17) . . . . ? P1 Au1 Au4 P4 143.00(5) . . . . ? Au2 Au1 Au4 P4 -115.91(4) . . . . ? C24 Au1 Au4 Au3 48.88(17) . . . . ? P1 Au1 Au4 Au3 -140.55(4) . . . . ? Au2 Au1 Au4 Au3 -39.461(7) . . . . ? C24 Au1 P1 C7 53.2(7) . . . . ? Au2 Au1 P1 C7 -166.24(18) . . . . ? Au4 Au1 P1 C7 -85.14(18) . . . . ? C24 Au1 P1 C13 -60.4(7) . . . . ? Au2 Au1 P1 C13 80.1(2) . . . . ? Au4 Au1 P1 C13 161.2(2) . . . . ? C24 Au1 P1 C1 176.6(7) . . . . ? Au2 Au1 P1 C1 -42.9(2) . . . . ? Au4 Au1 P1 C1 38.2(2) . . . . ? C42 Au2 P2 C19 -174.1(6) . . . . ? Au3 Au2 P2 C19 41.6(2) . . . . ? Au1 Au2 P2 C19 -33.82(19) . . . . ? C42 Au2 P2 C25 60.8(6) . . . . ? Au3 Au2 P2 C25 -83.46(19) . . . . ? Au1 Au2 P2 C25 -158.9(2) . . . . ? C42 Au2 P2 C31 -51.3(6) . . . . ? Au3 Au2 P2 C31 164.49(18) . . . . ? Au1 Au2 P2 C31 89.05(18) . . . . ? C60 Au3 P3 C37 161.1(7) . . . . ? Au4 Au3 P3 C37 -55.37(19) . . . . ? Au2 Au3 P3 C37 30.97(19) . . . . ? C60 Au3 P3 C43 -75.8(7) . . . . ? Au4 Au3 P3 C43 67.71(19) . . . . ? Au2 Au3 P3 C43 154.0(2) . . . . ? C60 Au3 P3 C49 38.6(7) . . . . ? Au4 Au3 P3 C49 -177.92(17) . . . . ? Au2 Au3 P3 C49 -91.58(17) . . . . ? Au3 Au4 P4 C55 -32.91(18) . . . . ? Au1 Au4 P4 C55 42.87(19) . . . . ? Au3 Au4 P4 C61 -152.54(19) . . . . ? Au1 Au4 P4 C61 -76.76(19) . . . . ? Au3 Au4 P4 C67 92.2(2) . . . . ? Au1 Au4 P4 C67 168.0(2) . . . . ? C7 P1 C1 C6 85.3(5) . . . . ? C13 P1 C1 C6 -163.8(4) . . . . ? Au1 P1 C1 C6 -38.7(5) . . . . ? C7 P1 C1 C2 -94.1(5) . . . . ? C13 P1 C1 C2 16.8(5) . . . . ? Au1 P1 C1 C2 141.9(4) . . . . ? C6 C1 C2 C3 -0.4(9) . . . . ? P1 C1 C2 C3 178.9(5) . . . . ? C1 C2 C3 C4 -0.4(9) . . . . ? C2 C3 C4 C5 0.8(10) . . . . ? C2 C3 C4 F1 -179.8(5) . . . . ? F1 C4 C5 C6 -179.8(5) . . . . ? C3 C4 C5 C6 -0.4(10) . . . . ? C2 C1 C6 C5 0.8(8) . . . . ? P1 C1 C6 C5 -178.5(4) . . . . ? C2 C1 C6 Au4 177.6(4) . . . . ? P1 C1 C6 Au4 -1.8(6) . . . . ? C4 C5 C6 C1 -0.4(8) . . . . ? C4 C5 C6 Au4 -177.3(4) . . . . ? Au3 Au4 C6 C1 100.3(4) . . . . ? Au1 Au4 C6 C1 24.0(4) . . . . ? Au3 Au4 C6 C5 -83.1(4) . . . . ? Au1 Au4 C6 C5 -159.4(4) . . . . ? C13 P1 C7 C8 -140.7(5) . . . . ? C1 P1 C7 C8 -29.2(5) . . . . ? Au1 P1 C7 C8 102.2(5) . . . . ? C13 P1 C7 C12 45.9(5) . . . . ? C1 P1 C7 C12 157.3(5) . . . . ? Au1 P1 C7 C12 -71.2(5) . . . . ? C12 C7 C8 C9 1.3(8) . . . . ? P1 C7 C8 C9 -172.3(4) . . . . ? C7 C8 C9 C10 -0.3(9) . . . . ? C8 C9 C10 C11 -1.6(9) . . . . ? C9 C10 C11 C12 2.7(9) . . . . ? C10 C11 C12 C7 -1.7(9) . . . . ? C8 C7 C12 C11 -0.2(9) . . . . ? P1 C7 C12 C11 173.5(5) . . . . ? C7 P1 C13 C18 -153.5(5) . . . . ? C1 P1 C13 C18 94.0(5) . . . . ? Au1 P1 C13 C18 -37.7(5) . . . . ? C7 P1 C13 C14 31.5(5) . . . . ? C1 P1 C13 C14 -81.0(5) . . . . ? Au1 P1 C13 C14 147.3(4) . . . . ? C18 C13 C14 C15 -0.3(9) . . . . ? P1 C13 C14 C15 174.7(5) . . . . ? C13 C14 C15 C16 0.0(10) . . . . ? C14 C15 C16 C17 0.4(10) . . . . ? C15 C16 C17 C18 -0.5(10) . . . . ? C14 C13 C18 C17 0.1(9) . . . . ? P1 C13 C18 C17 -175.1(5) . . . . ? C16 C17 C18 C13 0.3(10) . . . . ? C25 P2 C19 C20 -20.6(5) . . . . ? C31 P2 C19 C20 87.8(5) . . . . ? Au2 P2 C19 C20 -147.1(4) . . . . ? C25 P2 C19 C24 159.4(4) . . . . ? C31 P2 C19 C24 -92.3(4) . . . . ? Au2 P2 C19 C24 32.8(4) . . . . ? C24 C19 C20 C21 2.4(8) . . . . ? P2 C19 C20 C21 -177.6(4) . . . . ? C19 C20 C21 C22 -1.0(8) . . . . ? C20 C21 C22 F2 180.0(5) . . . . ? C20 C21 C22 C23 0.6(8) . . . . ? C21 C22 C23 C24 -1.5(8) . . . . ? F2 C22 C23 C24 179.0(5) . . . . ? C22 C23 C24 C19 2.8(7) . . . . ? C22 C23 C24 Au1 178.9(4) . . . . ? C20 C19 C24 C23 -3.2(7) . . . . ? P2 C19 C24 C23 176.8(4) . . . . ? C20 C19 C24 Au1 -179.2(4) . . . . ? P2 C19 C24 Au1 0.9(6) . . . . ? P1 Au1 C24 C23 -56.0(9) . . . . ? Au2 Au1 C24 C23 162.9(4) . . . . ? Au4 Au1 C24 C23 78.6(4) . . . . ? P1 Au1 C24 C19 119.7(6) . . . . ? Au2 Au1 C24 C19 -21.3(4) . . . . ? Au4 Au1 C24 C19 -105.6(4) . . . . ? C19 P2 C25 C30 -91.8(5) . . . . ? C31 P2 C25 C30 157.4(5) . . . . ? Au2 P2 C25 C30 40.2(5) . . . . ? C19 P2 C25 C26 88.2(5) . . . . ? C31 P2 C25 C26 -22.6(5) . . . . ? Au2 P2 C25 C26 -139.8(4) . . . . ? C30 C25 C26 C27 -0.3(9) . . . . ? P2 C25 C26 C27 179.7(5) . . . . ? C25 C26 C27 C28 0.6(9) . . . . ? C26 C27 C28 C29 -0.5(9) . . . . ? C27 C28 C29 C30 0.2(9) . . . . ? C28 C29 C30 C25 0.1(9) . . . . ? C26 C25 C30 C29 0.0(8) . . . . ? P2 C25 C30 C29 180.0(4) . . . . ? C19 P2 C31 C32 158.9(4) . . . . ? C25 P2 C31 C32 -89.2(5) . . . . ? Au2 P2 C31 C32 28.1(5) . . . . ? C19 P2 C31 C36 -24.3(5) . . . . ? C25 P2 C31 C36 87.7(5) . . . . ? Au2 P2 C31 C36 -155.1(4) . . . . ? C36 C31 C32 C33 -2.2(9) . . . . ? P2 C31 C32 C33 174.7(5) . . . . ? C31 C32 C33 C34 0.6(9) . . . . ? C32 C33 C34 C35 1.5(10) . . . . ? C33 C34 C35 C36 -2.2(10) . . . . ? C34 C35 C36 C31 0.6(9) . . . . ? C32 C31 C36 C35 1.5(9) . . . . ? P2 C31 C36 C35 -175.3(5) . . . . ? C43 P3 C37 C38 27.3(5) . . . . ? C49 P3 C37 C38 -82.9(5) . . . . ? Au3 P3 C37 C38 153.6(4) . . . . ? C43 P3 C37 C42 -152.5(4) . . . . ? C49 P3 C37 C42 97.3(4) . . . . ? Au3 P3 C37 C42 -26.2(5) . . . . ? C42 C37 C38 C39 0.6(9) . . . . ? P3 C37 C38 C39 -179.2(4) . . . . ? C37 C38 C39 C40 0.3(9) . . . . ? C38 C39 C40 F3 179.8(6) . . . . ? C38 C39 C40 C41 -0.6(10) . . . . ? F3 C40 C41 C42 179.5(5) . . . . ? C39 C40 C41 C42 -0.1(10) . . . . ? C40 C41 C42 C37 1.0(8) . . . . ? C40 C41 C42 Au2 -173.0(5) . . . . ? C38 C37 C42 C41 -1.2(8) . . . . ? P3 C37 C42 C41 178.6(4) . . . . ? C38 C37 C42 Au2 172.4(4) . . . . ? P3 C37 C42 Au2 -7.8(6) . . . . ? P2 Au2 C42 C41 54.0(9) . . . . ? Au3 Au2 C42 C41 -160.9(4) . . . . ? Au1 Au2 C42 C41 -82.6(4) . . . . ? P2 Au2 C42 C37 -119.5(6) . . . . ? Au3 Au2 C42 C37 25.6(4) . . . . ? Au1 Au2 C42 C37 103.9(4) . . . . ? C37 P3 C43 C44 -83.9(5) . . . . ? C49 P3 C43 C44 28.3(6) . . . . ? Au3 P3 C43 C44 145.6(4) . . . . ? C37 P3 C43 C48 95.6(5) . . . . ? C49 P3 C43 C48 -152.2(4) . . . . ? Au3 P3 C43 C48 -34.8(5) . . . . ? C48 C43 C44 C45 -3.8(9) . . . . ? P3 C43 C44 C45 175.7(5) . . . . ? C43 C44 C45 C46 2.1(10) . . . . ? C44 C45 C46 C47 1.3(10) . . . . ? C45 C46 C47 C48 -3.0(10) . . . . ? C46 C47 C48 C43 1.2(9) . . . . ? C44 C43 C48 C47 2.2(9) . . . . ? P3 C43 C48 C47 -177.4(4) . . . . ? C37 P3 C49 C54 26.6(5) . . . . ? C43 P3 C49 C54 -84.5(5) . . . . ? Au3 P3 C49 C54 156.1(4) . . . . ? C37 P3 C49 C50 -156.1(4) . . . . ? C43 P3 C49 C50 92.8(4) . . . . ? Au3 P3 C49 C50 -26.6(5) . . . . ? C54 C49 C50 C51 -1.0(8) . . . . ? P3 C49 C50 C51 -178.5(4) . . . . ? C49 C50 C51 C52 0.6(8) . . . . ? C50 C51 C52 C53 -0.6(9) . . . . ? C51 C52 C53 C54 1.2(9) . . . . ? C52 C53 C54 C49 -1.7(9) . . . . ? C50 C49 C54 C53 1.6(8) . . . . ? P3 C49 C54 C53 178.9(4) . . . . ? C61 P4 C55 C60 150.7(4) . . . . ? C67 P4 C55 C60 -98.3(4) . . . . ? Au4 P4 C55 C60 29.7(4) . . . . ? C61 P4 C55 C56 -28.8(5) . . . . ? C67 P4 C55 C56 82.2(4) . . . . ? Au4 P4 C55 C56 -149.8(3) . . . . ? C60 C55 C56 C57 0.7(8) . . . . ? P4 C55 C56 C57 -179.9(4) . . . . ? C55 C56 C57 C58 -0.9(7) . . . . ? C56 C57 C58 C59 1.4(8) . . . . ? C56 C57 C58 F4 -179.7(4) . . . . ? F4 C58 C59 C60 179.5(4) . . . . ? C57 C58 C59 C60 -1.6(8) . . . . ? C56 C55 C60 C59 -0.8(7) . . . . ? P4 C55 C60 C59 179.7(4) . . . . ? C56 C55 C60 Au3 -176.3(4) . . . . ? P4 C55 C60 Au3 4.2(6) . . . . ? C58 C59 C60 C55 1.2(7) . . . . ? C58 C59 C60 Au3 177.0(4) . . . . ? P3 Au3 C60 C55 119.8(7) . . . . ? Au4 Au3 C60 C55 -24.4(4) . . . . ? Au2 Au3 C60 C55 -112.9(4) . . . . ? P3 Au3 C60 C59 -55.7(9) . . . . ? Au4 Au3 C60 C59 160.1(4) . . . . ? Au2 Au3 C60 C59 71.5(4) . . . . ? C55 P4 C61 C62 111.9(5) . . . . ? C67 P4 C61 C62 -1.5(6) . . . . ? Au4 P4 C61 C62 -122.5(5) . . . . ? C55 P4 C61 C66 -70.1(5) . . . . ? C67 P4 C61 C66 176.4(5) . . . . ? Au4 P4 C61 C66 55.4(5) . . . . ? C66 C61 C62 C63 -0.8(9) . . . . ? P4 C61 C62 C63 177.1(5) . . . . ? C61 C62 C63 C64 1.3(10) . . . . ? C62 C63 C64 C65 -0.3(10) . . . . ? C63 C64 C65 C66 -1.2(9) . . . . ? C64 C65 C66 C61 1.8(9) . . . . ? C62 C61 C66 C65 -0.8(9) . . . . ? P4 C61 C66 C65 -178.8(5) . . . . ? C55 P4 C67 C68 160.6(5) . . . . ? C61 P4 C67 C68 -87.0(5) . . . . ? Au4 P4 C67 C68 31.1(5) . . . . ? C55 P4 C67 C72 -22.0(6) . . . . ? C61 P4 C67 C72 90.4(6) . . . . ? Au4 P4 C67 C72 -151.5(5) . . . . ? C72 C67 C68 C69 -0.3(10) . . . . ? P4 C67 C68 C69 177.1(5) . . . . ? C67 C68 C69 C70 0.4(11) . . . . ? C68 C69 C70 C71 0.2(13) . . . . ? C69 C70 C71 C72 -0.8(15) . . . . ? C68 C67 C72 C71 -0.4(12) . . . . ? P4 C67 C72 C71 -177.8(7) . . . . ? C70 C71 C72 C67 1.0(14) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.505 _refine_diff_density_min -1.756 _refine_diff_density_rms 0.192 # Attachment 'neda02301.cif.txt' data_neda02301 _database_code_depnum_ccdc_archive 'CCDC 726004' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 Br2 F2 P2' _chemical_formula_sum 'C36 H26 Au2 Br2 F2 P2' _chemical_formula_weight 1112.26 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c _symmetry_space_group_name_Hall -P2ybc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 11.03440(10) _cell_length_b 16.0528(2) _cell_length_c 18.4780(2) _cell_angle_alpha 90.00 _cell_angle_beta 91.6760(10) _cell_angle_gamma 90.00 _cell_volume 3271.66(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 82746 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 35.631 _exptl_crystal_description polyhedron _exptl_crystal_colour colorless _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.19 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.258 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2072 _exptl_absorpt_coefficient_mu 11.536 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.032 _exptl_absorpt_correction_T_max 0.112 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 70789 _diffrn_reflns_av_R_equivalents 0.0748 _diffrn_reflns_av_sigmaI/netI 0.0421 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 35.00 _reflns_number_total 14374 _reflns_number_gt 11796 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0350P)^2^+3.9771P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 14374 _refine_ls_number_parameters 397 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0454 _refine_ls_R_factor_gt 0.0318 _refine_ls_wR_factor_ref 0.0756 _refine_ls_wR_factor_gt 0.0721 _refine_ls_goodness_of_fit_ref 1.025 _refine_ls_restrained_S_all 1.025 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.103574(10) 0.770240(7) 0.425209(6) 0.01664(3) Uani 1 1 d . . . Au2 Au 0.414978(11) 0.742433(7) 0.471841(6) 0.01849(3) Uani 1 1 d . . . P1 P 0.16498(7) 0.89002(5) 0.37643(4) 0.01495(13) Uani 1 1 d . . . P2 P 0.42461(7) 0.65721(5) 0.37668(4) 0.01635(13) Uani 1 1 d . . . Br1 Br 0.02205(3) 0.64679(2) 0.47932(2) 0.02502(7) Uani 1 1 d . . . Br2 Br 0.41895(4) 0.82621(2) 0.579707(19) 0.02893(7) Uani 1 1 d . . . F1 F 0.67459(17) 0.90742(13) 0.28339(13) 0.0284(4) Uani 1 1 d . . . F2 F 0.0596(2) 0.71411(14) 0.13977(12) 0.0298(5) Uani 1 1 d . . . C1 C 0.1523(3) 0.97715(18) 0.43865(16) 0.0162(5) Uani 1 1 d . . . C2 C 0.1699(3) 0.9623(2) 0.51233(17) 0.0199(5) Uani 1 1 d . . . H2 H 0.1778 0.9067 0.5296 0.024 Uiso 1 1 calc R . . C3 C 0.1760(3) 1.0284(2) 0.56081(18) 0.0217(6) Uani 1 1 d . . . H3 H 0.1895 1.0181 0.6110 0.026 Uiso 1 1 calc R . . C4 C 0.1624(3) 1.1097(2) 0.53589(19) 0.0228(6) Uani 1 1 d . . . H4 H 0.1685 1.1549 0.5689 0.027 Uiso 1 1 calc R . . C5 C 0.1399(3) 1.12480(19) 0.46288(19) 0.0218(6) Uani 1 1 d . . . H5 H 0.1282 1.1803 0.4462 0.026 Uiso 1 1 calc R . . C6 C 0.1345(3) 1.05894(19) 0.41403(18) 0.0191(5) Uani 1 1 d . . . H6 H 0.1187 1.0694 0.3640 0.023 Uiso 1 1 calc R . . C7 C 0.0866(3) 0.92019(18) 0.29274(16) 0.0169(5) Uani 1 1 d . . . C8 C 0.1415(3) 0.97424(19) 0.24413(17) 0.0190(5) Uani 1 1 d . . . H8 H 0.2178 0.9985 0.2566 0.023 Uiso 1 1 calc R . . C9 C 0.0856(3) 0.9928(2) 0.17801(18) 0.0219(6) Uani 1 1 d . . . H9 H 0.1231 1.0302 0.1457 0.026 Uiso 1 1 calc R . . C10 C -0.0254(3) 0.9566(2) 0.15883(18) 0.0223(6) Uani 1 1 d . . . H10 H -0.0632 0.9685 0.1132 0.027 Uiso 1 1 calc R . . C11 C -0.0803(3) 0.9033(2) 0.20636(18) 0.0221(6) Uani 1 1 d . . . H11 H -0.1561 0.8787 0.1933 0.027 Uiso 1 1 calc R . . C12 C -0.0255(3) 0.8852(2) 0.27351(17) 0.0189(5) Uani 1 1 d . . . H12 H -0.0645 0.8489 0.3062 0.023 Uiso 1 1 calc R . . C13 C 0.3237(3) 0.89062(17) 0.35127(16) 0.0155(5) Uani 1 1 d . . . C14 C 0.4016(3) 0.95283(18) 0.37781(17) 0.0181(5) Uani 1 1 d . . . H14 H 0.3720 0.9922 0.4114 0.022 Uiso 1 1 calc R . . C15 C 0.5209(3) 0.95881(19) 0.35654(18) 0.0196(5) Uani 1 1 d . . . H15 H 0.5737 1.0006 0.3757 0.024 Uiso 1 1 calc R . . C16 C 0.5599(3) 0.90198(19) 0.30667(18) 0.0190(5) Uani 1 1 d . . . C17 C 0.4868(3) 0.83844(18) 0.27910(17) 0.0177(5) Uani 1 1 d . . . H17 H 0.5172 0.8007 0.2444 0.021 Uiso 1 1 calc R . . C18 C 0.3687(3) 0.83039(17) 0.30255(16) 0.0156(5) Uani 1 1 d . . . C19 C 0.2943(3) 0.75752(17) 0.27556(16) 0.0153(5) Uani 1 1 d . . . C20 C 0.2117(3) 0.76810(18) 0.21849(17) 0.0186(5) Uani 1 1 d . . . H20 H 0.2031 0.8210 0.1958 0.022 Uiso 1 1 calc R . . C21 C 0.1413(3) 0.7014(2) 0.19444(17) 0.0215(6) Uani 1 1 d . . . C22 C 0.1512(3) 0.6227(2) 0.22504(18) 0.0214(6) Uani 1 1 d . . . H22 H 0.1009 0.5781 0.2085 0.026 Uiso 1 1 calc R . . C23 C 0.2365(3) 0.61112(19) 0.28019(18) 0.0196(5) Uani 1 1 d . . . H23 H 0.2461 0.5574 0.3011 0.023 Uiso 1 1 calc R . . C24 C 0.3092(3) 0.67683(17) 0.30601(16) 0.0155(5) Uani 1 1 d . . . C25 C 0.4055(3) 0.54885(18) 0.40276(17) 0.0190(5) Uani 1 1 d . . . C26 C 0.3138(3) 0.5297(2) 0.4504(2) 0.0264(7) Uani 1 1 d . . . H26 H 0.2670 0.5732 0.4706 0.032 Uiso 1 1 calc R . . C27 C 0.2908(3) 0.4473(2) 0.4684(2) 0.0309(8) Uani 1 1 d . . . H27 H 0.2271 0.4340 0.4999 0.037 Uiso 1 1 calc R . . C28 C 0.3615(4) 0.3847(2) 0.4399(2) 0.0324(8) Uani 1 1 d . . . H28 H 0.3449 0.3283 0.4514 0.039 Uiso 1 1 calc R . . C29 C 0.4560(4) 0.4033(2) 0.3953(2) 0.0317(8) Uani 1 1 d . . . H29 H 0.5062 0.3600 0.3780 0.038 Uiso 1 1 calc R . . C30 C 0.4773(4) 0.4853(2) 0.3757(2) 0.0272(7) Uani 1 1 d . . . H30 H 0.5408 0.4981 0.3439 0.033 Uiso 1 1 calc R . . C31 C 0.5668(3) 0.66201(18) 0.32935(17) 0.0181(5) Uani 1 1 d . . . C32 C 0.6718(3) 0.6897(2) 0.36545(18) 0.0212(6) Uani 1 1 d . . . H32 H 0.6709 0.7019 0.4157 0.025 Uiso 1 1 calc R . . C33 C 0.7786(3) 0.6994(2) 0.3274(2) 0.0241(6) Uani 1 1 d . . . H33 H 0.8510 0.7165 0.3522 0.029 Uiso 1 1 calc R . . C34 C 0.7788(3) 0.6840(2) 0.2534(2) 0.0262(7) Uani 1 1 d . . . H34 H 0.8506 0.6931 0.2274 0.031 Uiso 1 1 calc R . . C35 C 0.6752(3) 0.6555(2) 0.21751(19) 0.0229(6) Uani 1 1 d . . . H35 H 0.6759 0.6445 0.1670 0.027 Uiso 1 1 calc R . . C36 C 0.5696(3) 0.64299(19) 0.25573(18) 0.0198(5) Uani 1 1 d . . . H36 H 0.4992 0.6214 0.2315 0.024 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01859(5) 0.01558(5) 0.01582(5) 0.00070(3) 0.00188(4) -0.00149(3) Au2 0.02552(6) 0.01642(5) 0.01342(5) -0.00132(4) -0.00158(4) 0.00045(4) P1 0.0162(3) 0.0148(3) 0.0139(3) -0.0001(2) 0.0008(2) -0.0004(2) P2 0.0203(3) 0.0143(3) 0.0144(3) -0.0007(2) -0.0007(3) -0.0008(2) Br1 0.02804(15) 0.02096(14) 0.02629(17) 0.00499(12) 0.00449(12) -0.00572(11) Br2 0.04127(19) 0.02559(15) 0.01954(15) -0.00836(12) -0.00580(13) 0.00745(13) F1 0.0182(9) 0.0277(10) 0.0396(13) -0.0063(9) 0.0078(8) -0.0041(7) F2 0.0343(11) 0.0268(10) 0.0273(11) -0.0015(8) -0.0162(9) 0.0005(8) C1 0.0166(12) 0.0182(12) 0.0138(12) -0.0016(9) -0.0001(9) 0.0021(9) C2 0.0190(13) 0.0222(13) 0.0182(14) 0.0019(10) -0.0007(10) 0.0022(10) C3 0.0205(13) 0.0267(15) 0.0179(14) -0.0030(11) 0.0010(11) 0.0017(11) C4 0.0205(13) 0.0250(15) 0.0231(16) -0.0079(12) 0.0025(11) 0.0007(11) C5 0.0233(14) 0.0172(12) 0.0250(16) -0.0028(11) 0.0005(11) 0.0012(10) C6 0.0189(13) 0.0203(13) 0.0183(14) -0.0013(10) 0.0014(10) 0.0015(10) C7 0.0183(12) 0.0172(12) 0.0153(13) -0.0019(9) 0.0001(10) 0.0016(9) C8 0.0197(13) 0.0185(12) 0.0188(14) -0.0013(10) 0.0004(10) -0.0019(10) C9 0.0275(15) 0.0216(13) 0.0165(14) 0.0025(11) 0.0000(11) 0.0021(11) C10 0.0263(15) 0.0250(14) 0.0155(13) -0.0018(11) -0.0034(11) 0.0061(11) C11 0.0186(13) 0.0277(15) 0.0198(14) -0.0061(11) -0.0028(11) 0.0008(11) C12 0.0171(12) 0.0231(13) 0.0165(13) -0.0005(10) 0.0021(10) 0.0001(10) C13 0.0165(11) 0.0160(11) 0.0142(12) -0.0005(9) 0.0007(9) -0.0001(9) C14 0.0189(12) 0.0154(12) 0.0201(14) -0.0028(10) 0.0002(10) 0.0008(9) C15 0.0179(13) 0.0167(12) 0.0242(15) -0.0019(10) 0.0001(11) -0.0020(9) C16 0.0179(12) 0.0179(12) 0.0212(14) 0.0004(10) 0.0027(10) -0.0007(10) C17 0.0187(12) 0.0166(12) 0.0178(13) 0.0000(10) 0.0016(10) 0.0008(9) C18 0.0177(12) 0.0139(11) 0.0151(12) 0.0007(9) -0.0008(9) 0.0001(9) C19 0.0173(12) 0.0148(11) 0.0140(12) -0.0023(9) 0.0018(9) -0.0003(9) C20 0.0223(13) 0.0157(12) 0.0175(13) -0.0007(10) -0.0029(11) 0.0022(9) C21 0.0247(14) 0.0239(14) 0.0155(13) -0.0032(11) -0.0054(11) 0.0012(11) C22 0.0232(14) 0.0199(13) 0.0212(15) -0.0039(11) -0.0016(11) -0.0049(10) C23 0.0232(14) 0.0170(12) 0.0184(13) -0.0017(10) -0.0018(11) -0.0025(10) C24 0.0176(12) 0.0158(11) 0.0131(12) 0.0000(9) 0.0006(9) -0.0003(9) C25 0.0256(14) 0.0150(12) 0.0162(13) 0.0008(10) -0.0026(11) -0.0018(10) C26 0.0249(15) 0.0221(14) 0.0321(19) 0.0078(13) 0.0004(13) -0.0002(11) C27 0.0270(16) 0.0279(17) 0.038(2) 0.0127(15) -0.0042(15) -0.0074(13) C28 0.048(2) 0.0203(15) 0.0277(18) 0.0076(13) -0.0157(16) -0.0076(14) C29 0.057(2) 0.0187(14) 0.0194(16) 0.0013(12) -0.0023(15) 0.0044(15) C30 0.0415(19) 0.0191(14) 0.0211(16) 0.0011(11) 0.0034(14) 0.0015(13) C31 0.0219(13) 0.0142(11) 0.0182(14) -0.0010(10) -0.0005(10) -0.0001(9) C32 0.0209(13) 0.0224(14) 0.0200(14) 0.0006(11) -0.0034(11) -0.0024(10) C33 0.0207(14) 0.0240(15) 0.0274(17) -0.0008(12) -0.0031(12) -0.0021(11) C34 0.0209(14) 0.0243(15) 0.0337(19) -0.0032(13) 0.0052(13) 0.0004(11) C35 0.0247(14) 0.0229(14) 0.0212(15) -0.0022(11) 0.0031(12) 0.0034(11) C36 0.0212(13) 0.0199(13) 0.0184(14) -0.0025(10) -0.0007(10) 0.0027(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 P1 2.2371(7) . ? Au1 Br1 2.4060(3) . ? Au1 Au2 3.54623(17) . ? Au2 P2 2.2329(8) . ? Au2 Br2 2.4037(3) . ? P1 C7 1.815(3) . ? P1 C1 1.819(3) . ? P1 C13 1.826(3) . ? P2 C25 1.819(3) . ? P2 C31 1.820(3) . ? P2 C24 1.824(3) . ? F1 C16 1.351(4) . ? F2 C21 1.350(4) . ? C1 C2 1.390(4) . ? C1 C6 1.401(4) . ? C2 C3 1.390(4) . ? C2 H2 0.9500 . ? C3 C4 1.390(5) . ? C3 H3 0.9500 . ? C4 C5 1.386(5) . ? C4 H4 0.9500 . ? C5 C6 1.390(4) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 C12 1.395(4) . ? C7 C8 1.400(4) . ? C8 C9 1.385(4) . ? C8 H8 0.9500 . ? C9 C10 1.392(5) . ? C9 H9 0.9500 . ? C10 C11 1.379(5) . ? C10 H10 0.9500 . ? C11 C12 1.395(4) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.397(4) . ? C13 C18 1.420(4) . ? C14 C15 1.389(4) . ? C14 H14 0.9500 . ? C15 C16 1.374(4) . ? C15 H15 0.9500 . ? C16 C17 1.388(4) . ? C17 C18 1.391(4) . ? C17 H17 0.9500 . ? C18 C19 1.505(4) . ? C19 C20 1.384(4) . ? C19 C24 1.420(4) . ? C20 C21 1.389(4) . ? C20 H20 0.9500 . ? C21 C22 1.387(5) . ? C22 C23 1.379(4) . ? C22 H22 0.9500 . ? C23 C24 1.401(4) . ? C23 H23 0.9500 . ? C25 C30 1.394(5) . ? C25 C26 1.394(5) . ? C26 C27 1.390(5) . ? C26 H26 0.9500 . ? C27 C28 1.385(6) . ? C27 H27 0.9500 . ? C28 C29 1.381(6) . ? C28 H28 0.9500 . ? C29 C30 1.387(5) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.393(4) . ? C31 C36 1.396(4) . ? C32 C33 1.398(5) . ? C32 H32 0.9500 . ? C33 C34 1.389(5) . ? C33 H33 0.9500 . ? C34 C35 1.383(5) . ? C34 H34 0.9500 . ? C35 C36 1.394(5) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag P1 Au1 Br1 175.37(2) . . ? P1 Au1 Au2 84.453(19) . . ? Br1 Au1 Au2 99.600(9) . . ? P2 Au2 Br2 174.64(2) . . ? P2 Au2 Au1 87.36(2) . . ? Br2 Au2 Au1 97.186(10) . . ? C7 P1 C1 106.85(13) . . ? C7 P1 C13 102.63(14) . . ? C1 P1 C13 104.43(13) . . ? C7 P1 Au1 115.47(10) . . ? C1 P1 Au1 112.12(10) . . ? C13 P1 Au1 114.29(10) . . ? C25 P2 C31 106.03(14) . . ? C25 P2 C24 105.71(14) . . ? C31 P2 C24 104.01(14) . . ? C25 P2 Au2 111.63(11) . . ? C31 P2 Au2 114.46(10) . . ? C24 P2 Au2 114.18(10) . . ? C2 C1 C6 119.6(3) . . ? C2 C1 P1 118.4(2) . . ? C6 C1 P1 121.9(2) . . ? C3 C2 C1 120.2(3) . . ? C3 C2 H2 119.9 . . ? C1 C2 H2 119.9 . . ? C2 C3 C4 120.1(3) . . ? C2 C3 H3 120.0 . . ? C4 C3 H3 120.0 . . ? C5 C4 C3 120.1(3) . . ? C5 C4 H4 120.0 . . ? C3 C4 H4 120.0 . . ? C4 C5 C6 120.1(3) . . ? C4 C5 H5 119.9 . . ? C6 C5 H5 119.9 . . ? C5 C6 C1 119.9(3) . . ? C5 C6 H6 120.0 . . ? C1 C6 H6 120.0 . . ? C12 C7 C8 118.9(3) . . ? C12 C7 P1 120.4(2) . . ? C8 C7 P1 120.5(2) . . ? C9 C8 C7 120.6(3) . . ? C9 C8 H8 119.7 . . ? C7 C8 H8 119.7 . . ? C8 C9 C10 120.0(3) . . ? C8 C9 H9 120.0 . . ? C10 C9 H9 120.0 . . ? C11 C10 C9 119.8(3) . . ? C11 C10 H10 120.1 . . ? C9 C10 H10 120.1 . . ? C10 C11 C12 120.6(3) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C7 C12 C11 120.0(3) . . ? C7 C12 H12 120.0 . . ? C11 C12 H12 120.0 . . ? C14 C13 C18 119.1(3) . . ? C14 C13 P1 119.9(2) . . ? C18 C13 P1 120.9(2) . . ? C15 C14 C13 121.9(3) . . ? C15 C14 H14 119.0 . . ? C13 C14 H14 119.0 . . ? C16 C15 C14 117.5(3) . . ? C16 C15 H15 121.3 . . ? C14 C15 H15 121.3 . . ? F1 C16 C15 119.0(3) . . ? F1 C16 C17 118.1(3) . . ? C15 C16 C17 123.0(3) . . ? C16 C17 C18 119.6(3) . . ? C16 C17 H17 120.2 . . ? C18 C17 H17 120.2 . . ? C17 C18 C13 118.8(3) . . ? C17 C18 C19 118.4(3) . . ? C13 C18 C19 122.8(3) . . ? C20 C19 C24 118.7(3) . . ? C20 C19 C18 119.8(3) . . ? C24 C19 C18 121.5(3) . . ? C19 C20 C21 119.9(3) . . ? C19 C20 H20 120.0 . . ? C21 C20 H20 120.0 . . ? F2 C21 C22 119.1(3) . . ? F2 C21 C20 118.5(3) . . ? C22 C21 C20 122.4(3) . . ? C23 C22 C21 117.9(3) . . ? C23 C22 H22 121.1 . . ? C21 C22 H22 121.1 . . ? C22 C23 C24 121.5(3) . . ? C22 C23 H23 119.3 . . ? C24 C23 H23 119.3 . . ? C23 C24 C19 119.6(3) . . ? C23 C24 P2 119.7(2) . . ? C19 C24 P2 120.8(2) . . ? C30 C25 C26 119.8(3) . . ? C30 C25 P2 122.2(3) . . ? C26 C25 P2 118.0(2) . . ? C27 C26 C25 120.1(3) . . ? C27 C26 H26 119.9 . . ? C25 C26 H26 119.9 . . ? C28 C27 C26 119.4(4) . . ? C28 C27 H27 120.3 . . ? C26 C27 H27 120.3 . . ? C29 C28 C27 120.9(3) . . ? C29 C28 H28 119.5 . . ? C27 C28 H28 119.5 . . ? C28 C29 C30 119.9(4) . . ? C28 C29 H29 120.1 . . ? C30 C29 H29 120.1 . . ? C29 C30 C25 119.9(4) . . ? C29 C30 H30 120.1 . . ? C25 C30 H30 120.1 . . ? C32 C31 C36 119.6(3) . . ? C32 C31 P2 120.0(2) . . ? C36 C31 P2 120.2(2) . . ? C31 C32 C33 119.8(3) . . ? C31 C32 H32 120.1 . . ? C33 C32 H32 120.1 . . ? C34 C33 C32 120.0(3) . . ? C34 C33 H33 120.0 . . ? C32 C33 H33 120.0 . . ? C35 C34 C33 120.4(3) . . ? C35 C34 H34 119.8 . . ? C33 C34 H34 119.8 . . ? C34 C35 C36 119.7(3) . . ? C34 C35 H35 120.1 . . ? C36 C35 H35 120.1 . . ? C35 C36 C31 120.3(3) . . ? C35 C36 H36 119.8 . . ? C31 C36 H36 119.8 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag P1 Au1 Au2 P2 -100.60(3) . . . . ? Br1 Au1 Au2 P2 81.67(2) . . . . ? P1 Au1 Au2 Br2 82.25(2) . . . . ? Br1 Au1 Au2 Br2 -95.477(14) . . . . ? Au2 Au1 P1 C7 142.86(11) . . . . ? Au2 Au1 P1 C1 -94.45(10) . . . . ? Au2 Au1 P1 C13 24.14(11) . . . . ? Au1 Au2 P2 C25 -95.11(11) . . . . ? Au1 Au2 P2 C31 144.44(11) . . . . ? Au1 Au2 P2 C24 24.72(10) . . . . ? C7 P1 C1 C2 160.1(2) . . . . ? C13 P1 C1 C2 -91.6(3) . . . . ? Au1 P1 C1 C2 32.7(3) . . . . ? C7 P1 C1 C6 -24.7(3) . . . . ? C13 P1 C1 C6 83.5(3) . . . . ? Au1 P1 C1 C6 -152.2(2) . . . . ? C6 C1 C2 C3 -3.3(4) . . . . ? P1 C1 C2 C3 172.0(2) . . . . ? C1 C2 C3 C4 1.1(5) . . . . ? C2 C3 C4 C5 1.5(5) . . . . ? C3 C4 C5 C6 -1.9(5) . . . . ? C4 C5 C6 C1 -0.3(5) . . . . ? C2 C1 C6 C5 2.9(4) . . . . ? P1 C1 C6 C5 -172.2(2) . . . . ? C1 P1 C7 C12 -106.9(3) . . . . ? C13 P1 C7 C12 143.5(2) . . . . ? Au1 P1 C7 C12 18.5(3) . . . . ? C1 P1 C7 C8 77.7(3) . . . . ? C13 P1 C7 C8 -31.8(3) . . . . ? Au1 P1 C7 C8 -156.8(2) . . . . ? C12 C7 C8 C9 0.0(5) . . . . ? P1 C7 C8 C9 175.4(2) . . . . ? C7 C8 C9 C10 -1.0(5) . . . . ? C8 C9 C10 C11 1.0(5) . . . . ? C9 C10 C11 C12 -0.1(5) . . . . ? C8 C7 C12 C11 0.9(4) . . . . ? P1 C7 C12 C11 -174.6(2) . . . . ? C10 C11 C12 C7 -0.8(5) . . . . ? C7 P1 C13 C14 108.8(3) . . . . ? C1 P1 C13 C14 -2.6(3) . . . . ? Au1 P1 C13 C14 -125.5(2) . . . . ? C7 P1 C13 C18 -68.7(3) . . . . ? C1 P1 C13 C18 179.9(2) . . . . ? Au1 P1 C13 C18 57.1(3) . . . . ? C18 C13 C14 C15 1.7(5) . . . . ? P1 C13 C14 C15 -175.9(2) . . . . ? C13 C14 C15 C16 1.4(5) . . . . ? C14 C15 C16 F1 178.3(3) . . . . ? C14 C15 C16 C17 -2.1(5) . . . . ? F1 C16 C17 C18 179.2(3) . . . . ? C15 C16 C17 C18 -0.4(5) . . . . ? C16 C17 C18 C13 3.5(4) . . . . ? C16 C17 C18 C19 -175.9(3) . . . . ? C14 C13 C18 C17 -4.1(4) . . . . ? P1 C13 C18 C17 173.4(2) . . . . ? C14 C13 C18 C19 175.3(3) . . . . ? P1 C13 C18 C19 -7.2(4) . . . . ? C17 C18 C19 C20 -98.8(4) . . . . ? C13 C18 C19 C20 81.7(4) . . . . ? C17 C18 C19 C24 79.4(4) . . . . ? C13 C18 C19 C24 -100.1(3) . . . . ? C24 C19 C20 C21 3.0(5) . . . . ? C18 C19 C20 C21 -178.7(3) . . . . ? C19 C20 C21 F2 178.5(3) . . . . ? C19 C20 C21 C22 -0.8(5) . . . . ? F2 C21 C22 C23 179.2(3) . . . . ? C20 C21 C22 C23 -1.5(5) . . . . ? C21 C22 C23 C24 1.4(5) . . . . ? C22 C23 C24 C19 0.8(5) . . . . ? C22 C23 C24 P2 -177.6(3) . . . . ? C20 C19 C24 C23 -3.0(4) . . . . ? C18 C19 C24 C23 178.8(3) . . . . ? C20 C19 C24 P2 175.4(2) . . . . ? C18 C19 C24 P2 -2.8(4) . . . . ? C25 P2 C24 C23 -4.8(3) . . . . ? C31 P2 C24 C23 106.7(3) . . . . ? Au2 P2 C24 C23 -127.9(2) . . . . ? C25 P2 C24 C19 176.8(2) . . . . ? C31 P2 C24 C19 -71.7(3) . . . . ? Au2 P2 C24 C19 53.7(3) . . . . ? C31 P2 C25 C30 -11.7(3) . . . . ? C24 P2 C25 C30 98.3(3) . . . . ? Au2 P2 C25 C30 -137.0(3) . . . . ? C31 P2 C25 C26 169.6(3) . . . . ? C24 P2 C25 C26 -80.4(3) . . . . ? Au2 P2 C25 C26 44.3(3) . . . . ? C30 C25 C26 C27 -2.7(5) . . . . ? P2 C25 C26 C27 176.0(3) . . . . ? C25 C26 C27 C28 1.6(5) . . . . ? C26 C27 C28 C29 1.3(6) . . . . ? C27 C28 C29 C30 -3.0(6) . . . . ? C28 C29 C30 C25 1.7(6) . . . . ? C26 C25 C30 C29 1.1(5) . . . . ? P2 C25 C30 C29 -177.6(3) . . . . ? C25 P2 C31 C32 -99.8(3) . . . . ? C24 P2 C31 C32 149.0(2) . . . . ? Au2 P2 C31 C32 23.7(3) . . . . ? C25 P2 C31 C36 84.2(3) . . . . ? C24 P2 C31 C36 -27.0(3) . . . . ? Au2 P2 C31 C36 -152.3(2) . . . . ? C36 C31 C32 C33 1.0(5) . . . . ? P2 C31 C32 C33 -175.1(2) . . . . ? C31 C32 C33 C34 2.0(5) . . . . ? C32 C33 C34 C35 -2.9(5) . . . . ? C33 C34 C35 C36 0.6(5) . . . . ? C34 C35 C36 C31 2.4(5) . . . . ? C32 C31 C36 C35 -3.2(5) . . . . ? P2 C31 C36 C35 172.8(2) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 35.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.685 _refine_diff_density_min -2.383 _refine_diff_density_rms 0.191 # Attachment 'neda02501.cif.txt' data_neda02501 _database_code_depnum_ccdc_archive 'CCDC 726005' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C36 H26 Au2 Cl2 F2 P2, 0.58(C H2 Cl2), 0.33(C H4 O)' _chemical_formula_sum 'C36.91 H28.48 Au2 Cl3.16 F2 O0.33 P2' _chemical_formula_weight 1083.17 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.57140(10) _cell_length_b 19.3795(3) _cell_length_c 20.7246(4) _cell_angle_alpha 72.6120(10) _cell_angle_beta 80.9120(10) _cell_angle_gamma 82.9700(10) _cell_volume 3610.92(10) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 348564 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 27.485 _exptl_crystal_description needle _exptl_crystal_colour yellow _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.992 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2049.2 _exptl_absorpt_coefficient_mu 8.476 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.489 _exptl_absorpt_correction_T_max 0.721 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 74858 _diffrn_reflns_av_R_equivalents 0.0674 _diffrn_reflns_av_sigmaI/netI 0.0462 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.62 _diffrn_reflns_theta_max 27.00 _reflns_number_total 15753 _reflns_number_gt 12519 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0366P)^2^+18.1009P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 15753 _refine_ls_number_parameters 864 _refine_ls_number_restraints 35 _refine_ls_R_factor_all 0.0563 _refine_ls_R_factor_gt 0.0376 _refine_ls_wR_factor_ref 0.0896 _refine_ls_wR_factor_gt 0.0841 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.57074(2) 0.280015(11) 0.837863(12) 0.01778(6) Uani 1 1 d . . . Au2 Au 0.61960(2) 0.216980(12) 0.744450(13) 0.02128(6) Uani 1 1 d . . . Cl1 Cl 0.48968(16) 0.33250(8) 0.92779(8) 0.0229(3) Uani 1 1 d . . . Cl2 Cl 0.6335(2) 0.15968(10) 0.65757(10) 0.0402(4) Uani 1 1 d . . . P1 P 0.54149(16) 0.16301(8) 0.91045(8) 0.0195(3) Uani 1 1 d . . . P2 P 0.48874(17) 0.31999(9) 0.68465(9) 0.0226(3) Uani 1 1 d . . . F1 F 0.9100(4) 0.1147(2) 0.7207(2) 0.0373(10) Uani 1 1 d . . . F2 F 0.7346(4) 0.41709(19) 0.8343(2) 0.0289(9) Uani 1 1 d . . . C1 C 0.6718(6) 0.1029(3) 0.8764(3) 0.0210(13) Uani 1 1 d . . . C2 C 0.7240(7) 0.0361(3) 0.9182(4) 0.0253(14) Uani 1 1 d . . . H2 H 0.6845 0.0189 0.9646 0.030 Uiso 1 1 calc R . . C3 C 0.8333(7) -0.0039(3) 0.8908(4) 0.0294(15) Uani 1 1 d . . . H3 H 0.8661 -0.0503 0.9175 0.035 Uiso 1 1 calc R . . C4 C 0.8951(7) 0.0233(3) 0.8246(3) 0.0270(15) Uani 1 1 d . . . H4 H 0.9737 -0.0030 0.8063 0.032 Uiso 1 1 calc R . . C5 C 0.8424(7) 0.0888(3) 0.7852(3) 0.0263(14) Uani 1 1 d . . . C6 C 0.7259(7) 0.1297(3) 0.8073(3) 0.0231(14) Uani 1 1 d . . . C7 C 0.5789(6) 0.1502(3) 0.9966(3) 0.0204(13) Uani 1 1 d . . . C8 C 0.7163(7) 0.1636(4) 1.0024(4) 0.0313(16) Uani 1 1 d . . . H8 H 0.7830 0.1789 0.9629 0.038 Uiso 1 1 calc R . . C9 C 0.7530(8) 0.1543(4) 1.0665(4) 0.0390(18) Uani 1 1 d . . . H9 H 0.8457 0.1634 1.0713 0.047 Uiso 1 1 calc R . . C10 C 0.6555(9) 0.1318(4) 1.1238(4) 0.0416(19) Uani 1 1 d . . . H10 H 0.6822 0.1252 1.1676 0.050 Uiso 1 1 calc R . . C11 C 0.5203(9) 0.1188(4) 1.1182(4) 0.0386(18) Uani 1 1 d . . . H11 H 0.4539 0.1036 1.1579 0.046 Uiso 1 1 calc R . . C12 C 0.4812(8) 0.1282(4) 1.0536(4) 0.0310(15) Uani 1 1 d . . . H12 H 0.3881 0.1195 1.0492 0.037 Uiso 1 1 calc R . . C13 C 0.3657(6) 0.1351(3) 0.9158(3) 0.0226(13) Uani 1 1 d . . . C14 C 0.2502(7) 0.1753(3) 0.9415(4) 0.0265(14) Uani 1 1 d . . . H14 H 0.2652 0.2158 0.9556 0.032 Uiso 1 1 calc R . . C15 C 0.1146(7) 0.1555(4) 0.9462(4) 0.0335(16) Uani 1 1 d . . . H15 H 0.0364 0.1826 0.9638 0.040 Uiso 1 1 calc R . . C16 C 0.0907(7) 0.0973(4) 0.9257(4) 0.0356(17) Uani 1 1 d . . . H16 H -0.0032 0.0837 0.9301 0.043 Uiso 1 1 calc R . . C17 C 0.2039(7) 0.0586(4) 0.8986(4) 0.0331(16) Uani 1 1 d . . . H17 H 0.1870 0.0194 0.8830 0.040 Uiso 1 1 calc R . . C18 C 0.3408(7) 0.0764(3) 0.8940(4) 0.0278(15) Uani 1 1 d . . . H18 H 0.4181 0.0489 0.8760 0.033 Uiso 1 1 calc R . . C19 C 0.5610(6) 0.3945(3) 0.7001(3) 0.0226(14) Uani 1 1 d . . . C20 C 0.5806(7) 0.4616(3) 0.6513(4) 0.0285(15) Uani 1 1 d . . . H20 H 0.5462 0.4722 0.6086 0.034 Uiso 1 1 calc R . . C21 C 0.6504(7) 0.5120(3) 0.6661(4) 0.0314(16) Uani 1 1 d . . . H21 H 0.6639 0.5578 0.6335 0.038 Uiso 1 1 calc R . . C22 C 0.7009(7) 0.4964(3) 0.7280(4) 0.0275(15) Uani 1 1 d . . . H22 H 0.7506 0.5308 0.7379 0.033 Uiso 1 1 calc R . . C23 C 0.6785(7) 0.4307(3) 0.7752(3) 0.0240(14) Uani 1 1 d . . . C24 C 0.6070(6) 0.3780(3) 0.7644(3) 0.0221(13) Uani 1 1 d . . . C25 C 0.3007(7) 0.3208(3) 0.7142(3) 0.0241(14) Uani 1 1 d . . . C26 C 0.2154(7) 0.3856(4) 0.7025(4) 0.0363(17) Uani 1 1 d . . . H26 H 0.2572 0.4303 0.6822 0.044 Uiso 1 1 calc R . . C27 C 0.0701(8) 0.3854(4) 0.7203(4) 0.0419(19) Uani 1 1 d . . . H27 H 0.0121 0.4298 0.7123 0.050 Uiso 1 1 calc R . . C28 C 0.0091(8) 0.3195(4) 0.7501(4) 0.0386(18) Uani 1 1 d . . . H28 H -0.0908 0.3191 0.7625 0.046 Uiso 1 1 calc R . . C29 C 0.0924(8) 0.2555(4) 0.7616(4) 0.0369(17) Uani 1 1 d . . . H29 H 0.0503 0.2108 0.7813 0.044 Uiso 1 1 calc R . . C30 C 0.2384(7) 0.2561(4) 0.7444(4) 0.0322(16) Uani 1 1 d . . . H30 H 0.2962 0.2116 0.7534 0.039 Uiso 1 1 calc R . . C31 C 0.5074(7) 0.3350(3) 0.5938(3) 0.0284(15) Uani 1 1 d . . . C32 C 0.3926(8) 0.3323(4) 0.5616(3) 0.0314(16) Uani 1 1 d . . . H32 H 0.3011 0.3259 0.5870 0.038 Uiso 1 1 calc R . . C33 C 0.4113(9) 0.3388(4) 0.4925(4) 0.0421(19) Uani 1 1 d . . . H33 H 0.3323 0.3361 0.4710 0.050 Uiso 1 1 calc R . . C34 C 0.5429(9) 0.3490(4) 0.4544(4) 0.044(2) Uani 1 1 d . . . H34 H 0.5550 0.3537 0.4069 0.053 Uiso 1 1 calc R . . C35 C 0.6581(9) 0.3524(4) 0.4870(4) 0.0418(19) Uani 1 1 d . . . H35 H 0.7492 0.3599 0.4614 0.050 Uiso 1 1 calc R . . C36 C 0.6408(8) 0.3450(4) 0.5557(4) 0.0342(17) Uani 1 1 d . . . H36 H 0.7201 0.3467 0.5774 0.041 Uiso 1 1 calc R . . Au3 Au 0.96564(2) 0.766583(11) 0.780173(12) 0.01774(6) Uani 1 1 d . A . Au4 Au 0.99071(2) 0.687577(12) 0.699629(12) 0.01817(6) Uani 1 1 d . A . Cl3 Cl 0.90501(17) 0.83170(8) 0.86212(8) 0.0262(3) Uani 1 1 d . . . Cl4 Cl 0.96988(18) 0.61252(8) 0.63039(9) 0.0287(4) Uani 1 1 d . . . P3 P 0.94331(16) 0.65646(8) 0.86486(8) 0.0179(3) Uani 1 1 d . . . P4 P 0.85039(17) 0.78406(8) 0.63706(9) 0.0220(3) Uani 1 1 d D . . F3 F 1.2661(4) 0.5780(2) 0.6761(2) 0.0343(9) Uani 1 1 d . . . F4 F 1.1258(4) 0.91421(19) 0.7482(2) 0.0316(9) Uani 1 1 d . . . C37 C 1.0703(6) 0.5915(3) 0.8368(3) 0.0196(13) Uani 1 1 d . A . C38 C 1.1406(7) 0.5346(3) 0.8822(3) 0.0239(14) Uani 1 1 d . . . H38 H 1.1120 0.5242 0.9299 0.029 Uiso 1 1 calc R . . C39 C 1.2522(7) 0.4934(3) 0.8569(4) 0.0258(14) Uani 1 1 d . . . H39 H 1.3004 0.4545 0.8874 0.031 Uiso 1 1 calc R . . C40 C 1.2938(7) 0.5088(3) 0.7874(4) 0.0287(15) Uani 1 1 d . . . H40 H 1.3721 0.4817 0.7698 0.034 Uiso 1 1 calc R . . C41 C 1.2199(7) 0.5641(3) 0.7441(3) 0.0256(14) Uani 1 1 d . A . C42 C 1.1058(6) 0.6077(3) 0.7657(3) 0.0216(13) Uani 1 1 d . . . C43 C 0.9843(6) 0.6574(3) 0.9468(3) 0.0206(13) Uani 1 1 d . . . C44 C 1.1254(6) 0.6659(3) 0.9527(3) 0.0248(14) Uani 1 1 d . . . H44 H 1.1960 0.6706 0.9142 0.030 Uiso 1 1 calc R . . C45 C 1.1617(7) 0.6674(3) 1.0139(4) 0.0279(15) Uani 1 1 d . . . H45 H 1.2575 0.6717 1.0181 0.033 Uiso 1 1 calc R . . C46 C 1.0573(7) 0.6626(3) 1.0698(4) 0.0281(15) Uani 1 1 d . . . H46 H 1.0812 0.6644 1.1120 0.034 Uiso 1 1 calc R . . C47 C 0.9186(7) 0.6552(3) 1.0634(3) 0.0271(15) Uani 1 1 d . . . H47 H 0.8474 0.6520 1.1015 0.033 Uiso 1 1 calc R . . C48 C 0.8821(7) 0.6522(3) 1.0025(3) 0.0224(13) Uani 1 1 d . . . H48 H 0.7866 0.6466 0.9990 0.027 Uiso 1 1 calc R . . C49 C 0.7654(6) 0.6282(3) 0.8797(3) 0.0199(13) Uani 1 1 d . . . C50 C 0.7398(7) 0.5552(3) 0.8928(4) 0.0269(15) Uani 1 1 d . . . H50 H 0.8164 0.5197 0.8901 0.032 Uiso 1 1 calc R . . C51 C 0.6014(7) 0.5356(4) 0.9099(4) 0.0341(17) Uani 1 1 d . . . H51 H 0.5832 0.4864 0.9183 0.041 Uiso 1 1 calc R . . C52 C 0.4887(7) 0.5871(4) 0.9149(4) 0.0333(17) Uani 1 1 d . . . H52 H 0.3943 0.5731 0.9280 0.040 Uiso 1 1 calc R . . C53 C 0.5159(7) 0.6591(4) 0.9007(4) 0.0306(16) Uani 1 1 d . . . H53 H 0.4388 0.6944 0.9035 0.037 Uiso 1 1 calc R . . C54 C 0.6524(7) 0.6808(3) 0.8824(3) 0.0246(14) Uani 1 1 d . . . H54 H 0.6692 0.7305 0.8720 0.030 Uiso 1 1 calc R . . C55 C 0.9117(7) 0.8663(3) 0.6425(3) 0.0272(15) Uani 1 1 d . A . C56 C 0.9025(9) 0.9320(4) 0.5903(4) 0.0414(19) Uani 1 1 d . . . H56 H 0.8536 0.9358 0.5528 0.050 Uiso 1 1 calc R A . C57 C 0.9652(12) 0.9911(4) 0.5941(4) 0.060(3) Uani 1 1 d . A . H57 H 0.9568 1.0361 0.5599 0.072 Uiso 1 1 calc R . . C58 C 1.0403(9) 0.9843(4) 0.6479(4) 0.043(2) Uani 1 1 d . . . H58 H 1.0866 1.0239 0.6504 0.052 Uiso 1 1 calc R A . C59 C 1.0462(7) 0.9195(3) 0.6970(4) 0.0272(15) Uani 1 1 d . A . C60 C 0.9805(6) 0.8591(3) 0.6988(3) 0.0214(13) Uani 1 1 d . . . C61 C 0.8543(7) 0.7937(3) 0.5475(3) 0.0230(13) Uani 1 1 d . A . C62 C 0.9818(8) 0.7818(4) 0.5083(4) 0.0338(16) Uani 1 1 d . . . H62 H 1.0653 0.7655 0.5298 0.041 Uiso 1 1 calc R A . C63 C 0.9896(8) 0.7931(4) 0.4394(4) 0.0371(17) Uani 1 1 d . A . H63 H 1.0780 0.7852 0.4135 0.045 Uiso 1 1 calc R . . C64 C 0.8693(8) 0.8159(4) 0.4078(4) 0.0369(18) Uani 1 1 d . . . H64 H 0.8741 0.8238 0.3601 0.044 Uiso 1 1 calc R A . C65 C 0.7425(9) 0.8271(5) 0.4458(4) 0.045(2) Uani 1 1 d . A . H65 H 0.6595 0.8426 0.4238 0.054 Uiso 1 1 calc R . . C66 C 0.7325(8) 0.8165(4) 0.5153(4) 0.0396(18) Uani 1 1 d . . . H66 H 0.6437 0.8246 0.5408 0.048 Uiso 1 1 calc R A . C67 C 0.6692(10) 0.7799(10) 0.6781(11) 0.024(3) Uani 0.66 1 d PD A 1 C68 C 0.5879(15) 0.8425(8) 0.6876(7) 0.033(3) Uani 0.66 1 d PD A 1 H68 H 0.6280 0.8878 0.6757 0.040 Uiso 0.66 1 calc PR A 1 C69 C 0.4453(14) 0.8354(8) 0.7153(8) 0.050(4) Uani 0.66 1 d PD A 1 H69 H 0.3874 0.8772 0.7208 0.060 Uiso 0.66 1 calc PR A 1 C70 C 0.3865(15) 0.7699(9) 0.7346(10) 0.053(4) Uani 0.66 1 d PD A 1 H70 H 0.2904 0.7666 0.7548 0.063 Uiso 0.66 1 calc PR A 1 C71 C 0.4662(16) 0.7094(8) 0.7246(12) 0.045(4) Uani 0.66 1 d PD A 1 H71 H 0.4252 0.6642 0.7372 0.054 Uiso 0.66 1 calc PR A 1 C72 C 0.6084(16) 0.7144(8) 0.6958(16) 0.034(3) Uani 0.66 1 d PD A 1 H72 H 0.6636 0.6726 0.6883 0.041 Uiso 0.66 1 calc PR A 1 C67A C 0.6671(17) 0.768(2) 0.670(2) 0.024(3) Uani 0.34 1 d PD A 2 C68A C 0.567(3) 0.8263(16) 0.6753(15) 0.033(3) Uani 0.34 1 d PD A 2 H68A H 0.5924 0.8750 0.6593 0.040 Uiso 0.34 1 calc PR A 2 C69A C 0.428(3) 0.8101(16) 0.7055(18) 0.050(4) Uani 0.34 1 d PD A 2 H69A H 0.3595 0.8486 0.7103 0.060 Uiso 0.34 1 calc PR A 2 C70A C 0.390(3) 0.7400(19) 0.728(2) 0.053(4) Uani 0.34 1 d PD A 2 H70A H 0.2946 0.7309 0.7473 0.063 Uiso 0.34 1 calc PR A 2 C71A C 0.486(4) 0.6836(16) 0.724(3) 0.045(4) Uani 0.34 1 d PD A 2 H71A H 0.4591 0.6352 0.7392 0.054 Uiso 0.34 1 calc PR A 2 C72A C 0.627(4) 0.6977(18) 0.695(3) 0.034(3) Uani 0.34 1 d PD A 2 H72A H 0.6954 0.6583 0.6941 0.041 Uiso 0.34 1 calc PR A 2 Cl5 Cl 0.6074(6) 0.0563(4) 0.5207(4) 0.1326(17) Uani 0.66 1 d PD B 1 C1S C 0.683(2) 0.1314(8) 0.4990(10) 0.1326(17) Uani 0.66 1 d PD B 1 H1S1 H 0.6281 0.1622 0.5262 0.159 Uiso 0.66 1 calc PR B 1 H1S2 H 0.7780 0.1195 0.5145 0.159 Uiso 0.66 1 calc PR B 1 Cl6 Cl 0.7057(6) 0.1819(4) 0.4210(4) 0.1326(17) Uani 0.66 1 d PD B 1 Cl7 Cl 0.9908(10) 0.4425(6) 0.5449(6) 0.093(2) Uani 0.40 1 d PD . 1 C2S C 0.920(3) 0.5163(8) 0.4815(15) 0.093(2) Uani 0.40 1 d PD C 1 H2S1 H 0.9259 0.4995 0.4404 0.111 Uiso 0.40 1 calc PR C 1 H2S2 H 0.8182 0.5238 0.4976 0.111 Uiso 0.40 1 calc PR C 1 Cl8 Cl 0.9871(10) 0.6032(6) 0.4535(6) 0.093(2) Uani 0.40 1 d PD . 1 Cl7A Cl 1.175(3) 0.492(2) 0.517(2) 0.093(2) Uani 0.10 1 d PD . 2 C2T C 0.993(3) 0.489(8) 0.551(3) 0.093(2) Uani 0.10 1 d PD D 2 H2T1 H 0.9760 0.4384 0.5769 0.111 Uiso 0.10 1 calc PR D 2 H2T2 H 0.9760 0.5174 0.5851 0.111 Uiso 0.10 1 calc PR D 2 Cl8A Cl 0.861(3) 0.522(2) 0.496(2) 0.093(2) Uani 0.10 1 d PD . 2 O1 O 0.5052(13) 0.9888(7) 0.2630(7) 0.090(3) Uani 0.66 1 d P E 1 H1 H 0.4850 0.9797 0.2285 0.135 Uiso 0.66 1 calc PR E 1 C3S C 0.646(2) 0.9576(10) 0.2757(10) 0.090(3) Uani 0.66 1 d PU E 1 H3S1 H 0.6680 0.9661 0.3172 0.135 Uiso 0.66 1 calc PR E 1 H3S2 H 0.7149 0.9801 0.2371 0.135 Uiso 0.66 1 calc PR E 1 H3S3 H 0.6517 0.9053 0.2816 0.135 Uiso 0.66 1 calc PR E 1 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01633(12) 0.01373(11) 0.02288(13) -0.00601(9) -0.00173(9) 0.00132(8) Au2 0.02215(13) 0.01755(11) 0.02382(13) -0.00792(10) -0.00105(10) 0.00229(9) Cl1 0.0231(8) 0.0189(7) 0.0275(8) -0.0103(6) -0.0033(6) 0.0043(6) Cl2 0.0561(12) 0.0348(9) 0.0350(10) -0.0197(8) -0.0077(9) 0.0036(8) P1 0.0179(8) 0.0145(7) 0.0248(9) -0.0060(6) -0.0001(6) 0.0006(6) P2 0.0216(8) 0.0213(8) 0.0242(9) -0.0068(7) -0.0027(7) 0.0018(6) F1 0.039(2) 0.028(2) 0.034(2) -0.0056(18) 0.0100(19) 0.0107(17) F2 0.028(2) 0.0228(18) 0.037(2) -0.0066(17) -0.0102(17) -0.0027(15) C1 0.016(3) 0.016(3) 0.032(4) -0.011(3) 0.000(3) -0.002(2) C2 0.027(3) 0.016(3) 0.033(4) -0.006(3) -0.005(3) -0.003(2) C3 0.033(4) 0.017(3) 0.042(4) -0.010(3) -0.010(3) 0.000(3) C4 0.026(3) 0.027(3) 0.031(4) -0.017(3) -0.005(3) 0.007(3) C5 0.026(3) 0.022(3) 0.030(4) -0.013(3) 0.004(3) 0.005(3) C6 0.027(3) 0.015(3) 0.025(3) -0.006(3) -0.003(3) 0.001(2) C7 0.022(3) 0.010(3) 0.031(4) -0.010(2) -0.006(3) 0.005(2) C8 0.028(4) 0.029(4) 0.039(4) -0.010(3) -0.009(3) 0.000(3) C9 0.039(4) 0.035(4) 0.051(5) -0.021(4) -0.022(4) 0.008(3) C10 0.052(5) 0.037(4) 0.039(5) -0.013(4) -0.020(4) 0.006(4) C11 0.050(5) 0.037(4) 0.029(4) -0.011(3) -0.003(4) -0.002(3) C12 0.032(4) 0.029(4) 0.031(4) -0.008(3) -0.004(3) -0.001(3) C13 0.021(3) 0.019(3) 0.026(3) -0.004(3) 0.000(3) -0.003(2) C14 0.022(3) 0.025(3) 0.034(4) -0.011(3) -0.004(3) -0.002(3) C15 0.023(4) 0.035(4) 0.042(4) -0.014(3) -0.001(3) 0.002(3) C16 0.024(4) 0.027(4) 0.055(5) -0.007(3) -0.010(3) -0.007(3) C17 0.033(4) 0.026(3) 0.045(5) -0.013(3) -0.014(3) -0.006(3) C18 0.030(4) 0.022(3) 0.034(4) -0.011(3) -0.007(3) 0.000(3) C19 0.021(3) 0.014(3) 0.028(4) -0.002(3) 0.001(3) 0.006(2) C20 0.029(4) 0.025(3) 0.028(4) -0.004(3) -0.002(3) 0.002(3) C21 0.032(4) 0.019(3) 0.036(4) 0.000(3) 0.001(3) -0.003(3) C22 0.025(3) 0.020(3) 0.036(4) -0.007(3) 0.000(3) -0.001(3) C23 0.025(3) 0.019(3) 0.028(4) -0.008(3) -0.004(3) 0.004(2) C24 0.014(3) 0.018(3) 0.029(4) -0.004(3) 0.001(3) 0.006(2) C25 0.023(3) 0.028(3) 0.026(4) -0.015(3) -0.007(3) 0.004(3) C26 0.023(4) 0.036(4) 0.052(5) -0.018(4) -0.008(3) 0.006(3) C27 0.027(4) 0.044(4) 0.057(5) -0.025(4) -0.001(4) 0.006(3) C28 0.026(4) 0.059(5) 0.034(4) -0.022(4) 0.002(3) -0.002(3) C29 0.035(4) 0.042(4) 0.037(4) -0.012(3) -0.005(3) -0.009(3) C30 0.031(4) 0.029(4) 0.035(4) -0.010(3) -0.005(3) 0.003(3) C31 0.034(4) 0.024(3) 0.025(4) -0.006(3) -0.002(3) 0.001(3) C32 0.034(4) 0.042(4) 0.021(4) -0.012(3) -0.002(3) -0.007(3) C33 0.050(5) 0.048(5) 0.029(4) -0.009(4) -0.010(4) -0.005(4) C34 0.062(6) 0.046(5) 0.025(4) -0.010(4) -0.001(4) -0.011(4) C35 0.045(5) 0.046(5) 0.028(4) -0.008(4) 0.005(4) 0.000(4) C36 0.031(4) 0.040(4) 0.027(4) -0.007(3) 0.000(3) 0.002(3) Au3 0.01628(11) 0.01312(10) 0.02338(13) -0.00606(9) -0.00148(9) 0.00131(8) Au4 0.01717(12) 0.01468(11) 0.02232(13) -0.00626(9) -0.00111(9) 0.00067(8) Cl3 0.0327(8) 0.0167(7) 0.0302(9) -0.0112(6) -0.0007(7) 0.0010(6) Cl4 0.0354(9) 0.0238(8) 0.0308(9) -0.0141(7) -0.0025(7) -0.0031(7) P3 0.0150(7) 0.0142(7) 0.0236(8) -0.0060(6) -0.0006(6) 0.0014(6) P4 0.0207(8) 0.0185(7) 0.0239(9) -0.0036(7) -0.0028(7) 0.0024(6) F3 0.033(2) 0.037(2) 0.028(2) -0.0095(18) 0.0029(17) 0.0099(17) F4 0.031(2) 0.0232(19) 0.041(2) -0.0126(17) 0.0040(18) -0.0075(16) C37 0.018(3) 0.017(3) 0.026(3) -0.008(3) -0.003(3) 0.001(2) C38 0.027(3) 0.017(3) 0.028(4) -0.004(3) -0.007(3) 0.001(2) C39 0.024(3) 0.012(3) 0.039(4) -0.004(3) -0.008(3) 0.004(2) C40 0.022(3) 0.020(3) 0.043(4) -0.012(3) 0.000(3) 0.005(3) C41 0.026(3) 0.021(3) 0.028(4) -0.010(3) 0.001(3) 0.006(3) C42 0.020(3) 0.017(3) 0.028(4) -0.007(3) -0.001(3) 0.000(2) C43 0.023(3) 0.014(3) 0.026(3) -0.006(2) -0.007(3) 0.000(2) C44 0.013(3) 0.032(3) 0.027(4) -0.009(3) 0.003(3) 0.000(3) C45 0.020(3) 0.026(3) 0.042(4) -0.013(3) -0.011(3) 0.000(3) C46 0.038(4) 0.020(3) 0.027(4) -0.007(3) -0.010(3) 0.000(3) C47 0.028(4) 0.027(3) 0.025(4) -0.010(3) 0.002(3) 0.002(3) C48 0.022(3) 0.020(3) 0.023(3) -0.003(3) -0.001(3) -0.001(2) C49 0.015(3) 0.023(3) 0.023(3) -0.011(3) 0.001(2) -0.001(2) C50 0.026(3) 0.016(3) 0.037(4) -0.007(3) 0.000(3) 0.001(2) C51 0.033(4) 0.027(3) 0.048(5) -0.018(3) 0.002(3) -0.014(3) C52 0.020(3) 0.035(4) 0.049(5) -0.018(3) -0.002(3) -0.006(3) C53 0.014(3) 0.034(4) 0.043(4) -0.015(3) -0.001(3) 0.004(3) C54 0.023(3) 0.026(3) 0.025(4) -0.009(3) 0.002(3) -0.006(3) C55 0.033(4) 0.016(3) 0.029(4) -0.006(3) 0.004(3) 0.003(3) C56 0.075(6) 0.021(3) 0.028(4) -0.003(3) -0.016(4) 0.000(4) C57 0.120(9) 0.020(4) 0.034(5) 0.002(3) -0.007(5) -0.009(4) C58 0.075(6) 0.017(3) 0.036(5) -0.007(3) 0.008(4) -0.014(3) C59 0.033(4) 0.019(3) 0.029(4) -0.010(3) 0.003(3) 0.000(3) C60 0.016(3) 0.016(3) 0.029(4) -0.005(3) 0.001(3) 0.000(2) C61 0.026(3) 0.023(3) 0.019(3) -0.004(3) -0.003(3) 0.000(3) C62 0.032(4) 0.040(4) 0.026(4) -0.008(3) -0.003(3) 0.002(3) C63 0.039(4) 0.041(4) 0.027(4) -0.011(3) 0.004(3) 0.001(3) C64 0.054(5) 0.032(4) 0.025(4) -0.006(3) -0.004(4) -0.012(3) C65 0.038(4) 0.066(6) 0.026(4) 0.000(4) -0.013(3) -0.003(4) C66 0.033(4) 0.051(5) 0.030(4) -0.004(4) -0.003(3) -0.004(3) C67 0.024(4) 0.038(7) 0.013(6) -0.012(4) -0.002(3) 0.001(3) C68 0.036(6) 0.036(8) 0.032(7) -0.019(5) -0.003(5) 0.004(5) C69 0.035(6) 0.066(11) 0.053(8) -0.034(7) -0.002(5) 0.020(7) C70 0.025(5) 0.075(15) 0.053(8) -0.020(10) 0.010(5) -0.005(8) C71 0.025(7) 0.059(11) 0.049(6) -0.015(10) 0.002(6) -0.007(9) C72 0.020(5) 0.043(9) 0.038(5) -0.013(8) 0.000(5) 0.003(5) C67A 0.024(4) 0.038(7) 0.013(6) -0.012(4) -0.002(3) 0.001(3) C68A 0.036(6) 0.036(8) 0.032(7) -0.019(5) -0.003(5) 0.004(5) C69A 0.035(6) 0.066(11) 0.053(8) -0.034(7) -0.002(5) 0.020(7) C70A 0.025(5) 0.075(15) 0.053(8) -0.020(10) 0.010(5) -0.005(8) C71A 0.025(7) 0.059(11) 0.049(6) -0.015(10) 0.002(6) -0.007(9) C72A 0.020(5) 0.043(9) 0.038(5) -0.013(8) 0.000(5) 0.003(5) Cl5 0.088(3) 0.152(4) 0.180(5) -0.069(4) -0.067(3) 0.023(3) C1S 0.088(3) 0.152(4) 0.180(5) -0.069(4) -0.067(3) 0.023(3) Cl6 0.088(3) 0.152(4) 0.180(5) -0.069(4) -0.067(3) 0.023(3) Cl7 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) C2S 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) Cl8 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) Cl7A 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) C2T 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) Cl8A 0.072(4) 0.120(6) 0.109(4) -0.065(5) -0.021(3) -0.003(5) O1 0.090(5) 0.075(4) 0.098(5) -0.003(4) -0.019(4) -0.023(4) C3S 0.090(5) 0.075(4) 0.098(5) -0.003(4) -0.019(4) -0.023(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.075(6) . ? Au1 P1 2.3381(15) . ? Au1 Cl1 2.3650(15) . ? Au1 Au2 2.5390(3) . ? Au2 C6 2.067(6) . ? Au2 P2 2.3429(16) . ? Au2 Cl2 2.3612(18) . ? P1 C13 1.806(6) . ? P1 C1 1.808(6) . ? P1 C7 1.814(7) . ? P2 C31 1.800(7) . ? P2 C19 1.805(7) . ? P2 C25 1.807(7) . ? F1 C5 1.364(7) . ? F2 C23 1.355(7) . ? C1 C6 1.406(9) . ? C1 C2 1.408(8) . ? C2 C3 1.376(9) . ? C2 H2 0.9500 . ? C3 C4 1.378(10) . ? C3 H3 0.9500 . ? C4 C5 1.373(9) . ? C4 H4 0.9500 . ? C5 C6 1.387(8) . ? C7 C12 1.378(9) . ? C7 C8 1.402(9) . ? C8 C9 1.383(10) . ? C8 H8 0.9500 . ? C9 C10 1.382(11) . ? C9 H9 0.9500 . ? C10 C11 1.377(11) . ? C10 H10 0.9500 . ? C11 C12 1.400(10) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.401(9) . ? C13 C18 1.403(9) . ? C14 C15 1.379(9) . ? C14 H14 0.9500 . ? C15 C16 1.374(10) . ? C15 H15 0.9500 . ? C16 C17 1.382(10) . ? C16 H16 0.9500 . ? C17 C18 1.377(9) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.400(9) . ? C19 C24 1.404(9) . ? C20 C21 1.378(10) . ? C20 H20 0.9500 . ? C21 C22 1.378(10) . ? C21 H21 0.9500 . ? C22 C23 1.371(9) . ? C22 H22 0.9500 . ? C23 C24 1.385(9) . ? C25 C30 1.385(9) . ? C25 C26 1.389(9) . ? C26 C27 1.381(10) . ? C26 H26 0.9500 . ? C27 C28 1.396(11) . ? C27 H27 0.9500 . ? C28 C29 1.368(11) . ? C28 H28 0.9500 . ? C29 C30 1.387(10) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C32 1.386(10) . ? C31 C36 1.393(10) . ? C32 C33 1.383(10) . ? C32 H32 0.9500 . ? C33 C34 1.380(11) . ? C33 H33 0.9500 . ? C34 C35 1.398(11) . ? C34 H34 0.9500 . ? C35 C36 1.373(10) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? Au3 C60 2.064(6) . ? Au3 P3 2.3313(15) . ? Au3 Cl3 2.3673(15) . ? Au3 Au4 2.5494(3) . ? Au4 C42 2.068(6) . ? Au4 P4 2.3383(16) . ? Au4 Cl4 2.3715(16) . ? P3 C37 1.799(6) . ? P3 C49 1.804(6) . ? P3 C43 1.809(7) . ? P4 C55 1.803(7) . ? P4 C61 1.805(7) . ? P4 C67 1.806(7) . ? P4 C67A 1.806(7) . ? F3 C41 1.364(7) . ? F4 C59 1.374(8) . ? C37 C38 1.398(8) . ? C37 C42 1.407(9) . ? C38 C39 1.384(9) . ? C38 H38 0.9500 . ? C39 C40 1.384(10) . ? C39 H39 0.9500 . ? C40 C41 1.376(9) . ? C40 H40 0.9500 . ? C41 C42 1.398(8) . ? C43 C48 1.377(9) . ? C43 C44 1.409(8) . ? C44 C45 1.377(9) . ? C44 H44 0.9500 . ? C45 C46 1.393(10) . ? C45 H45 0.9500 . ? C46 C47 1.384(9) . ? C46 H46 0.9500 . ? C47 C48 1.381(9) . ? C47 H47 0.9500 . ? C48 H48 0.9500 . ? C49 C54 1.399(8) . ? C49 C50 1.403(8) . ? C50 C51 1.386(9) . ? C50 H50 0.9500 . ? C51 C52 1.390(10) . ? C51 H51 0.9500 . ? C52 C53 1.385(9) . ? C52 H52 0.9500 . ? C53 C54 1.382(9) . ? C53 H53 0.9500 . ? C54 H54 0.9500 . ? C55 C60 1.393(9) . ? C55 C56 1.406(9) . ? C56 C57 1.383(11) . ? C56 H56 0.9500 . ? C57 C58 1.385(12) . ? C57 H57 0.9500 . ? C58 C59 1.361(9) . ? C58 H58 0.9500 . ? C59 C60 1.383(9) . ? C61 C62 1.390(9) . ? C61 C66 1.394(10) . ? C62 C63 1.370(10) . ? C62 H62 0.9500 . ? C63 C64 1.375(11) . ? C63 H63 0.9500 . ? C64 C65 1.369(11) . ? C64 H64 0.9500 . ? C65 C66 1.382(10) . ? C65 H65 0.9500 . ? C66 H66 0.9500 . ? C67 C72 1.387(13) . ? C67 C68 1.407(12) . ? C68 C69 1.400(14) . ? C68 H68 0.9500 . ? C69 C70 1.374(18) . ? C69 H69 0.9500 . ? C70 C71 1.370(17) . ? C70 H70 0.9500 . ? C71 C72 1.400(13) . ? C71 H71 0.9500 . ? C72 H72 0.9500 . ? C67A C72A 1.388(18) . ? C67A C68A 1.408(17) . ? C68A C69A 1.404(19) . ? C68A H68A 0.9500 . ? C69A C70A 1.37(2) . ? C69A H69A 0.9500 . ? C70A C71A 1.36(2) . ? C70A H70A 0.9500 . ? C71A C72A 1.402(17) . ? C71A H71A 0.9500 . ? C72A H72A 0.9500 . ? Cl5 C1S 1.616(12) . ? C1S Cl6 1.616(12) . ? C1S H1S1 0.9900 . ? C1S H1S2 0.9900 . ? Cl7 C2S 1.774(15) . ? C2S Cl8 1.774(15) . ? C2S H2S1 0.9900 . ? C2S H2S2 0.9900 . ? Cl7A C2T 1.774(15) . ? C2T Cl8A 1.774(15) . ? C2T H2T1 0.9900 . ? C2T H2T2 0.9900 . ? O1 C3S 1.44(2) . ? O1 H1 0.8400 . ? C3S H3S1 0.9800 . ? C3S H3S2 0.9800 . ? C3S H3S3 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 P1 173.13(18) . . ? C24 Au1 Cl1 95.01(18) . . ? P1 Au1 Cl1 91.84(5) . . ? C24 Au1 Au2 89.07(18) . . ? P1 Au1 Au2 84.22(4) . . ? Cl1 Au1 Au2 171.15(4) . . ? C6 Au2 P2 173.31(18) . . ? C6 Au2 Cl2 93.33(18) . . ? P2 Au2 Cl2 92.93(6) . . ? C6 Au2 Au1 90.62(17) . . ? P2 Au2 Au1 82.91(4) . . ? Cl2 Au2 Au1 172.73(5) . . ? C13 P1 C1 109.8(3) . . ? C13 P1 C7 107.9(3) . . ? C1 P1 C7 105.4(3) . . ? C13 P1 Au1 112.7(2) . . ? C1 P1 Au1 106.6(2) . . ? C7 P1 Au1 114.27(19) . . ? C31 P2 C19 107.6(3) . . ? C31 P2 C25 106.7(3) . . ? C19 P2 C25 109.7(3) . . ? C31 P2 Au2 115.2(2) . . ? C19 P2 Au2 104.0(2) . . ? C25 P2 Au2 113.3(2) . . ? C6 C1 C2 122.3(6) . . ? C6 C1 P1 115.7(4) . . ? C2 C1 P1 121.7(5) . . ? C3 C2 C1 119.0(6) . . ? C3 C2 H2 120.5 . . ? C1 C2 H2 120.5 . . ? C2 C3 C4 120.0(6) . . ? C2 C3 H3 120.0 . . ? C4 C3 H3 120.0 . . ? C5 C4 C3 119.6(6) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? F1 C5 C4 117.5(5) . . ? F1 C5 C6 118.7(6) . . ? C4 C5 C6 123.8(6) . . ? C5 C6 C1 114.9(6) . . ? C5 C6 Au2 124.6(5) . . ? C1 C6 Au2 120.1(4) . . ? C12 C7 C8 120.9(6) . . ? C12 C7 P1 123.5(5) . . ? C8 C7 P1 115.6(5) . . ? C9 C8 C7 118.9(7) . . ? C9 C8 H8 120.5 . . ? C7 C8 H8 120.5 . . ? C10 C9 C8 120.2(7) . . ? C10 C9 H9 119.9 . . ? C8 C9 H9 119.9 . . ? C11 C10 C9 121.0(7) . . ? C11 C10 H10 119.5 . . ? C9 C10 H10 119.5 . . ? C10 C11 C12 119.5(7) . . ? C10 C11 H11 120.2 . . ? C12 C11 H11 120.2 . . ? C7 C12 C11 119.4(7) . . ? C7 C12 H12 120.3 . . ? C11 C12 H12 120.3 . . ? C14 C13 C18 119.2(6) . . ? C14 C13 P1 118.1(5) . . ? C18 C13 P1 122.7(5) . . ? C15 C14 C13 119.5(6) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C16 C15 C14 121.1(6) . . ? C16 C15 H15 119.5 . . ? C14 C15 H15 119.5 . . ? C15 C16 C17 119.6(6) . . ? C15 C16 H16 120.2 . . ? C17 C16 H16 120.2 . . ? C18 C17 C16 120.7(6) . . ? C18 C17 H17 119.6 . . ? C16 C17 H17 119.6 . . ? C17 C18 C13 119.7(6) . . ? C17 C18 H18 120.1 . . ? C13 C18 H18 120.1 . . ? C20 C19 C24 121.8(6) . . ? C20 C19 P2 124.1(5) . . ? C24 C19 P2 114.0(4) . . ? C21 C20 C19 119.2(7) . . ? C21 C20 H20 120.4 . . ? C19 C20 H20 120.4 . . ? C22 C21 C20 120.3(6) . . ? C22 C21 H21 119.9 . . ? C20 C21 H21 119.9 . . ? C23 C22 C21 119.3(6) . . ? C23 C22 H22 120.3 . . ? C21 C22 H22 120.3 . . ? F2 C23 C22 116.9(6) . . ? F2 C23 C24 119.5(5) . . ? C22 C23 C24 123.6(6) . . ? C23 C24 C19 115.8(6) . . ? C23 C24 Au1 122.6(5) . . ? C19 C24 Au1 121.6(5) . . ? C30 C25 C26 119.2(6) . . ? C30 C25 P2 119.9(5) . . ? C26 C25 P2 120.7(5) . . ? C27 C26 C25 120.5(7) . . ? C27 C26 H26 119.7 . . ? C25 C26 H26 119.7 . . ? C26 C27 C28 119.5(7) . . ? C26 C27 H27 120.3 . . ? C28 C27 H27 120.3 . . ? C29 C28 C27 120.4(7) . . ? C29 C28 H28 119.8 . . ? C27 C28 H28 119.8 . . ? C28 C29 C30 119.9(7) . . ? C28 C29 H29 120.1 . . ? C30 C29 H29 120.1 . . ? C25 C30 C29 120.6(6) . . ? C25 C30 H30 119.7 . . ? C29 C30 H30 119.7 . . ? C32 C31 C36 119.2(7) . . ? C32 C31 P2 121.0(5) . . ? C36 C31 P2 119.6(6) . . ? C33 C32 C31 120.1(7) . . ? C33 C32 H32 119.9 . . ? C31 C32 H32 119.9 . . ? C34 C33 C32 121.0(8) . . ? C34 C33 H33 119.5 . . ? C32 C33 H33 119.5 . . ? C33 C34 C35 118.7(7) . . ? C33 C34 H34 120.7 . . ? C35 C34 H34 120.7 . . ? C36 C35 C34 120.7(7) . . ? C36 C35 H35 119.7 . . ? C34 C35 H35 119.7 . . ? C35 C36 C31 120.3(7) . . ? C35 C36 H36 119.8 . . ? C31 C36 H36 119.8 . . ? C60 Au3 P3 174.47(18) . . ? C60 Au3 Cl3 93.77(18) . . ? P3 Au3 Cl3 91.14(5) . . ? C60 Au3 Au4 91.04(17) . . ? P3 Au3 Au4 83.74(4) . . ? Cl3 Au3 Au4 170.35(4) . . ? C42 Au4 P4 172.48(18) . . ? C42 Au4 Cl4 93.67(17) . . ? P4 Au4 Cl4 93.00(6) . . ? C42 Au4 Au3 90.06(17) . . ? P4 Au4 Au3 82.79(4) . . ? Cl4 Au4 Au3 169.78(4) . . ? C37 P3 C49 111.4(3) . . ? C37 P3 C43 106.9(3) . . ? C49 P3 C43 106.0(3) . . ? C37 P3 Au3 106.5(2) . . ? C49 P3 Au3 111.8(2) . . ? C43 P3 Au3 114.26(19) . . ? C55 P4 C61 106.4(3) . . ? C55 P4 C67 106.8(5) . . ? C61 P4 C67 109.6(7) . . ? C55 P4 C67A 116.8(11) . . ? C61 P4 C67A 102.2(15) . . ? C55 P4 Au4 106.8(2) . . ? C61 P4 Au4 117.7(2) . . ? C67 P4 Au4 109.0(7) . . ? C67A P4 Au4 107.5(15) . . ? C38 C37 C42 122.5(6) . . ? C38 C37 P3 122.4(5) . . ? C42 C37 P3 114.7(4) . . ? C39 C38 C37 119.4(6) . . ? C39 C38 H38 120.3 . . ? C37 C38 H38 120.3 . . ? C40 C39 C38 120.1(6) . . ? C40 C39 H39 119.9 . . ? C38 C39 H39 119.9 . . ? C41 C40 C39 118.9(6) . . ? C41 C40 H40 120.5 . . ? C39 C40 H40 120.5 . . ? F3 C41 C40 116.9(5) . . ? F3 C41 C42 118.9(6) . . ? C40 C41 C42 124.2(6) . . ? C41 C42 C37 114.8(6) . . ? C41 C42 Au4 123.6(5) . . ? C37 C42 Au4 121.6(4) . . ? C48 C43 C44 119.4(6) . . ? C48 C43 P3 122.3(5) . . ? C44 C43 P3 118.2(5) . . ? C45 C44 C43 120.4(6) . . ? C45 C44 H44 119.8 . . ? C43 C44 H44 119.8 . . ? C44 C45 C46 119.7(6) . . ? C44 C45 H45 120.2 . . ? C46 C45 H45 120.2 . . ? C47 C46 C45 119.6(6) . . ? C47 C46 H46 120.2 . . ? C45 C46 H46 120.2 . . ? C48 C47 C46 121.0(6) . . ? C48 C47 H47 119.5 . . ? C46 C47 H47 119.5 . . ? C43 C48 C47 119.9(6) . . ? C43 C48 H48 120.1 . . ? C47 C48 H48 120.1 . . ? C54 C49 C50 120.4(6) . . ? C54 C49 P3 117.8(5) . . ? C50 C49 P3 121.6(5) . . ? C51 C50 C49 119.2(6) . . ? C51 C50 H50 120.4 . . ? C49 C50 H50 120.4 . . ? C50 C51 C52 120.8(6) . . ? C50 C51 H51 119.6 . . ? C52 C51 H51 119.6 . . ? C53 C52 C51 119.2(6) . . ? C53 C52 H52 120.4 . . ? C51 C52 H52 120.4 . . ? C54 C53 C52 121.6(6) . . ? C54 C53 H53 119.2 . . ? C52 C53 H53 119.2 . . ? C53 C54 C49 118.8(6) . . ? C53 C54 H54 120.6 . . ? C49 C54 H54 120.6 . . ? C60 C55 C56 121.7(6) . . ? C60 C55 P4 115.6(5) . . ? C56 C55 P4 122.4(6) . . ? C57 C56 C55 119.5(7) . . ? C57 C56 H56 120.2 . . ? C55 C56 H56 120.2 . . ? C56 C57 C58 119.8(7) . . ? C56 C57 H57 120.1 . . ? C58 C57 H57 120.1 . . ? C59 C58 C57 118.4(7) . . ? C59 C58 H58 120.8 . . ? C57 C58 H58 120.8 . . ? C58 C59 F4 116.6(6) . . ? C58 C59 C60 125.3(7) . . ? F4 C59 C60 118.1(6) . . ? C59 C60 C55 115.0(6) . . ? C59 C60 Au3 124.8(5) . . ? C55 C60 Au3 119.9(4) . . ? C62 C61 C66 118.5(6) . . ? C62 C61 P4 120.0(5) . . ? C66 C61 P4 121.4(5) . . ? C63 C62 C61 121.3(7) . . ? C63 C62 H62 119.3 . . ? C61 C62 H62 119.3 . . ? C62 C63 C64 120.0(7) . . ? C62 C63 H63 120.0 . . ? C64 C63 H63 120.0 . . ? C65 C64 C63 119.5(7) . . ? C65 C64 H64 120.3 . . ? C63 C64 H64 120.3 . . ? C64 C65 C66 121.5(7) . . ? C64 C65 H65 119.2 . . ? C66 C65 H65 119.2 . . ? C65 C66 C61 119.2(7) . . ? C65 C66 H66 120.4 . . ? C61 C66 H66 120.4 . . ? C72 C67 C68 120.3(9) . . ? C72 C67 P4 118.3(11) . . ? C68 C67 P4 121.2(11) . . ? C69 C68 C67 117.4(10) . . ? C69 C68 H68 121.3 . . ? C67 C68 H68 121.3 . . ? C70 C69 C68 122.1(11) . . ? C70 C69 H69 119.0 . . ? C68 C69 H69 119.0 . . ? C71 C70 C69 120.1(11) . . ? C71 C70 H70 119.9 . . ? C69 C70 H70 120.0 . . ? C70 C71 C72 119.6(12) . . ? C70 C71 H71 120.2 . . ? C72 C71 H71 120.2 . . ? C67 C72 C71 120.4(11) . . ? C67 C72 H72 119.8 . . ? C71 C72 H72 119.8 . . ? C72A C67A C68A 119.2(16) . . ? C72A C67A P4 120(2) . . ? C68A C67A P4 120(2) . . ? C69A C68A C67A 117.9(18) . . ? C69A C68A H68A 121.1 . . ? C67A C68A H68A 121.0 . . ? C70A C69A C68A 122(2) . . ? C70A C69A H69A 119.2 . . ? C68A C69A H69A 119.2 . . ? C71A C70A C69A 121(2) . . ? C71A C70A H70A 119.6 . . ? C69A C70A H70A 119.6 . . ? C70A C71A C72A 119(2) . . ? C70A C71A H71A 120.5 . . ? C72A C71A H71A 120.5 . . ? C67A C72A C71A 121(2) . . ? C67A C72A H72A 119.3 . . ? C71A C72A H72A 119.3 . . ? Cl6 C1S Cl5 122.4(16) . . ? Cl6 C1S H1S1 106.7 . . ? Cl5 C1S H1S1 106.7 . . ? Cl6 C1S H1S2 106.7 . . ? Cl5 C1S H1S2 106.7 . . ? H1S1 C1S H1S2 106.6 . . ? Cl8 C2S Cl7 123.5(19) . . ? Cl8 C2S H2S1 106.5 . . ? Cl7 C2S H2S1 106.5 . . ? Cl8 C2S H2S2 106.5 . . ? Cl7 C2S H2S2 106.5 . . ? H2S1 C2S H2S2 106.5 . . ? Cl8A C2T Cl7A 120(3) . . ? Cl8A C2T H2T1 107.4 . . ? Cl7A C2T H2T1 107.4 . . ? Cl8A C2T H2T2 107.4 . . ? Cl7A C2T H2T2 107.4 . . ? H2T1 C2T H2T2 106.9 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 141.1(2) . . . . ? P1 Au1 Au2 C6 -37.39(18) . . . . ? C24 Au1 Au2 P2 -40.55(17) . . . . ? P1 Au1 Au2 P2 140.92(6) . . . . ? Cl1 Au1 P1 C13 88.8(2) . . . . ? Au2 Au1 P1 C13 -83.2(2) . . . . ? Cl1 Au1 P1 C1 -150.7(2) . . . . ? Au2 Au1 P1 C1 37.2(2) . . . . ? Cl1 Au1 P1 C7 -34.8(2) . . . . ? Au2 Au1 P1 C7 153.2(2) . . . . ? Cl2 Au2 P2 C31 -22.8(3) . . . . ? Au1 Au2 P2 C31 163.2(3) . . . . ? Cl2 Au2 P2 C19 -140.3(2) . . . . ? Au1 Au2 P2 C19 45.7(2) . . . . ? Cl2 Au2 P2 C25 100.6(2) . . . . ? Au1 Au2 P2 C25 -73.5(2) . . . . ? C13 P1 C1 C6 101.9(5) . . . . ? C7 P1 C1 C6 -142.2(5) . . . . ? Au1 P1 C1 C6 -20.4(5) . . . . ? C13 P1 C1 C2 -83.3(6) . . . . ? C7 P1 C1 C2 32.6(6) . . . . ? Au1 P1 C1 C2 154.4(5) . . . . ? C6 C1 C2 C3 0.9(9) . . . . ? P1 C1 C2 C3 -173.5(5) . . . . ? C1 C2 C3 C4 3.6(10) . . . . ? C2 C3 C4 C5 -3.3(10) . . . . ? C3 C4 C5 F1 177.8(6) . . . . ? C3 C4 C5 C6 -1.7(11) . . . . ? F1 C5 C6 C1 -173.7(6) . . . . ? C4 C5 C6 C1 5.9(10) . . . . ? F1 C5 C6 Au2 13.4(9) . . . . ? C4 C5 C6 Au2 -167.0(5) . . . . ? C2 C1 C6 C5 -5.5(9) . . . . ? P1 C1 C6 C5 169.3(5) . . . . ? C2 C1 C6 Au2 167.8(5) . . . . ? P1 C1 C6 Au2 -17.4(7) . . . . ? Cl2 Au2 C6 C5 40.3(6) . . . . ? Au1 Au2 C6 C5 -145.8(6) . . . . ? Cl2 Au2 C6 C1 -132.3(5) . . . . ? Au1 Au2 C6 C1 41.6(5) . . . . ? C13 P1 C7 C12 -4.6(6) . . . . ? C1 P1 C7 C12 -121.8(5) . . . . ? Au1 P1 C7 C12 121.5(5) . . . . ? C13 P1 C7 C8 175.0(4) . . . . ? C1 P1 C7 C8 57.8(5) . . . . ? Au1 P1 C7 C8 -58.9(5) . . . . ? C12 C7 C8 C9 0.2(9) . . . . ? P1 C7 C8 C9 -179.4(5) . . . . ? C7 C8 C9 C10 0.2(10) . . . . ? C8 C9 C10 C11 -0.5(11) . . . . ? C9 C10 C11 C12 0.3(11) . . . . ? C8 C7 C12 C11 -0.4(10) . . . . ? P1 C7 C12 C11 179.2(5) . . . . ? C10 C11 C12 C7 0.1(10) . . . . ? C1 P1 C13 C14 179.7(5) . . . . ? C7 P1 C13 C14 65.4(6) . . . . ? Au1 P1 C13 C14 -61.7(6) . . . . ? C1 P1 C13 C18 -1.8(7) . . . . ? C7 P1 C13 C18 -116.1(6) . . . . ? Au1 P1 C13 C18 116.8(5) . . . . ? C18 C13 C14 C15 1.3(10) . . . . ? P1 C13 C14 C15 179.9(5) . . . . ? C13 C14 C15 C16 -0.4(11) . . . . ? C14 C15 C16 C17 -1.3(12) . . . . ? C15 C16 C17 C18 2.1(11) . . . . ? C16 C17 C18 C13 -1.1(11) . . . . ? C14 C13 C18 C17 -0.6(10) . . . . ? P1 C13 C18 C17 -179.1(5) . . . . ? C31 P2 C19 C20 19.8(6) . . . . ? C25 P2 C19 C20 -95.9(6) . . . . ? Au2 P2 C19 C20 142.5(5) . . . . ? C31 P2 C19 C24 -155.6(5) . . . . ? C25 P2 C19 C24 88.7(5) . . . . ? Au2 P2 C19 C24 -32.9(5) . . . . ? C24 C19 C20 C21 1.9(9) . . . . ? P2 C19 C20 C21 -173.2(5) . . . . ? C19 C20 C21 C22 0.3(10) . . . . ? C20 C21 C22 C23 -1.2(10) . . . . ? C21 C22 C23 F2 177.7(6) . . . . ? C21 C22 C23 C24 0.0(10) . . . . ? F2 C23 C24 C19 -175.7(5) . . . . ? C22 C23 C24 C19 2.0(9) . . . . ? F2 C23 C24 Au1 3.9(8) . . . . ? C22 C23 C24 Au1 -178.5(5) . . . . ? C20 C19 C24 C23 -2.9(9) . . . . ? P2 C19 C24 C23 172.6(4) . . . . ? C20 C19 C24 Au1 177.6(5) . . . . ? P2 C19 C24 Au1 -6.9(6) . . . . ? Cl1 Au1 C24 C23 46.9(5) . . . . ? Au2 Au1 C24 C23 -141.0(5) . . . . ? Cl1 Au1 C24 C19 -133.6(5) . . . . ? Au2 Au1 C24 C19 38.5(5) . . . . ? C31 P2 C25 C30 100.7(6) . . . . ? C19 P2 C25 C30 -142.9(6) . . . . ? Au2 P2 C25 C30 -27.1(6) . . . . ? C31 P2 C25 C26 -74.5(6) . . . . ? C19 P2 C25 C26 41.8(7) . . . . ? Au2 P2 C25 C26 157.6(5) . . . . ? C30 C25 C26 C27 -0.5(11) . . . . ? P2 C25 C26 C27 174.8(6) . . . . ? C25 C26 C27 C28 -0.1(12) . . . . ? C26 C27 C28 C29 0.0(12) . . . . ? C27 C28 C29 C30 0.9(12) . . . . ? C26 C25 C30 C29 1.3(11) . . . . ? P2 C25 C30 C29 -174.0(6) . . . . ? C28 C29 C30 C25 -1.5(11) . . . . ? C19 P2 C31 C32 -128.8(6) . . . . ? C25 P2 C31 C32 -11.1(6) . . . . ? Au2 P2 C31 C32 115.7(5) . . . . ? C19 P2 C31 C36 55.3(6) . . . . ? C25 P2 C31 C36 173.1(5) . . . . ? Au2 P2 C31 C36 -60.2(6) . . . . ? C36 C31 C32 C33 0.5(11) . . . . ? P2 C31 C32 C33 -175.4(6) . . . . ? C31 C32 C33 C34 -0.9(12) . . . . ? C32 C33 C34 C35 0.3(12) . . . . ? C33 C34 C35 C36 0.6(12) . . . . ? C34 C35 C36 C31 -0.9(12) . . . . ? C32 C31 C36 C35 0.3(11) . . . . ? P2 C31 C36 C35 176.3(6) . . . . ? C60 Au3 Au4 C42 144.2(2) . . . . ? P3 Au3 Au4 C42 -37.58(17) . . . . ? C60 Au3 Au4 P4 -38.09(17) . . . . ? P3 Au3 Au4 P4 140.09(5) . . . . ? C60 Au3 Au4 Cl4 -104.3(3) . . . . ? P3 Au3 Au4 Cl4 73.9(2) . . . . ? Cl3 Au3 P3 C37 -147.9(2) . . . . ? Au4 Au3 P3 C37 40.3(2) . . . . ? Cl3 Au3 P3 C49 90.3(2) . . . . ? Au4 Au3 P3 C49 -81.5(2) . . . . ? Cl3 Au3 P3 C43 -30.2(2) . . . . ? Au4 Au3 P3 C43 158.0(2) . . . . ? Cl4 Au4 P4 C55 -150.1(2) . . . . ? Au3 Au4 P4 C55 39.3(2) . . . . ? Cl4 Au4 P4 C61 -30.6(2) . . . . ? Au3 Au4 P4 C61 158.7(2) . . . . ? Cl4 Au4 P4 C67 94.9(5) . . . . ? Au3 Au4 P4 C67 -75.8(5) . . . . ? Cl4 Au4 P4 C67A 83.9(13) . . . . ? Au3 Au4 P4 C67A -86.7(13) . . . . ? C49 P3 C37 C38 -91.5(6) . . . . ? C43 P3 C37 C38 23.9(6) . . . . ? Au3 P3 C37 C38 146.4(5) . . . . ? C49 P3 C37 C42 95.9(5) . . . . ? C43 P3 C37 C42 -148.7(5) . . . . ? Au3 P3 C37 C42 -26.2(5) . . . . ? C42 C37 C38 C39 1.9(9) . . . . ? P3 C37 C38 C39 -170.1(5) . . . . ? C37 C38 C39 C40 0.2(9) . . . . ? C38 C39 C40 C41 -1.8(10) . . . . ? C39 C40 C41 F3 179.0(6) . . . . ? C39 C40 C41 C42 1.6(10) . . . . ? F3 C41 C42 C37 -177.0(5) . . . . ? C40 C41 C42 C37 0.4(10) . . . . ? F3 C41 C42 Au4 5.3(9) . . . . ? C40 C41 C42 Au4 -177.3(5) . . . . ? C38 C37 C42 C41 -2.2(9) . . . . ? P3 C37 C42 C41 170.4(5) . . . . ? C38 C37 C42 Au4 175.6(5) . . . . ? P3 C37 C42 Au4 -11.8(7) . . . . ? Cl4 Au4 C42 C41 45.8(5) . . . . ? Au3 Au4 C42 C41 -143.7(5) . . . . ? Cl4 Au4 C42 C37 -131.7(5) . . . . ? Au3 Au4 C42 C37 38.7(5) . . . . ? C37 P3 C43 C48 -131.1(5) . . . . ? C49 P3 C43 C48 -12.2(6) . . . . ? Au3 P3 C43 C48 111.4(5) . . . . ? C37 P3 C43 C44 50.7(5) . . . . ? C49 P3 C43 C44 169.6(5) . . . . ? Au3 P3 C43 C44 -66.7(5) . . . . ? C48 C43 C44 C45 1.4(9) . . . . ? P3 C43 C44 C45 179.6(5) . . . . ? C43 C44 C45 C46 -1.8(9) . . . . ? C44 C45 C46 C47 1.1(9) . . . . ? C45 C46 C47 C48 0.2(9) . . . . ? C44 C43 C48 C47 -0.2(9) . . . . ? P3 C43 C48 C47 -178.3(5) . . . . ? C46 C47 C48 C43 -0.6(9) . . . . ? C37 P3 C49 C54 -162.0(5) . . . . ? C43 P3 C49 C54 82.1(5) . . . . ? Au3 P3 C49 C54 -43.1(6) . . . . ? C37 P3 C49 C50 22.4(7) . . . . ? C43 P3 C49 C50 -93.5(6) . . . . ? Au3 P3 C49 C50 141.4(5) . . . . ? C54 C49 C50 C51 -1.2(10) . . . . ? P3 C49 C50 C51 174.2(5) . . . . ? C49 C50 C51 C52 -0.8(11) . . . . ? C50 C51 C52 C53 1.9(12) . . . . ? C51 C52 C53 C54 -0.9(12) . . . . ? C52 C53 C54 C49 -1.1(11) . . . . ? C50 C49 C54 C53 2.2(10) . . . . ? P3 C49 C54 C53 -173.4(5) . . . . ? C61 P4 C55 C60 -150.5(5) . . . . ? C67 P4 C55 C60 92.5(9) . . . . ? C67A P4 C55 C60 96.2(19) . . . . ? Au4 P4 C55 C60 -24.0(5) . . . . ? C61 P4 C55 C56 23.9(7) . . . . ? C67 P4 C55 C56 -93.1(10) . . . . ? C67A P4 C55 C56 -89.4(19) . . . . ? Au4 P4 C55 C56 150.4(6) . . . . ? C60 C55 C56 C57 1.1(12) . . . . ? P4 C55 C56 C57 -173.0(7) . . . . ? C55 C56 C57 C58 2.2(14) . . . . ? C56 C57 C58 C59 -2.1(13) . . . . ? C57 C58 C59 F4 177.8(7) . . . . ? C57 C58 C59 C60 -1.3(12) . . . . ? C58 C59 C60 C55 4.3(10) . . . . ? F4 C59 C60 C55 -174.7(5) . . . . ? C58 C59 C60 Au3 -170.6(6) . . . . ? F4 C59 C60 Au3 10.3(8) . . . . ? C56 C55 C60 C59 -4.1(9) . . . . ? P4 C55 C60 C59 170.4(5) . . . . ? C56 C55 C60 Au3 171.1(6) . . . . ? P4 C55 C60 Au3 -14.4(7) . . . . ? Cl3 Au3 C60 C59 43.7(5) . . . . ? Au4 Au3 C60 C59 -144.7(5) . . . . ? Cl3 Au3 C60 C55 -131.0(5) . . . . ? Au4 Au3 C60 C55 40.6(5) . . . . ? C55 P4 C61 C62 79.3(6) . . . . ? C67 P4 C61 C62 -165.6(8) . . . . ? C67A P4 C61 C62 -157.7(13) . . . . ? Au4 P4 C61 C62 -40.3(6) . . . . ? C55 P4 C61 C66 -97.5(6) . . . . ? C67 P4 C61 C66 17.7(8) . . . . ? C67A P4 C61 C66 25.5(13) . . . . ? Au4 P4 C61 C66 142.9(5) . . . . ? C66 C61 C62 C63 1.0(11) . . . . ? P4 C61 C62 C63 -175.9(6) . . . . ? C61 C62 C63 C64 -0.7(11) . . . . ? C62 C63 C64 C65 0.0(11) . . . . ? C63 C64 C65 C66 0.4(12) . . . . ? C64 C65 C66 C61 -0.1(12) . . . . ? C62 C61 C66 C65 -0.6(11) . . . . ? P4 C61 C66 C65 176.2(6) . . . . ? C55 P4 C67 C72 -164.5(14) . . . . ? C61 P4 C67 C72 80.6(15) . . . . ? C67A P4 C67 C72 34(12) . . . . ? Au4 P4 C67 C72 -49.4(15) . . . . ? C55 P4 C67 C68 20.0(15) . . . . ? C61 P4 C67 C68 -94.9(13) . . . . ? C67A P4 C67 C68 -142(13) . . . . ? Au4 P4 C67 C68 135.1(12) . . . . ? C72 C67 C68 C69 0.0(15) . . . . ? P4 C67 C68 C69 175.4(15) . . . . ? C67 C68 C69 C70 1.9(15) . . . . ? C68 C69 C70 C71 -3(2) . . . . ? C69 C70 C71 C72 1(3) . . . . ? C68 C67 C72 C71 -1(3) . . . . ? P4 C67 C72 C71 -177(2) . . . . ? C70 C71 C72 C67 1(3) . . . . ? C55 P4 C67A C72A -151(3) . . . . ? C61 P4 C67A C72A 93(3) . . . . ? C67 P4 C67A C72A -132(13) . . . . ? Au4 P4 C67A C72A -32(3) . . . . ? C55 P4 C67A C68A 22(3) . . . . ? C61 P4 C67A C68A -93(3) . . . . ? C67 P4 C67A C68A 42(10) . . . . ? Au4 P4 C67A C68A 142(2) . . . . ? C72A C67A C68A C69A -2(2) . . . . ? P4 C67A C68A C69A -176(3) . . . . ? C67A C68A C69A C70A -1(2) . . . . ? C68A C69A C70A C71A 2(5) . . . . ? C69A C70A C71A C72A 0(6) . . . . ? C68A C67A C72A C71A 4(5) . . . . ? P4 C67A C72A C71A 177(4) . . . . ? C70A C71A C72A C67A -3(7) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 2.450 _refine_diff_density_min -1.945 _refine_diff_density_rms 0.187 # Attachment 'neda02601.cif.txt' data_neda02601 _database_code_depnum_ccdc_archive 'CCDC 726006' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexe [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C48 H20 Au2 F18 P2, 0.25(C H2 Cl2) ' _chemical_formula_sum 'C48.25 H20.50 Au2 Cl0.50 F18 P2' _chemical_formula_weight 1415.74 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.2743(3) _cell_length_b 13.8378(3) _cell_length_c 15.6632(3) _cell_angle_alpha 72.6380(10) _cell_angle_beta 72.0350(10) _cell_angle_gamma 86.0370(10) _cell_volume 2217.89(9) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 128584 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 29.131 _exptl_crystal_description piece _exptl_crystal_colour yellow _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.120 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1337 _exptl_absorpt_coefficient_mu 6.822 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.444 _exptl_absorpt_correction_T_max 0.619 _exptl_absorpt_process_details SORTAV _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 55739 _diffrn_reflns_av_R_equivalents 0.0559 _diffrn_reflns_av_sigmaI/netI 0.0395 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.70 _diffrn_reflns_theta_max 29.00 _reflns_number_total 11780 _reflns_number_gt 9672 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0397P)^2^+4.6099P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 11780 _refine_ls_number_parameters 733 _refine_ls_number_restraints 136 _refine_ls_R_factor_all 0.0473 _refine_ls_R_factor_gt 0.0332 _refine_ls_wR_factor_ref 0.0810 _refine_ls_wR_factor_gt 0.0770 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.047 _refine_ls_shift/su_max 0.004 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.114513(14) 0.722011(12) 0.213918(10) 0.01674(5) Uani 1 1 d . A . Au2 Au 0.191486(14) 0.642409(12) 0.358703(10) 0.01732(5) Uani 1 1 d . A . P1 P 0.28838(10) 0.64449(8) 0.13935(7) 0.0179(2) Uani 1 1 d D . . P2 P 0.13051(11) 0.79739(9) 0.38645(8) 0.0213(2) Uani 1 1 d D . . F1 F 0.4213(3) 0.4515(2) 0.09972(18) 0.0289(6) Uani 1 1 d . A . F2 F 0.4172(3) 0.2701(2) 0.2268(2) 0.0375(7) Uani 1 1 d . . . F3 F 0.2994(3) 0.2462(2) 0.4108(2) 0.0401(7) Uani 1 1 d . A . F4 F 0.1883(3) 0.3985(2) 0.47084(17) 0.0287(6) Uani 1 1 d . . . F5 F -0.0963(3) 0.9207(2) 0.4712(2) 0.0359(7) Uani 1 1 d . B . F6 F -0.3205(3) 0.9330(2) 0.4413(2) 0.0400(7) Uani 1 1 d . . . F7 F -0.3597(3) 0.8442(2) 0.3195(2) 0.0381(7) Uani 1 1 d . B . F8 F -0.1792(2) 0.7492(2) 0.22398(19) 0.0282(6) Uani 1 1 d . . . F9 F 0.1889(3) 0.9447(2) 0.06850(18) 0.0255(6) Uani 1 1 d . . . F10 F 0.1700(3) 1.0330(2) -0.10416(19) 0.0345(7) Uani 1 1 d . A . F11 F 0.0435(3) 0.9379(2) -0.18024(19) 0.0388(7) Uani 1 1 d . . . F12 F -0.0624(3) 0.7505(2) -0.0810(2) 0.0344(7) Uani 1 1 d . A . F13 F -0.0406(2) 0.6590(2) 0.09001(18) 0.0271(6) Uani 1 1 d . . . F14 F 0.4653(3) 0.6636(2) 0.36882(19) 0.0304(6) Uani 1 1 d . . . F15 F 0.5623(3) 0.6266(3) 0.5119(2) 0.0427(8) Uani 1 1 d . A . F16 F 0.4199(4) 0.5343(3) 0.6908(2) 0.0521(9) Uani 1 1 d . . . F17 F 0.1760(4) 0.4806(3) 0.7250(2) 0.0501(9) Uani 1 1 d . A . F18 F 0.0777(3) 0.5207(2) 0.5831(2) 0.0385(7) Uani 1 1 d . . . C1 C 0.3026(4) 0.5237(3) 0.2201(3) 0.0191(8) Uani 1 1 d . A . C2 C 0.3619(4) 0.4420(4) 0.1911(3) 0.0237(9) Uani 1 1 d . . . C3 C 0.3619(4) 0.3488(3) 0.2550(3) 0.0267(10) Uani 1 1 d . A . C4 C 0.3016(5) 0.3369(3) 0.3487(3) 0.0272(10) Uani 1 1 d . . . C5 C 0.2451(4) 0.4184(3) 0.3778(3) 0.0223(9) Uani 1 1 d . A . C6 C 0.2456(4) 0.5135(3) 0.3162(3) 0.0191(8) Uani 1 1 d . . . C7 C 0.274(2) 0.6264(16) 0.0323(8) 0.0181(17) Uani 0.43 1 d PDU A 1 C8 C 0.322(3) 0.6947(14) -0.0560(12) 0.022(3) Uani 0.43 1 d PD A 1 H8 H 0.3670 0.7535 -0.0635 0.026 Uiso 0.43 1 calc PR A 1 C9 C 0.303(3) 0.676(2) -0.1334(12) 0.037(4) Uani 0.43 1 d PD A 1 H9 H 0.3404 0.7199 -0.1945 0.044 Uiso 0.43 1 calc PR A 1 C10 C 0.230(4) 0.595(3) -0.1224(14) 0.038(4) Uani 0.43 1 d PD A 1 H10 H 0.2170 0.5829 -0.1756 0.045 Uiso 0.43 1 calc PR A 1 C11 C 0.175(3) 0.532(2) -0.0341(15) 0.032(3) Uani 0.43 1 d PD A 1 H11 H 0.1242 0.4758 -0.0264 0.038 Uiso 0.43 1 calc PR A 1 C12 C 0.194(5) 0.548(3) 0.0443(16) 0.025(3) Uani 0.43 1 d PD A 1 H12 H 0.1519 0.5065 0.1055 0.030 Uiso 0.43 1 calc PR A 1 C7A C 0.2634(15) 0.6088(12) 0.0429(6) 0.0181(17) Uani 0.57 1 d PD A 2 C8A C 0.3206(18) 0.6656(9) -0.0490(9) 0.022(3) Uani 0.57 1 d PD A 2 H8A H 0.3790 0.7184 -0.0624 0.026 Uiso 0.57 1 calc PR A 2 C9A C 0.291(2) 0.6436(14) -0.1211(9) 0.037(4) Uani 0.57 1 d PD A 2 H9A H 0.3262 0.6837 -0.1841 0.044 Uiso 0.57 1 calc PR A 2 C10A C 0.210(3) 0.5646(18) -0.1021(9) 0.038(4) Uani 0.57 1 d PD A 2 H10A H 0.1914 0.5499 -0.1522 0.045 Uiso 0.57 1 calc PR A 2 C11A C 0.156(3) 0.5065(16) -0.0114(10) 0.032(3) Uani 0.57 1 d PD A 2 H11A H 0.0995 0.4522 0.0013 0.038 Uiso 0.57 1 calc PR A 2 C12A C 0.184(4) 0.528(2) 0.0617(11) 0.025(3) Uani 0.57 1 d PD A 2 H12A H 0.1480 0.4873 0.1245 0.030 Uiso 0.57 1 calc PR A 2 C13 C 0.4344(8) 0.7149(11) 0.100(3) 0.0210(10) Uani 0.25 1 d PD A 1 C14 C 0.4396(15) 0.8096(14) 0.1117(18) 0.0381(19) Uani 0.25 1 d PD A 1 H14 H 0.3651 0.8412 0.1372 0.046 Uiso 0.25 1 calc PR A 1 C15 C 0.5550(16) 0.8583(17) 0.086(2) 0.045(2) Uani 0.25 1 d PD A 1 H15 H 0.5601 0.9210 0.0977 0.054 Uiso 0.25 1 calc PR A 1 C16 C 0.6603(19) 0.8154(17) 0.043(3) 0.0341(19) Uani 0.25 1 d PD A 1 H16 H 0.7373 0.8526 0.0184 0.041 Uiso 0.25 1 calc PR A 1 C17 C 0.6571(13) 0.7200(16) 0.036(2) 0.048(2) Uani 0.25 1 d PD A 1 H17 H 0.7325 0.6883 0.0124 0.057 Uiso 0.25 1 calc PR A 1 C18 C 0.5430(13) 0.6690(15) 0.0629(18) 0.0400(18) Uani 0.25 1 d PD A 1 H18 H 0.5398 0.6035 0.0558 0.048 Uiso 0.25 1 calc PR A 1 C13A C 0.4371(5) 0.7101(4) 0.1039(9) 0.0210(10) Uani 0.75 1 d PD A 2 C14A C 0.4470(6) 0.8139(5) 0.0633(6) 0.0381(19) Uani 0.75 1 d PD A 2 H14A H 0.3762 0.8511 0.0529 0.046 Uiso 0.75 1 calc PR A 2 C15A C 0.5616(6) 0.8637(6) 0.0378(6) 0.045(2) Uani 0.75 1 d PD A 2 H15A H 0.5692 0.9346 0.0078 0.054 Uiso 0.75 1 calc PR A 2 C16A C 0.6629(7) 0.8118(5) 0.0555(9) 0.0341(19) Uani 0.75 1 d PD A 2 H16A H 0.7398 0.8468 0.0397 0.041 Uiso 0.75 1 calc PR A 2 C17A C 0.6534(6) 0.7096(6) 0.0959(7) 0.048(2) Uani 0.75 1 d PD A 2 H17A H 0.7244 0.6734 0.1071 0.057 Uiso 0.75 1 calc PR A 2 C18A C 0.5404(6) 0.6576(5) 0.1209(6) 0.0400(18) Uani 0.75 1 d PD A 2 H18A H 0.5344 0.5865 0.1496 0.048 Uiso 0.75 1 calc PR A 2 C19 C -0.0183(4) 0.8225(3) 0.3647(3) 0.0217(9) Uani 1 1 d . A . C20 C -0.1137(5) 0.8761(4) 0.4107(3) 0.0272(10) Uani 1 1 d . . . C21 C -0.2281(4) 0.8838(4) 0.3958(3) 0.0281(10) Uani 1 1 d . B . C22 C -0.2486(4) 0.8390(4) 0.3335(3) 0.0273(10) Uani 1 1 d . . . C23 C -0.1522(4) 0.7890(3) 0.2848(3) 0.0230(9) Uani 1 1 d . A . C24 C -0.0357(4) 0.7796(3) 0.2975(3) 0.0206(9) Uani 1 1 d . . . C25 C 0.096(3) 0.786(2) 0.5101(5) 0.0242(13) Uani 0.25 1 d PD B 1 C26 C 0.015(3) 0.710(2) 0.5778(14) 0.0319(19) Uani 0.25 1 d PD B 1 H26 H -0.0224 0.6622 0.5601 0.038 Uiso 0.25 1 calc PR B 1 C27 C -0.011(3) 0.705(2) 0.6719(14) 0.040(2) Uani 0.25 1 d PD B 1 H27 H -0.0657 0.6526 0.7187 0.047 Uiso 0.25 1 calc PR B 1 C28 C 0.041(2) 0.7738(17) 0.6986(13) 0.044(2) Uani 0.25 1 d PD B 1 H28 H 0.0222 0.7693 0.7631 0.053 Uiso 0.25 1 calc PR B 1 C29 C 0.121(2) 0.8494(16) 0.6313(12) 0.047(2) Uani 0.25 1 d PD B 1 H29 H 0.1568 0.8974 0.6495 0.056 Uiso 0.25 1 calc PR B 1 C30 C 0.150(2) 0.8555(16) 0.5367(12) 0.0355(17) Uani 0.25 1 d PD B 1 H30 H 0.2058 0.9069 0.4904 0.043 Uiso 0.25 1 calc PR B 1 C25A C 0.1175(7) 0.7996(9) 0.5042(3) 0.0242(13) Uani 0.75 1 d PD B 2 C26A C 0.0190(8) 0.7440(6) 0.5772(4) 0.0319(19) Uani 0.75 1 d PD B 2 H26A H -0.0440 0.7140 0.5638 0.038 Uiso 0.75 1 calc PR B 2 C27A C 0.0133(10) 0.7325(7) 0.6698(5) 0.040(2) Uani 0.75 1 d PD B 2 H27A H -0.0541 0.6954 0.7198 0.047 Uiso 0.75 1 calc PR B 2 C28A C 0.1060(6) 0.7751(6) 0.6887(5) 0.044(2) Uani 0.75 1 d PD B 2 H28A H 0.1020 0.7672 0.7518 0.053 Uiso 0.75 1 calc PR B 2 C29A C 0.2043(8) 0.8290(6) 0.6163(5) 0.047(2) Uani 0.75 1 d PD B 2 H29A H 0.2678 0.8575 0.6303 0.056 Uiso 0.75 1 calc PR B 2 C30A C 0.2115(7) 0.8423(5) 0.5232(5) 0.0355(17) Uani 0.75 1 d PD B 2 H30A H 0.2791 0.8796 0.4735 0.043 Uiso 0.75 1 calc PR B 2 C31 C 0.2275(13) 0.9086(14) 0.318(4) 0.025(2) Uani 0.25 1 d PD B 1 C32 C 0.184(2) 0.999(3) 0.270(6) 0.043(3) Uani 0.25 1 d PD B 1 H32 H 0.0972 1.0071 0.2790 0.052 Uiso 0.25 1 calc PR B 1 C33 C 0.267(2) 1.077(4) 0.210(6) 0.050(5) Uani 0.25 1 d PD B 1 H33 H 0.2392 1.1344 0.1708 0.060 Uiso 0.25 1 calc PR B 1 C34 C 0.391(2) 1.068(3) 0.207(5) 0.047(4) Uani 0.25 1 d PD B 1 H34 H 0.4478 1.1224 0.1681 0.056 Uiso 0.25 1 calc PR B 1 C35 C 0.4319(18) 0.9824(16) 0.2609(17) 0.0425(19) Uani 0.25 1 d PD B 1 H35 H 0.5165 0.9798 0.2604 0.051 Uiso 0.25 1 calc PR B 1 C36 C 0.3530(17) 0.9002(14) 0.3151(16) 0.0343(16) Uani 0.25 1 d PD B 1 H36 H 0.3829 0.8399 0.3492 0.041 Uiso 0.25 1 calc PR B 1 C31A C 0.2340(5) 0.9012(4) 0.3074(11) 0.025(2) Uani 0.75 1 d PD B 2 C32A C 0.1862(9) 0.9976(9) 0.2806(19) 0.043(3) Uani 0.75 1 d PD B 2 H32A H 0.0989 1.0069 0.3017 0.052 Uiso 0.75 1 calc PR B 2 C33A C 0.2645(9) 1.0794(12) 0.2239(18) 0.050(5) Uani 0.75 1 d PD B 2 H33A H 0.2314 1.1449 0.2069 0.060 Uiso 0.75 1 calc PR B 2 C34A C 0.3911(8) 1.0655(8) 0.1920(13) 0.047(4) Uani 0.75 1 d PD B 2 H34A H 0.4451 1.1218 0.1531 0.056 Uiso 0.75 1 calc PR B 2 C35A C 0.4402(7) 0.9705(5) 0.2160(6) 0.0425(19) Uani 0.75 1 d PD B 2 H35A H 0.5274 0.9617 0.1935 0.051 Uiso 0.75 1 calc PR B 2 C36A C 0.3623(6) 0.8885(5) 0.2728(5) 0.0343(16) Uani 0.75 1 d PD B 2 H36A H 0.3960 0.8231 0.2885 0.041 Uiso 0.75 1 calc PR B 2 C37 C 0.0738(4) 0.7970(3) 0.0865(3) 0.0188(8) Uani 1 1 d . . . C38 C 0.1257(4) 0.8928(3) 0.0337(3) 0.0196(8) Uani 1 1 d . A . C39 C 0.1177(4) 0.9407(3) -0.0553(3) 0.0242(9) Uani 1 1 d . . . C40 C 0.0528(4) 0.8930(4) -0.0939(3) 0.0263(10) Uani 1 1 d . A . C41 C 0.0003(4) 0.7975(4) -0.0433(3) 0.0251(10) Uani 1 1 d . . . C42 C 0.0124(4) 0.7525(3) 0.0450(3) 0.0200(8) Uani 1 1 d . A . C43 C 0.2675(4) 0.5938(3) 0.4725(3) 0.0205(9) Uani 1 1 d . . . C44 C 0.3895(4) 0.6192(4) 0.4573(3) 0.0233(9) Uani 1 1 d . A . C45 C 0.4428(5) 0.6003(4) 0.5291(4) 0.0321(11) Uani 1 1 d . . . C46 C 0.3703(6) 0.5533(4) 0.6197(4) 0.0350(12) Uani 1 1 d . A . C47 C 0.2471(6) 0.5259(4) 0.6375(3) 0.0358(12) Uani 1 1 d . . . C48 C 0.1991(5) 0.5484(4) 0.5637(3) 0.0288(10) Uani 1 1 d . A . Cl1 Cl 0.6561(5) 0.0959(5) 0.2531(4) 0.0423(12) Uani 0.25 1 d P C 1 C1S C 0.5339(19) 0.1006(16) 0.3545(15) 0.033(4) Uani 0.25 1 d PU C 1 H1S1 H 0.5242 0.0342 0.4029 0.040 Uiso 0.25 1 calc PR C 1 H1S2 H 0.4547 0.1149 0.3387 0.040 Uiso 0.25 1 calc PR C 1 Cl2 Cl 0.5655(7) 0.1958(7) 0.3994(5) 0.067(2) Uani 0.25 1 d P C 1 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.01796(8) 0.02005(9) 0.01457(8) -0.00614(6) -0.00727(6) 0.00086(6) Au2 0.01942(8) 0.02076(9) 0.01478(8) -0.00713(6) -0.00778(6) 0.00179(6) P1 0.0192(5) 0.0211(5) 0.0159(5) -0.0074(4) -0.0066(4) -0.0003(4) P2 0.0241(6) 0.0240(6) 0.0208(5) -0.0106(5) -0.0109(5) 0.0045(4) F1 0.0358(15) 0.0276(15) 0.0208(13) -0.0096(11) -0.0039(11) 0.0063(12) F2 0.0499(19) 0.0225(14) 0.0370(16) -0.0138(13) -0.0055(14) 0.0075(13) F3 0.060(2) 0.0183(14) 0.0357(17) -0.0042(12) -0.0095(15) 0.0053(13) F4 0.0404(16) 0.0268(14) 0.0170(12) -0.0052(11) -0.0070(12) -0.0003(12) F5 0.0410(17) 0.0440(18) 0.0320(15) -0.0249(14) -0.0138(13) 0.0163(14) F6 0.0329(16) 0.0470(19) 0.0371(17) -0.0178(15) -0.0042(13) 0.0159(14) F7 0.0215(14) 0.0457(18) 0.0463(18) -0.0103(15) -0.0142(13) 0.0105(13) F8 0.0265(14) 0.0365(16) 0.0279(14) -0.0128(12) -0.0137(12) 0.0005(12) F9 0.0355(15) 0.0230(14) 0.0230(13) -0.0081(11) -0.0140(12) -0.0020(11) F10 0.0491(18) 0.0249(15) 0.0257(14) -0.0008(12) -0.0113(13) -0.0037(13) F11 0.058(2) 0.0420(18) 0.0217(14) -0.0057(13) -0.0249(14) 0.0084(15) F12 0.0409(17) 0.0438(18) 0.0319(15) -0.0166(13) -0.0241(13) 0.0000(13) F13 0.0287(14) 0.0267(14) 0.0276(14) -0.0067(11) -0.0112(11) -0.0037(11) F14 0.0273(14) 0.0365(16) 0.0294(15) -0.0106(13) -0.0105(12) 0.0000(12) F15 0.0394(18) 0.0476(19) 0.060(2) -0.0250(17) -0.0349(16) 0.0098(15) F16 0.079(3) 0.060(2) 0.0383(18) -0.0191(16) -0.0447(19) 0.0127(19) F17 0.084(3) 0.048(2) 0.0177(14) -0.0063(14) -0.0147(16) -0.0093(18) F18 0.0397(17) 0.052(2) 0.0230(14) -0.0142(13) -0.0025(13) -0.0122(14) C1 0.021(2) 0.020(2) 0.018(2) -0.0069(17) -0.0073(16) -0.0002(16) C2 0.026(2) 0.027(2) 0.020(2) -0.0116(18) -0.0044(18) 0.0010(18) C3 0.031(2) 0.021(2) 0.029(2) -0.0121(19) -0.007(2) 0.0041(19) C4 0.035(3) 0.018(2) 0.025(2) -0.0030(18) -0.008(2) -0.0005(19) C5 0.027(2) 0.023(2) 0.018(2) -0.0080(17) -0.0076(18) 0.0003(18) C6 0.020(2) 0.020(2) 0.020(2) -0.0089(17) -0.0077(17) 0.0008(16) C7 0.019(3) 0.019(5) 0.018(2) -0.007(3) -0.007(2) 0.001(3) C8 0.030(3) 0.016(8) 0.019(3) -0.007(4) -0.007(2) 0.001(6) C9 0.034(5) 0.059(13) 0.015(4) -0.009(5) -0.005(4) -0.005(7) C10 0.025(9) 0.075(15) 0.022(7) -0.029(8) -0.006(8) -0.002(7) C11 0.034(8) 0.028(11) 0.047(8) -0.023(7) -0.020(8) 0.000(5) C12 0.029(6) 0.018(11) 0.029(6) -0.003(6) -0.011(7) -0.003(5) C7A 0.019(3) 0.019(5) 0.018(2) -0.007(3) -0.007(2) 0.001(3) C8A 0.030(3) 0.016(8) 0.019(3) -0.007(4) -0.007(2) 0.001(6) C9A 0.034(5) 0.059(13) 0.015(4) -0.009(5) -0.005(4) -0.005(7) C10A 0.025(9) 0.075(15) 0.022(7) -0.029(8) -0.006(8) -0.002(7) C11A 0.034(8) 0.028(11) 0.047(8) -0.023(7) -0.020(8) 0.000(5) C12A 0.029(6) 0.018(11) 0.029(6) -0.003(6) -0.011(7) -0.003(5) C13 0.022(2) 0.023(2) 0.021(2) -0.0089(19) -0.0081(17) -0.0022(17) C14 0.024(3) 0.026(3) 0.058(5) -0.008(4) -0.007(4) 0.004(2) C15 0.029(3) 0.024(3) 0.070(7) -0.007(5) -0.004(4) -0.006(2) C16 0.026(3) 0.037(3) 0.040(5) -0.015(3) -0.006(2) -0.007(2) C17 0.026(3) 0.038(4) 0.081(7) -0.011(5) -0.025(4) 0.005(3) C18 0.025(3) 0.031(3) 0.064(5) -0.006(4) -0.021(4) -0.004(3) C13A 0.022(2) 0.023(2) 0.021(2) -0.0089(19) -0.0081(17) -0.0022(17) C14A 0.024(3) 0.026(3) 0.058(5) -0.008(4) -0.007(4) 0.004(2) C15A 0.029(3) 0.024(3) 0.070(7) -0.007(5) -0.004(4) -0.006(2) C16A 0.026(3) 0.037(3) 0.040(5) -0.015(3) -0.006(2) -0.007(2) C17A 0.026(3) 0.038(4) 0.081(7) -0.011(5) -0.025(4) 0.005(3) C18A 0.025(3) 0.031(3) 0.064(5) -0.006(4) -0.021(4) -0.004(3) C19 0.025(2) 0.024(2) 0.017(2) -0.0063(17) -0.0077(17) 0.0011(18) C20 0.033(3) 0.029(2) 0.020(2) -0.0096(19) -0.0062(19) 0.006(2) C21 0.027(2) 0.031(3) 0.024(2) -0.008(2) -0.0061(19) 0.010(2) C22 0.017(2) 0.032(3) 0.028(2) -0.003(2) -0.0056(18) 0.0041(18) C23 0.026(2) 0.024(2) 0.019(2) -0.0037(17) -0.0095(18) 0.0005(18) C24 0.021(2) 0.022(2) 0.018(2) -0.0059(17) -0.0057(17) 0.0024(17) C25 0.035(4) 0.022(4) 0.024(2) -0.013(2) -0.016(2) 0.008(3) C26 0.035(3) 0.040(6) 0.023(3) -0.015(3) -0.007(2) 0.003(4) C27 0.052(6) 0.038(6) 0.027(3) -0.014(3) -0.008(3) 0.010(4) C28 0.071(6) 0.045(4) 0.032(3) -0.027(3) -0.028(5) 0.021(5) C29 0.075(6) 0.041(4) 0.040(4) -0.012(3) -0.040(5) 0.001(4) C30 0.050(5) 0.030(3) 0.037(4) -0.010(3) -0.029(4) 0.001(4) C25A 0.035(4) 0.022(4) 0.024(2) -0.013(2) -0.016(2) 0.008(3) C26A 0.035(3) 0.040(6) 0.023(3) -0.015(3) -0.007(2) 0.003(4) C27A 0.052(6) 0.038(6) 0.027(3) -0.014(3) -0.008(3) 0.010(4) C28A 0.071(6) 0.045(4) 0.032(3) -0.027(3) -0.028(5) 0.021(5) C29A 0.075(6) 0.041(4) 0.040(4) -0.012(3) -0.040(5) 0.001(4) C30A 0.050(5) 0.030(3) 0.037(4) -0.010(3) -0.029(4) 0.001(4) C31 0.030(3) 0.025(3) 0.026(5) -0.014(3) -0.011(2) 0.003(2) C32 0.033(3) 0.037(3) 0.053(8) -0.004(3) -0.012(3) 0.007(2) C33 0.048(4) 0.027(3) 0.066(10) -0.007(4) -0.012(4) 0.005(3) C34 0.045(3) 0.034(3) 0.060(8) -0.015(4) -0.009(3) -0.008(3) C35 0.036(4) 0.039(4) 0.049(5) -0.013(4) -0.005(4) -0.001(3) C36 0.032(3) 0.028(3) 0.043(5) -0.013(3) -0.011(4) 0.009(3) C31A 0.030(3) 0.025(3) 0.026(5) -0.014(3) -0.011(2) 0.003(2) C32A 0.033(3) 0.037(3) 0.053(8) -0.004(3) -0.012(3) 0.007(2) C33A 0.048(4) 0.027(3) 0.066(10) -0.007(4) -0.012(4) 0.005(3) C34A 0.045(3) 0.034(3) 0.060(8) -0.015(4) -0.009(3) -0.008(3) C35A 0.036(4) 0.039(4) 0.049(5) -0.013(4) -0.005(4) -0.001(3) C36A 0.032(3) 0.028(3) 0.043(5) -0.013(3) -0.011(4) 0.009(3) C37 0.023(2) 0.018(2) 0.0140(19) -0.0068(16) -0.0010(16) 0.0015(16) C38 0.020(2) 0.023(2) 0.021(2) -0.0110(17) -0.0092(17) 0.0038(17) C39 0.029(2) 0.019(2) 0.023(2) -0.0024(18) -0.0097(19) 0.0017(18) C40 0.031(2) 0.033(3) 0.018(2) -0.0087(19) -0.0118(19) 0.008(2) C41 0.028(2) 0.030(2) 0.024(2) -0.0092(19) -0.0175(19) 0.0060(19) C42 0.020(2) 0.025(2) 0.018(2) -0.0100(17) -0.0075(17) 0.0034(17) C43 0.018(2) 0.026(2) 0.025(2) -0.0168(18) -0.0108(17) 0.0066(17) C44 0.026(2) 0.027(2) 0.020(2) -0.0086(18) -0.0097(18) 0.0024(18) C45 0.039(3) 0.028(3) 0.043(3) -0.017(2) -0.028(2) 0.011(2) C46 0.063(4) 0.028(3) 0.029(3) -0.014(2) -0.033(3) 0.012(2) C47 0.056(3) 0.034(3) 0.018(2) -0.008(2) -0.011(2) 0.002(2) C48 0.037(3) 0.035(3) 0.019(2) -0.017(2) -0.007(2) 0.000(2) Cl1 0.043(3) 0.048(3) 0.043(3) -0.023(3) -0.016(2) 0.007(2) C1S 0.031(6) 0.033(6) 0.035(6) -0.010(4) -0.009(4) 0.008(4) Cl2 0.048(4) 0.097(6) 0.064(4) -0.043(4) -0.012(3) 0.020(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.071(4) . ? Au1 C37 2.129(4) . ? Au1 P1 2.3243(11) . ? Au1 Au2 2.5885(2) . ? Au2 C6 2.074(4) . ? Au2 C43 2.124(4) . ? Au2 P2 2.3301(12) . ? P1 C1 1.801(4) . ? P1 C13 1.810(4) . ? P1 C13A 1.810(4) . ? P1 C7A 1.825(5) . ? P1 C7 1.825(5) . ? P2 C31 1.799(5) . ? P2 C31A 1.799(5) . ? P2 C19 1.803(4) . ? P2 C25A 1.814(5) . ? P2 C25 1.814(5) . ? F1 C2 1.350(5) . ? F2 C3 1.339(5) . ? F3 C4 1.335(5) . ? F4 C5 1.349(5) . ? F5 C20 1.342(5) . ? F6 C21 1.338(5) . ? F7 C22 1.330(5) . ? F8 C23 1.348(5) . ? F9 C38 1.366(5) . ? F10 C39 1.344(5) . ? F11 C40 1.342(5) . ? F12 C41 1.349(5) . ? F13 C42 1.354(5) . ? F14 C44 1.364(5) . ? F15 C45 1.344(6) . ? F16 C46 1.346(5) . ? F17 C47 1.339(6) . ? F18 C48 1.364(6) . ? C1 C2 1.395(6) . ? C1 C6 1.411(6) . ? C2 C3 1.377(6) . ? C3 C4 1.377(7) . ? C4 C5 1.384(6) . ? C5 C6 1.380(6) . ? C7 C8 1.388(5) . ? C7 C12 1.388(5) . ? C8 C9 1.392(5) . ? C8 H8 0.9500 . ? C9 C10 1.374(6) . ? C9 H9 0.9500 . ? C10 C11 1.374(6) . ? C10 H10 0.9500 . ? C11 C12 1.392(5) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C7A C8A 1.388(5) . ? C7A C12A 1.388(5) . ? C8A C9A 1.392(5) . ? C8A H8A 0.9500 . ? C9A C10A 1.374(6) . ? C9A H9A 0.9500 . ? C10A C11A 1.374(6) . ? C10A H10A 0.9500 . ? C11A C12A 1.392(5) . ? C11A H11A 0.9500 . ? C12A H12A 0.9500 . ? C13 C18 1.384(5) . ? C13 C14 1.384(5) . ? C14 C15 1.394(6) . ? C14 H14 0.9500 . ? C15 C16 1.363(6) . ? C15 H15 0.9500 . ? C16 C17 1.363(6) . ? C16 H16 0.9500 . ? C17 C18 1.394(6) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C13A C14A 1.384(5) . ? C13A C18A 1.384(5) . ? C14A C15A 1.394(6) . ? C14A H14A 0.9500 . ? C15A C16A 1.363(6) . ? C15A H15A 0.9500 . ? C16A C17A 1.363(6) . ? C16A H16A 0.9500 . ? C17A C18A 1.394(6) . ? C17A H17A 0.9500 . ? C18A H18A 0.9500 . ? C19 C20 1.398(6) . ? C19 C24 1.419(6) . ? C20 C21 1.372(7) . ? C21 C22 1.383(7) . ? C22 C23 1.393(7) . ? C23 C24 1.380(6) . ? C25 C30 1.394(5) . ? C25 C26 1.394(5) . ? C26 C27 1.393(6) . ? C26 H26 0.9500 . ? C27 C28 1.380(7) . ? C27 H27 0.9500 . ? C28 C29 1.380(7) . ? C28 H28 0.9500 . ? C29 C30 1.393(6) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C25A C26A 1.394(5) . ? C25A C30A 1.394(5) . ? C26A C27A 1.393(6) . ? C26A H26A 0.9500 . ? C27A C28A 1.380(7) . ? C27A H27A 0.9500 . ? C28A C29A 1.380(7) . ? C28A H28A 0.9500 . ? C29A C30A 1.393(6) . ? C29A H29A 0.9500 . ? C30A H30A 0.9500 . ? C31 C32 1.398(6) . ? C31 C36 1.398(6) . ? C32 C33 1.380(6) . ? C32 H32 0.9500 . ? C33 C34 1.380(7) . ? C33 H33 0.9500 . ? C34 C35 1.380(7) . ? C34 H34 0.9500 . ? C35 C36 1.380(6) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C31A C32A 1.398(6) . ? C31A C36A 1.398(6) . ? C32A C33A 1.380(6) . ? C32A H32A 0.9500 . ? C33A C34A 1.380(7) . ? C33A H33A 0.9500 . ? C34A C35A 1.380(7) . ? C34A H34A 0.9500 . ? C35A C36A 1.380(6) . ? C35A H35A 0.9500 . ? C36A H36A 0.9500 . ? C37 C42 1.362(6) . ? C37 C38 1.392(6) . ? C38 C39 1.382(6) . ? C39 C40 1.384(7) . ? C40 C41 1.385(7) . ? C41 C42 1.383(6) . ? C43 C48 1.372(6) . ? C43 C44 1.374(6) . ? C44 C45 1.383(6) . ? C45 C46 1.383(8) . ? C46 C47 1.388(8) . ? C47 C48 1.368(7) . ? Cl1 C1S 1.77(2) . ? C1S Cl2 1.77(2) . ? C1S H1S1 0.9900 . ? C1S H1S2 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 C37 94.78(16) . . ? C24 Au1 P1 172.05(12) . . ? C37 Au1 P1 93.15(11) . . ? C24 Au1 Au2 89.21(11) . . ? C37 Au1 Au2 172.71(12) . . ? P1 Au1 Au2 82.96(3) . . ? C6 Au2 C43 93.30(16) . . ? C6 Au2 P2 172.54(12) . . ? C43 Au2 P2 93.56(12) . . ? C6 Au2 Au1 90.98(11) . . ? C43 Au2 Au1 172.99(12) . . ? P2 Au2 Au1 81.91(3) . . ? C1 P1 C13 108.5(9) . . ? C1 P1 C13A 105.8(3) . . ? C1 P1 C7A 102.7(5) . . ? C13 P1 C7A 110.4(13) . . ? C13A P1 C7A 111.6(6) . . ? C1 P1 C7 109.9(7) . . ? C13 P1 C7 103.8(14) . . ? C13A P1 C7 105.2(7) . . ? C1 P1 Au1 107.75(15) . . ? C13 P1 Au1 115.4(6) . . ? C13A P1 Au1 116.6(3) . . ? C7A P1 Au1 111.3(6) . . ? C7 P1 Au1 111.5(8) . . ? C31 P2 C19 106.4(8) . . ? C31A P2 C19 106.7(4) . . ? C31 P2 C25A 100(2) . . ? C31A P2 C25A 106.4(6) . . ? C19 P2 C25A 110.2(3) . . ? C31 P2 C25 109(2) . . ? C31A P2 C25 115.3(9) . . ? C19 P2 C25 104.1(11) . . ? C31 P2 Au2 119.5(14) . . ? C31A P2 Au2 113.3(4) . . ? C19 P2 Au2 106.04(15) . . ? C25A P2 Au2 114.0(4) . . ? C25 P2 Au2 110.4(12) . . ? C2 C1 C6 120.5(4) . . ? C2 C1 P1 123.0(3) . . ? C6 C1 P1 116.4(3) . . ? F1 C2 C3 117.7(4) . . ? F1 C2 C1 121.3(4) . . ? C3 C2 C1 120.9(4) . . ? F2 C3 C2 120.8(4) . . ? F2 C3 C4 120.2(4) . . ? C2 C3 C4 119.0(4) . . ? F3 C4 C3 119.2(4) . . ? F3 C4 C5 120.6(4) . . ? C3 C4 C5 120.2(4) . . ? F4 C5 C6 121.9(4) . . ? F4 C5 C4 115.4(4) . . ? C6 C5 C4 122.6(4) . . ? C5 C6 C1 116.7(4) . . ? C5 C6 Au2 123.5(3) . . ? C1 C6 Au2 119.2(3) . . ? C8 C7 C12 119.6(12) . . ? C8 C7 P1 123.4(13) . . ? C12 C7 P1 116.2(13) . . ? C7 C8 C9 119.4(12) . . ? C7 C8 H8 120.3 . . ? C9 C8 H8 120.3 . . ? C10 C9 C8 120.6(14) . . ? C10 C9 H9 119.7 . . ? C8 C9 H9 119.7 . . ? C9 C10 C11 119.7(13) . . ? C9 C10 H10 120.1 . . ? C11 C10 H10 120.1 . . ? C10 C11 C12 120.6(14) . . ? C10 C11 H11 119.7 . . ? C12 C11 H11 119.7 . . ? C7 C12 C11 119.5(13) . . ? C7 C12 H12 120.3 . . ? C11 C12 H12 120.3 . . ? C8A C7A C12A 120.3(9) . . ? C8A C7A P1 119.6(9) . . ? C12A C7A P1 120.1(10) . . ? C7A C8A C9A 118.8(9) . . ? C7A C8A H8A 120.6 . . ? C9A C8A H8A 120.6 . . ? C10A C9A C8A 120.6(10) . . ? C10A C9A H9A 119.7 . . ? C8A C9A H9A 119.7 . . ? C9A C10A C11A 120.8(10) . . ? C9A C10A H10A 119.6 . . ? C11A C10A H10A 119.6 . . ? C10A C11A C12A 119.3(10) . . ? C10A C11A H11A 120.3 . . ? C12A C11A H11A 120.3 . . ? C7A C12A C11A 120.1(9) . . ? C7A C12A H12A 120.0 . . ? C11A C12A H12A 120.0 . . ? C18 C13 C14 120.2(10) . . ? C18 C13 P1 118.2(10) . . ? C14 C13 P1 121.5(11) . . ? C13 C14 C15 119.5(13) . . ? C13 C14 H14 120.3 . . ? C15 C14 H14 120.3 . . ? C16 C15 C14 119.7(17) . . ? C16 C15 H15 120.2 . . ? C14 C15 H15 120.2 . . ? C17 C16 C15 121.0(17) . . ? C17 C16 H16 119.5 . . ? C15 C16 H16 119.5 . . ? C16 C17 C18 119.9(16) . . ? C16 C17 H17 120.0 . . ? C18 C17 H17 120.0 . . ? C13 C18 C17 119.3(13) . . ? C13 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? C14A C13A C18A 119.3(5) . . ? C14A C13A P1 120.2(4) . . ? C18A C13A P1 120.4(4) . . ? C13A C14A C15A 119.6(5) . . ? C13A C14A H14A 120.2 . . ? C15A C14A H14A 120.2 . . ? C16A C15A C14A 120.8(6) . . ? C16A C15A H15A 119.6 . . ? C14A C15A H15A 119.6 . . ? C17A C16A C15A 119.8(7) . . ? C17A C16A H16A 120.1 . . ? C15A C16A H16A 120.1 . . ? C16A C17A C18A 120.7(6) . . ? C16A C17A H17A 119.7 . . ? C18A C17A H17A 119.7 . . ? C13A C18A C17A 119.8(6) . . ? C13A C18A H18A 120.1 . . ? C17A C18A H18A 120.1 . . ? C20 C19 C24 120.5(4) . . ? C20 C19 P2 125.0(3) . . ? C24 C19 P2 114.5(3) . . ? F5 C20 C21 118.1(4) . . ? F5 C20 C19 121.0(4) . . ? C21 C20 C19 120.9(4) . . ? F6 C21 C20 121.1(4) . . ? F6 C21 C22 119.5(4) . . ? C20 C21 C22 119.4(4) . . ? F7 C22 C21 120.1(4) . . ? F7 C22 C23 120.1(4) . . ? C21 C22 C23 119.8(4) . . ? F8 C23 C24 121.3(4) . . ? F8 C23 C22 116.0(4) . . ? C24 C23 C22 122.7(4) . . ? C23 C24 C19 116.6(4) . . ? C23 C24 Au1 123.0(3) . . ? C19 C24 Au1 120.0(3) . . ? C30 C25 C26 120.3(12) . . ? C30 C25 P2 119.2(12) . . ? C26 C25 P2 120.4(14) . . ? C27 C26 C25 118.7(15) . . ? C27 C26 H26 120.7 . . ? C25 C26 H26 120.7 . . ? C28 C27 C26 121.3(17) . . ? C28 C27 H27 119.4 . . ? C26 C27 H27 119.4 . . ? C27 C28 C29 119.9(16) . . ? C27 C28 H28 120.0 . . ? C29 C28 H28 120.0 . . ? C28 C29 C30 120.0(16) . . ? C28 C29 H29 120.0 . . ? C30 C29 H29 120.0 . . ? C29 C30 C25 119.9(14) . . ? C29 C30 H30 120.1 . . ? C25 C30 H30 120.1 . . ? C26A C25A C30A 120.6(6) . . ? C26A C25A P2 117.2(4) . . ? C30A C25A P2 121.6(4) . . ? C27A C26A C25A 119.6(7) . . ? C27A C26A H26A 120.2 . . ? C25A C26A H26A 120.2 . . ? C28A C27A C26A 119.9(7) . . ? C28A C27A H27A 120.1 . . ? C26A C27A H27A 120.1 . . ? C27A C28A C29A 120.4(6) . . ? C27A C28A H28A 119.8 . . ? C29A C28A H28A 119.8 . . ? C28A C29A C30A 120.8(6) . . ? C28A C29A H29A 119.6 . . ? C30A C29A H29A 119.6 . . ? C29A C30A C25A 118.7(6) . . ? C29A C30A H30A 120.6 . . ? C25A C30A H30A 120.6 . . ? C32 C31 C36 120.4(13) . . ? C32 C31 P2 123.8(14) . . ? C36 C31 P2 115.8(12) . . ? C33 C32 C31 120.3(17) . . ? C33 C32 H32 119.8 . . ? C31 C32 H32 119.8 . . ? C32 C33 C34 119(2) . . ? C32 C33 H33 120.7 . . ? C34 C33 H33 120.7 . . ? C35 C34 C33 120.8(17) . . ? C35 C34 H34 119.6 . . ? C33 C34 H34 119.6 . . ? C36 C35 C34 121.4(17) . . ? C36 C35 H35 119.3 . . ? C34 C35 H35 119.3 . . ? C35 C36 C31 117.9(13) . . ? C35 C36 H36 121.1 . . ? C31 C36 H36 121.1 . . ? C32A C31A C36A 118.7(6) . . ? C32A C31A P2 119.6(5) . . ? C36A C31A P2 121.7(4) . . ? C33A C32A C31A 120.7(9) . . ? C33A C32A H32A 119.6 . . ? C31A C32A H32A 119.7 . . ? C32A C33A C34A 119.6(10) . . ? C32A C33A H33A 120.2 . . ? C34A C33A H33A 120.2 . . ? C33A C34A C35A 120.7(8) . . ? C33A C34A H34A 119.7 . . ? C35A C34A H34A 119.7 . . ? C36A C35A C34A 119.9(7) . . ? C36A C35A H35A 120.0 . . ? C34A C35A H35A 120.0 . . ? C35A C36A C31A 120.4(6) . . ? C35A C36A H36A 119.8 . . ? C31A C36A H36A 119.8 . . ? C42 C37 C38 115.6(4) . . ? C42 C37 Au1 124.2(3) . . ? C38 C37 Au1 119.7(3) . . ? F9 C38 C39 116.2(4) . . ? F9 C38 C37 120.6(4) . . ? C39 C38 C37 123.2(4) . . ? F10 C39 C38 121.3(4) . . ? F10 C39 C40 119.7(4) . . ? C38 C39 C40 119.0(4) . . ? F11 C40 C39 120.2(4) . . ? F11 C40 C41 120.6(4) . . ? C39 C40 C41 119.2(4) . . ? F12 C41 C42 121.3(4) . . ? F12 C41 C40 119.3(4) . . ? C42 C41 C40 119.4(4) . . ? F13 C42 C37 120.4(4) . . ? F13 C42 C41 116.0(4) . . ? C37 C42 C41 123.6(4) . . ? C48 C43 C44 116.6(4) . . ? C48 C43 Au2 124.2(3) . . ? C44 C43 Au2 118.8(3) . . ? F14 C44 C43 120.8(4) . . ? F14 C44 C45 116.5(4) . . ? C43 C44 C45 122.7(4) . . ? F15 C45 C46 120.3(4) . . ? F15 C45 C44 121.2(5) . . ? C46 C45 C44 118.6(5) . . ? F16 C46 C45 119.7(5) . . ? F16 C46 C47 120.0(5) . . ? C45 C46 C47 120.3(4) . . ? F17 C47 C48 120.9(5) . . ? F17 C47 C46 120.7(5) . . ? C48 C47 C46 118.4(5) . . ? F18 C48 C47 117.2(4) . . ? F18 C48 C43 119.3(4) . . ? C47 C48 C43 123.5(5) . . ? Cl1 C1S Cl2 110.6(12) . . ? Cl1 C1S H1S1 109.5 . . ? Cl2 C1S H1S1 109.5 . . ? Cl1 C1S H1S2 109.5 . . ? Cl2 C1S H1S2 109.5 . . ? H1S1 C1S H1S2 108.1 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 141.20(17) . . . . ? P1 Au1 Au2 C6 -37.39(12) . . . . ? C24 Au1 Au2 P2 -41.07(13) . . . . ? P1 Au1 Au2 P2 140.35(4) . . . . ? C37 Au1 P1 C1 -148.04(19) . . . . ? Au2 Au1 P1 C1 38.15(14) . . . . ? C37 Au1 P1 C13 90.6(13) . . . . ? Au2 Au1 P1 C13 -83.2(13) . . . . ? C37 Au1 P1 C13A 93.3(4) . . . . ? Au2 Au1 P1 C13A -80.5(4) . . . . ? C37 Au1 P1 C7A -36.2(5) . . . . ? Au2 Au1 P1 C7A 150.0(5) . . . . ? C37 Au1 P1 C7 -27.4(6) . . . . ? Au2 Au1 P1 C7 158.8(6) . . . . ? C43 Au2 P2 C31 98.5(18) . . . . ? Au1 Au2 P2 C31 -76.1(18) . . . . ? C43 Au2 P2 C31A 101.9(5) . . . . ? Au1 Au2 P2 C31A -72.8(5) . . . . ? C43 Au2 P2 C19 -141.45(19) . . . . ? Au1 Au2 P2 C19 43.94(15) . . . . ? C43 Au2 P2 C25A -20.0(2) . . . . ? Au1 Au2 P2 C25A 165.3(2) . . . . ? C43 Au2 P2 C25 -29.2(8) . . . . ? Au1 Au2 P2 C25 156.2(8) . . . . ? C13 P1 C1 C2 -80.0(11) . . . . ? C13A P1 C1 C2 -80.2(6) . . . . ? C7A P1 C1 C2 36.9(7) . . . . ? C7 P1 C1 C2 32.8(8) . . . . ? Au1 P1 C1 C2 154.5(3) . . . . ? C13 P1 C1 C6 102.5(11) . . . . ? C13A P1 C1 C6 102.4(5) . . . . ? C7A P1 C1 C6 -140.6(6) . . . . ? C7 P1 C1 C6 -144.6(8) . . . . ? Au1 P1 C1 C6 -23.0(4) . . . . ? C6 C1 C2 F1 -177.3(4) . . . . ? P1 C1 C2 F1 5.3(6) . . . . ? C6 C1 C2 C3 2.5(7) . . . . ? P1 C1 C2 C3 -174.8(4) . . . . ? F1 C2 C3 F2 -1.2(7) . . . . ? C1 C2 C3 F2 179.0(4) . . . . ? F1 C2 C3 C4 -179.8(4) . . . . ? C1 C2 C3 C4 0.4(7) . . . . ? F2 C3 C4 F3 0.2(7) . . . . ? C2 C3 C4 F3 178.8(4) . . . . ? F2 C3 C4 C5 179.6(4) . . . . ? C2 C3 C4 C5 -1.8(7) . . . . ? F3 C4 C5 F4 -0.8(7) . . . . ? C3 C4 C5 F4 179.8(4) . . . . ? F3 C4 C5 C6 179.6(4) . . . . ? C3 C4 C5 C6 0.2(7) . . . . ? F4 C5 C6 C1 -176.9(4) . . . . ? C4 C5 C6 C1 2.6(7) . . . . ? F4 C5 C6 Au2 12.2(6) . . . . ? C4 C5 C6 Au2 -168.3(4) . . . . ? C2 C1 C6 C5 -3.9(6) . . . . ? P1 C1 C6 C5 173.6(3) . . . . ? C2 C1 C6 Au2 167.3(3) . . . . ? P1 C1 C6 Au2 -15.1(4) . . . . ? C43 Au2 C6 C5 36.1(4) . . . . ? Au1 Au2 C6 C5 -149.5(4) . . . . ? C43 Au2 C6 C1 -134.6(3) . . . . ? Au1 Au2 C6 C1 39.9(3) . . . . ? C1 P1 C7 C8 -146(2) . . . . ? C13 P1 C7 C8 -31(2) . . . . ? C13A P1 C7 C8 -33(2) . . . . ? C7A P1 C7 C8 -175(11) . . . . ? Au1 P1 C7 C8 94(2) . . . . ? C1 P1 C7 C12 44(3) . . . . ? C13 P1 C7 C12 160(3) . . . . ? C13A P1 C7 C12 157(3) . . . . ? C7A P1 C7 C12 15(8) . . . . ? Au1 P1 C7 C12 -76(3) . . . . ? C12 C7 C8 C9 -9(5) . . . . ? P1 C7 C8 C9 -178(2) . . . . ? C7 C8 C9 C10 5(5) . . . . ? C8 C9 C10 C11 0(7) . . . . ? C9 C10 C11 C12 0(7) . . . . ? C8 C7 C12 C11 8(7) . . . . ? P1 C7 C12 C11 178(4) . . . . ? C10 C11 C12 C7 -4(8) . . . . ? C1 P1 C7A C8A -140.2(15) . . . . ? C13 P1 C7A C8A -24.7(18) . . . . ? C13A P1 C7A C8A -27.3(17) . . . . ? C7 P1 C7A C8A 12(8) . . . . ? Au1 P1 C7A C8A 104.8(15) . . . . ? C1 P1 C7A C12A 42(3) . . . . ? C13 P1 C7A C12A 158(3) . . . . ? C13A P1 C7A C12A 155(2) . . . . ? C7 P1 C7A C12A -165(11) . . . . ? Au1 P1 C7A C12A -73(3) . . . . ? C12A C7A C8A C9A 4(4) . . . . ? P1 C7A C8A C9A -173.6(17) . . . . ? C7A C8A C9A C10A -3(4) . . . . ? C8A C9A C10A C11A 1(5) . . . . ? C9A C10A C11A C12A 0(5) . . . . ? C8A C7A C12A C11A -3(5) . . . . ? P1 C7A C12A C11A 174(3) . . . . ? C10A C11A C12A C7A 1(6) . . . . ? C1 P1 C13 C18 53(3) . . . . ? C13A P1 C13 C18 57(27) . . . . ? C7A P1 C13 C18 -59(3) . . . . ? C7 P1 C13 C18 -64(3) . . . . ? Au1 P1 C13 C18 174(2) . . . . ? C1 P1 C13 C14 -123(3) . . . . ? C13A P1 C13 C14 -119(31) . . . . ? C7A P1 C13 C14 125(3) . . . . ? C7 P1 C13 C14 120(3) . . . . ? Au1 P1 C13 C14 -2(3) . . . . ? C18 C13 C14 C15 0(5) . . . . ? P1 C13 C14 C15 176(2) . . . . ? C13 C14 C15 C16 5(5) . . . . ? C14 C15 C16 C17 -8(6) . . . . ? C15 C16 C17 C18 7(6) . . . . ? C14 C13 C18 C17 -1(5) . . . . ? P1 C13 C18 C17 -177(2) . . . . ? C16 C17 C18 C13 -2(5) . . . . ? C1 P1 C13A C14A -162.0(9) . . . . ? C13 P1 C13A C14A 22(28) . . . . ? C7A P1 C13A C14A 87.1(12) . . . . ? C7 P1 C13A C14A 81.7(13) . . . . ? Au1 P1 C13A C14A -42.3(12) . . . . ? C1 P1 C13A C18A 15.0(11) . . . . ? C13 P1 C13A C18A -161(30) . . . . ? C7A P1 C13A C18A -95.9(12) . . . . ? C7 P1 C13A C18A -101.2(13) . . . . ? Au1 P1 C13A C18A 134.8(9) . . . . ? C18A C13A C14A C15A 1.8(17) . . . . ? P1 C13A C14A C15A 178.9(8) . . . . ? C13A C14A C15A C16A -2.4(16) . . . . ? C14A C15A C16A C17A 2.1(17) . . . . ? C15A C16A C17A C18A -1.2(18) . . . . ? C14A C13A C18A C17A -0.9(17) . . . . ? P1 C13A C18A C17A -178.0(8) . . . . ? C16A C17A C18A C13A 0.6(16) . . . . ? C31 P2 C19 C20 -83(2) . . . . ? C31A P2 C19 C20 -90.3(7) . . . . ? C25A P2 C19 C20 24.9(6) . . . . ? C25 P2 C19 C20 32.1(11) . . . . ? Au2 P2 C19 C20 148.7(4) . . . . ? C31 P2 C19 C24 99(2) . . . . ? C31A P2 C19 C24 92.0(6) . . . . ? C25A P2 C19 C24 -152.8(4) . . . . ? C25 P2 C19 C24 -145.6(10) . . . . ? Au2 P2 C19 C24 -29.0(4) . . . . ? C24 C19 C20 F5 -177.1(4) . . . . ? P2 C19 C20 F5 5.4(7) . . . . ? C24 C19 C20 C21 3.5(7) . . . . ? P2 C19 C20 C21 -174.1(4) . . . . ? F5 C20 C21 F6 -1.1(7) . . . . ? C19 C20 C21 F6 178.4(4) . . . . ? F5 C20 C21 C22 179.8(4) . . . . ? C19 C20 C21 C22 -0.8(7) . . . . ? F6 C21 C22 F7 -0.4(7) . . . . ? C20 C21 C22 F7 178.8(4) . . . . ? F6 C21 C22 C23 179.0(4) . . . . ? C20 C21 C22 C23 -1.8(7) . . . . ? F7 C22 C23 F8 0.8(6) . . . . ? C21 C22 C23 F8 -178.6(4) . . . . ? F7 C22 C23 C24 -178.8(4) . . . . ? C21 C22 C23 C24 1.7(7) . . . . ? F8 C23 C24 C19 -178.7(4) . . . . ? C22 C23 C24 C19 0.9(7) . . . . ? F8 C23 C24 Au1 8.5(6) . . . . ? C22 C23 C24 Au1 -172.0(3) . . . . ? C20 C19 C24 C23 -3.5(6) . . . . ? P2 C19 C24 C23 174.3(3) . . . . ? C20 C19 C24 Au1 169.6(3) . . . . ? P2 C19 C24 Au1 -12.6(5) . . . . ? C37 Au1 C24 C23 40.4(4) . . . . ? Au2 Au1 C24 C23 -145.7(4) . . . . ? C37 Au1 C24 C19 -132.2(4) . . . . ? Au2 Au1 C24 C19 41.7(3) . . . . ? C31 P2 C25 C30 -3(3) . . . . ? C31A P2 C25 C30 0(3) . . . . ? C19 P2 C25 C30 -117(3) . . . . ? C25A P2 C25 C30 16(8) . . . . ? Au2 P2 C25 C30 130(3) . . . . ? C31 P2 C25 C26 175(3) . . . . ? C31A P2 C25 C26 179(3) . . . . ? C19 P2 C25 C26 62(3) . . . . ? C25A P2 C25 C26 -166(13) . . . . ? Au2 P2 C25 C26 -51(3) . . . . ? C30 C25 C26 C27 0(5) . . . . ? P2 C25 C26 C27 -179(3) . . . . ? C25 C26 C27 C28 1(6) . . . . ? C26 C27 C28 C29 0(5) . . . . ? C27 C28 C29 C30 0(5) . . . . ? C28 C29 C30 C25 1(4) . . . . ? C26 C25 C30 C29 -1(5) . . . . ? P2 C25 C30 C29 178(2) . . . . ? C31 P2 C25A C26A 160.5(10) . . . . ? C31A P2 C25A C26A 163.9(8) . . . . ? C19 P2 C25A C26A 48.6(10) . . . . ? C25 P2 C25A C26A -1(9) . . . . ? Au2 P2 C25A C26A -70.5(9) . . . . ? C31 P2 C25A C30A -28.7(11) . . . . ? C31A P2 C25A C30A -25.3(10) . . . . ? C19 P2 C25A C30A -140.7(8) . . . . ? C25 P2 C25A C30A 169(11) . . . . ? Au2 P2 C25A C30A 100.3(9) . . . . ? C30A C25A C26A C27A 1.1(16) . . . . ? P2 C25A C26A C27A 172.0(8) . . . . ? C25A C26A C27A C28A -0.8(15) . . . . ? C26A C27A C28A C29A 0.0(14) . . . . ? C27A C28A C29A C30A 0.5(13) . . . . ? C28A C29A C30A C25A -0.2(13) . . . . ? C26A C25A C30A C29A -0.6(15) . . . . ? P2 C25A C30A C29A -171.1(8) . . . . ? C31A P2 C31 C32 101(13) . . . . ? C19 P2 C31 C32 8(6) . . . . ? C25A P2 C31 C32 -107(5) . . . . ? C25 P2 C31 C32 -104(6) . . . . ? Au2 P2 C31 C32 128(5) . . . . ? C31A P2 C31 C36 -79(7) . . . . ? C19 P2 C31 C36 -172(4) . . . . ? C25A P2 C31 C36 73(4) . . . . ? C25 P2 C31 C36 76(4) . . . . ? Au2 P2 C31 C36 -52(5) . . . . ? C36 C31 C32 C33 8(11) . . . . ? P2 C31 C32 C33 -172(8) . . . . ? C31 C32 C33 C34 -8(13) . . . . ? C32 C33 C34 C35 3(11) . . . . ? C33 C34 C35 C36 3(8) . . . . ? C34 C35 C36 C31 -3(6) . . . . ? C32 C31 C36 C35 -2(7) . . . . ? P2 C31 C36 C35 178(3) . . . . ? C31 P2 C31A C32A -58(10) . . . . ? C19 P2 C31A C32A 31.1(16) . . . . ? C25A P2 C31A C32A -86.5(16) . . . . ? C25 P2 C31A C32A -84(2) . . . . ? Au2 P2 C31A C32A 147.4(15) . . . . ? C31 P2 C31A C36A 121(11) . . . . ? C19 P2 C31A C36A -149.9(11) . . . . ? C25A P2 C31A C36A 92.5(13) . . . . ? C25 P2 C31A C36A 95.0(18) . . . . ? Au2 P2 C31A C36A -33.6(14) . . . . ? C36A C31A C32A C33A -2(3) . . . . ? P2 C31A C32A C33A 177(3) . . . . ? C31A C32A C33A C34A 1(4) . . . . ? C32A C33A C34A C35A 0(3) . . . . ? C33A C34A C35A C36A 0(2) . . . . ? C34A C35A C36A C31A -1.0(18) . . . . ? C32A C31A C36A C35A 2.2(19) . . . . ? P2 C31A C36A C35A -176.8(9) . . . . ? C24 Au1 C37 C42 -98.3(4) . . . . ? P1 Au1 C37 C42 81.1(4) . . . . ? C24 Au1 C37 C38 90.7(4) . . . . ? P1 Au1 C37 C38 -89.8(3) . . . . ? C42 C37 C38 F9 179.7(4) . . . . ? Au1 C37 C38 F9 -8.7(5) . . . . ? C42 C37 C38 C39 -0.6(6) . . . . ? Au1 C37 C38 C39 171.1(3) . . . . ? F9 C38 C39 F10 0.2(6) . . . . ? C37 C38 C39 F10 -179.5(4) . . . . ? F9 C38 C39 C40 -178.7(4) . . . . ? C37 C38 C39 C40 1.5(7) . . . . ? F10 C39 C40 F11 1.0(7) . . . . ? C38 C39 C40 F11 179.9(4) . . . . ? F10 C39 C40 C41 179.4(4) . . . . ? C38 C39 C40 C41 -1.7(7) . . . . ? F11 C40 C41 F12 -1.2(7) . . . . ? C39 C40 C41 F12 -179.6(4) . . . . ? F11 C40 C41 C42 179.4(4) . . . . ? C39 C40 C41 C42 1.0(7) . . . . ? C38 C37 C42 F13 179.4(4) . . . . ? Au1 C37 C42 F13 8.1(6) . . . . ? C38 C37 C42 C41 -0.2(7) . . . . ? Au1 C37 C42 C41 -171.4(3) . . . . ? F12 C41 C42 F13 1.0(6) . . . . ? C40 C41 C42 F13 -179.6(4) . . . . ? F12 C41 C42 C37 -179.5(4) . . . . ? C40 C41 C42 C37 -0.1(7) . . . . ? C6 Au2 C43 C48 -98.5(4) . . . . ? P2 Au2 C43 C48 84.4(4) . . . . ? C6 Au2 C43 C44 89.4(4) . . . . ? P2 Au2 C43 C44 -87.6(3) . . . . ? C48 C43 C44 F14 179.3(4) . . . . ? Au2 C43 C44 F14 -8.1(6) . . . . ? C48 C43 C44 C45 0.3(7) . . . . ? Au2 C43 C44 C45 172.9(4) . . . . ? F14 C44 C45 F15 1.4(7) . . . . ? C43 C44 C45 F15 -179.6(4) . . . . ? F14 C44 C45 C46 -178.6(4) . . . . ? C43 C44 C45 C46 0.4(7) . . . . ? F15 C45 C46 F16 0.2(7) . . . . ? C44 C45 C46 F16 -179.8(4) . . . . ? F15 C45 C46 C47 -179.8(5) . . . . ? C44 C45 C46 C47 0.1(8) . . . . ? F16 C46 C47 F17 0.1(8) . . . . ? C45 C46 C47 F17 -179.8(5) . . . . ? F16 C46 C47 C48 178.5(5) . . . . ? C45 C46 C47 C48 -1.4(8) . . . . ? F17 C47 C48 F18 -1.5(8) . . . . ? C46 C47 C48 F18 -179.9(4) . . . . ? F17 C47 C48 C43 -179.4(5) . . . . ? C46 C47 C48 C43 2.2(8) . . . . ? C44 C43 C48 F18 -179.5(4) . . . . ? Au2 C43 C48 F18 8.3(6) . . . . ? C44 C43 C48 C47 -1.7(7) . . . . ? Au2 C43 C48 C47 -173.9(4) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 29.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 3.005 _refine_diff_density_min -1.953 _refine_diff_density_rms 0.167 # Attachment 'neda_repeat_ben0608.cif.txt' data_neda_repeat_ben0608 _database_code_depnum_ccdc_archive 'CCDC 726007' _publ_section_abstract ; Treatment of [AuXL] (X = Br, L = AsPh3; X = Cl, L = tht) with the lithium or trimethyltin derivatives of the carbanions [2-C6F4PPh2] and [C6H3-n-F-2-PPh2] (n = 5, 6) gives digold(I) complexes [Au2(m-carbanion)2] (carbanion = 2-C6F4PPh2 2, C6H3-5-F-2-PPh2 3, C6H3-6-F-2-PPh2 4) which, like their 2?C6H4PPh2 counterpart, undergo oxidative addition with halogens X2 (X = Cl, Br, I) to give the corresponding, metal-metal bonded digold(II) complexes [Au2X2(m-carbanion)2] (carbanion = 2?C6F4PPh2, X = Cl 5, Br 8, I 11; carbanion = C6H3-5-F-2-PPh2, X = Cl 6, Br 9, I 12; carbanion = C6H3-6-F-2-PPh2, X = Cl 7, Br 10, I 13). In the case of 2-C6F4PPh2 and C6H3-6-F-2-PPh2, the dihalodigold(II) complexes rearrange on heating to isomeric gold(I)-gold(III) complexes [XAuI(m-P,C-carbanion)(k2-P,C-carbanion)AuIIIX] (carbanion = 2-C6F4PPh2, X = Cl 25, Br 26, I 27; carbanion = C6H3-6-F-2-PPh2, X = Cl 28, Br 29, I 30), in which one of the carbanions chelates to the gold(III) atom. This isomerisation is similar to, but occurs more slowly than that in the corresponding C6H3-6-Me-2-PPh2 system. The Au2X2 complexes 6 and 9, on the other hand, rearrange on heating via C-C coupling to give digold(I) complexes of the corresponding 2,2'-biphenylyldiphenylphosphine, [Au2X2(2,2'-Ph2P-5-F-C6H3C6H3-5-F-PPh2)] (X = Cl 32, Br 33, I 34), this behaviour resembling that of the 2-C6H4PPh2 and C6H3-5-Me-2-PPh2 systems. Since the C-C coupling probably occurs via undetected gold(I)-gold(III) intermediates, the presence of a 6-fluoro substituent is evidently sufficient to suppress the reductive eliminations, possibly because of an electronic effect that strengthens the gold(III)-aryl bond. Anation of 5 or 8 gives the bis(oxyanion)digold(II) complexes [Au2Y2(m-2-C6F4PPh2)2] (Y = OAc 14, ONO2 15, OBz 16, O2CCF3 17 and OTf 20), which do not isomerise to the corresponding gold(I)-gold(III) complexes [YAu(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuY] on heating, though the latter [Y = OAc 35, ONO2 36, OBz 37, O2CCF3 38] can be made by anation of 25-27. Reaction of the bis(benzoato)digold(II) complex 16 with dimethylzinc gives a dimethyl gold(I)-gold(III) complex, [AuI(m-2-C6F4PPh2)2AuIII(CH3)2] 19, in which both 2-C6F4PPh2 groups are bridging. In contrast, the corresponding reaction of 16 with C6F5Li gives a digold(II) complex [AuII2(C6F5)2(m-2-C6F4PPh2)2] 18, which on heating isomerises to a gold(I)-gold(III) complex, [(C6F5)AuI(m-2-C6F4PPh2)(k2-2-C6F4PPh2)AuIII(C6F5)] 31, analogous to 25-27. The bis(triflato)digold(II) complex 20 is reduced by methanol or cyclohexanol in CH2Cl2 to a tetranuclear gold(I) complex [Au4(m-2-C6F4PPh2)4] 21 in which the four carbanions bridge a square array of metal atoms, as shown by a single-crystal X-ray diffraction study. The corresponding tetramers [Au4(m-C6H3-n-F-2-PPh2)4] (n = 5 22, 6 23) are formed as minor by-product in the preparation of dimers 3 and 4; the tetramers do not interconvert readily with, and are not in equilibrium with the corresponding dimers 2-4. Addition of an excess of chlorine or bromine (X2) to the digold(II) complexes 5 and 8, and to their gold(I)-gold(III) isomers 25 and 26, gives isomeric digold(III) complexes [Au2X4(m-2-C6F4PPh2)2] (X = Cl 39, Br 40) and [X3Au(m-2-C6F4PPh2)AuX(k2-2-C6F4PPh2)] (X = Cl 41, Br 42), respectively. The structures of the digold(I) complexes 2, 4 and 32, the digold(II) complexes 5-11 and 14-18, the gold(I)-gold(III) complexes 19, 25, 35 and 38, the tetragold(I) complexes 21 and 22, and the digold(III) complexes 41 and 42, have been determined by single-crystal X-ray diffraction. In the digold(II) (5d9-5d9) series, there is a systematic lengthening, and presumably weakening, of the Au-Au distance in the range 2.5012(4)-2.5885(2) \%A with increasing trans-influence of the axial ligand, in the order X = NO2 < O2CCF3 < OBz < Cl < Br < I < C6F5. The strength of the Au-Au interaction is probably the main factor that determines whether the digold(II) compounds isomerise to gold(I)-gold(III). The gold-gold separations in the digold(I) and gold(I)-gold(III) complexes are in the range 2.8-3.6 \%A suggestive of aurophilic interactions, but these are probably absent in the digold(III) compounds (Au...Au separation ca. 5.8 \%A). Attempted recrystallisation of complex 10 gave a trinuclear gold(II)-gold(II)-gold(I) complex, [Au3Br2(m-C6H3-6-F-2-PPh2)3] 24, which consists of the expected digold(II) framework in which one of the axial bromide ligands has been replaced by a s-carbon bonded (C6H3-6-F-2-PPh2)AuIBr fragment. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '2(C40 H20 Au2 F14 O4 P2), 0.89(C H2 Cl2)' _chemical_formula_sum 'C80.89 H41.78 Au4 Cl1.78 F28 O8 P4' _chemical_formula_weight 2648.45 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Au Au -2.0133 8.8022 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall -P1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.17170(10) _cell_length_b 19.9849(2) _cell_length_c 21.4899(3) _cell_angle_alpha 64.4990(10) _cell_angle_beta 80.8060(10) _cell_angle_gamma 75.6400(10) _cell_volume 4187.51(9) _cell_formula_units_Z 2 _cell_measurement_temperature 130(2) _cell_measurement_reflns_used 46693 _cell_measurement_theta_min 2.546 _cell_measurement_theta_max 27.485 _exptl_crystal_description piece _exptl_crystal_colour colorless _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.100 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2499 _exptl_absorpt_coefficient_mu 7.236 _exptl_absorpt_correction_type integration _exptl_absorpt_correction_T_min 0.324 _exptl_absorpt_correction_T_max 0.470 _exptl_absorpt_process_details ; Gaussian integration (Coppens, 1970) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 130(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Nonius Kappa CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 73448 _diffrn_reflns_av_R_equivalents 0.0427 _diffrn_reflns_av_sigmaI/netI 0.0363 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 25 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.66 _diffrn_reflns_theta_max 27.50 _reflns_number_total 19224 _reflns_number_gt 15668 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Nonius Collect, KappaCCD' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'Denzo and Scalepak (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP32 for windows (Farugia)' _computing_publication_material 'Ciftab (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0551P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.00114(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 19224 _refine_ls_number_parameters 1208 _refine_ls_number_restraints 157 _refine_ls_R_factor_all 0.0466 _refine_ls_R_factor_gt 0.0337 _refine_ls_wR_factor_ref 0.0906 _refine_ls_wR_factor_gt 0.0847 _refine_ls_goodness_of_fit_ref 1.047 _refine_ls_restrained_S_all 1.079 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Au1 Au 0.518748(16) 0.824594(9) 0.452728(9) 0.02876(6) Uani 1 1 d . . . Au2 Au 0.304814(16) 0.895433(10) 0.416217(9) 0.03049(6) Uani 1 1 d . . . P1 P 0.44542(12) 0.71981(7) 0.46394(6) 0.0322(3) Uani 1 1 d . . . P2 P 0.41463(11) 0.98275(7) 0.33163(6) 0.0302(2) Uani 1 1 d . . . F1 F 0.2925(3) 0.59986(19) 0.56532(19) 0.0653(10) Uani 1 1 d . . . F2 F 0.0819(4) 0.6277(2) 0.63795(19) 0.0787(12) Uani 1 1 d . . . F3 F -0.0315(4) 0.7717(3) 0.6158(2) 0.0819(13) Uani 1 1 d . . . F4 F 0.0677(3) 0.8883(2) 0.5259(2) 0.0662(10) Uani 1 1 d . . . F5 F 0.5276(3) 1.12146(17) 0.31211(17) 0.0538(8) Uani 1 1 d . . . F6 F 0.6722(3) 1.12305(17) 0.39992(18) 0.0562(8) Uani 1 1 d . . . F7 F 0.7479(3) 0.99594(17) 0.51223(16) 0.0479(7) Uani 1 1 d . . . F8 F 0.6714(3) 0.86907(16) 0.54142(14) 0.0447(7) Uani 1 1 d . . . O2A O 0.745(8) 0.734(3) 0.3952(9) 0.073(5) Uani 0.55 1 d PD A 1 C38A C 0.8987(7) 0.7029(4) 0.4724(5) 0.059(2) Uani 0.55 1 d PD A 1 F9A F 0.8988(12) 0.6600(6) 0.5389(5) 0.094(3) Uani 0.55 1 d PDU A 1 F10A F 0.9645(9) 0.7548(5) 0.4559(5) 0.100(2) Uani 0.55 1 d PDU A 1 F11A F 0.9611(9) 0.6593(6) 0.4418(5) 0.094(2) Uani 0.55 1 d PDU A 1 O2B O 0.745(10) 0.748(4) 0.3897(11) 0.073(5) Uani 0.45 1 d PD A 2 C38B C 0.8886(8) 0.6851(5) 0.4784(6) 0.059(2) Uani 0.45 1 d PD A 2 F9B F 0.9065(16) 0.6852(8) 0.5372(7) 0.094(2) Uani 0.45 1 d PD A 2 F10B F 0.9823(10) 0.7127(8) 0.4390(6) 0.094(3) Uani 0.45 1 d PD A 2 F11B F 0.9007(11) 0.6157(6) 0.4844(7) 0.100(2) Uani 0.45 1 d PD A 2 O4A O 0.152(6) 0.9202(17) 0.297(2) 0.088(7) Uani 0.61 1 d PD B 3 C40A C -0.0456(7) 0.9787(5) 0.3243(4) 0.073(3) Uani 0.61 1 d PD B 3 F12A F -0.0674(8) 0.9992(6) 0.2595(5) 0.103(2) Uani 0.61 1 d PDU B 3 F13A F -0.1167(8) 0.9302(6) 0.3628(5) 0.110(3) Uani 0.61 1 d PDU B 3 F14A F -0.0950(11) 1.0290(5) 0.3502(5) 0.085(3) Uani 0.61 1 d PDU B 3 O4B O 0.150(9) 0.903(3) 0.311(4) 0.088(7) Uani 0.39 1 d PD B 4 C40B C -0.0312(8) 0.9980(7) 0.3082(7) 0.073(3) Uani 0.39 1 d PD B 4 F12B F -0.0321(13) 1.0480(8) 0.2435(7) 0.103(2) Uani 0.39 1 d PD B 4 F13B F -0.1080(14) 0.9541(9) 0.3161(9) 0.110(3) Uani 0.39 1 d PD B 4 F14B F -0.0785(18) 1.0538(8) 0.3275(8) 0.085(3) Uani 0.39 1 d PD B 4 O1 O 0.6964(3) 0.76421(19) 0.48668(18) 0.0389(8) Uani 1 1 d D A . O3 O 0.1252(3) 0.9553(2) 0.3853(2) 0.0471(9) Uani 1 1 d D B . C1 C 0.2946(5) 0.7318(3) 0.5076(3) 0.0387(11) Uani 1 1 d . . . C2 C 0.2407(5) 0.6725(3) 0.5537(3) 0.0486(13) Uani 1 1 d . . . C3 C 0.1325(6) 0.6849(4) 0.5914(3) 0.0539(15) Uani 1 1 d . . . C4 C 0.0770(6) 0.7572(4) 0.5806(3) 0.0567(16) Uani 1 1 d . . . C5 C 0.1277(5) 0.8184(3) 0.5328(3) 0.0487(14) Uani 1 1 d . . . C6 C 0.2347(5) 0.8068(3) 0.4948(2) 0.0390(11) Uani 1 1 d . . . C7 C 0.5361(5) 0.6321(3) 0.5205(2) 0.0387(11) Uani 1 1 d . . . C8 C 0.5810(6) 0.5707(3) 0.5024(3) 0.0514(14) Uani 1 1 d . . . H8 H 0.5678 0.5744 0.4584 0.062 Uiso 1 1 calc R . . C9 C 0.6455(7) 0.5038(3) 0.5504(4) 0.070(2) Uani 1 1 d . . . H9 H 0.6764 0.4616 0.5389 0.084 Uiso 1 1 calc R . . C10 C 0.6652(7) 0.4982(3) 0.6143(4) 0.078(2) Uani 1 1 d . . . H10 H 0.7086 0.4521 0.6467 0.093 Uiso 1 1 calc R . . C11 C 0.6214(7) 0.5601(4) 0.6316(3) 0.071(2) Uani 1 1 d . . . H11 H 0.6353 0.5562 0.6756 0.085 Uiso 1 1 calc R . . C12 C 0.5578(6) 0.6270(3) 0.5847(3) 0.0537(15) Uani 1 1 d . . . H12 H 0.5289 0.6694 0.5961 0.064 Uiso 1 1 calc R . . C13 C 0.4240(5) 0.7114(3) 0.3862(2) 0.0354(10) Uani 1 1 d . . . C14 C 0.5240(6) 0.7050(3) 0.3406(3) 0.0476(13) Uani 1 1 d . . . H14 H 0.6035 0.7073 0.3490 0.057 Uiso 1 1 calc R . . C15 C 0.5078(7) 0.6953(3) 0.2828(3) 0.0576(16) Uani 1 1 d . . . H15 H 0.5769 0.6902 0.2519 0.069 Uiso 1 1 calc R . . C16 C 0.3924(7) 0.6929(3) 0.2696(3) 0.0613(18) Uani 1 1 d . . . H16 H 0.3818 0.6862 0.2297 0.074 Uiso 1 1 calc R . . C17 C 0.2940(7) 0.7001(3) 0.3142(3) 0.0589(16) Uani 1 1 d . . . H17 H 0.2145 0.6987 0.3049 0.071 Uiso 1 1 calc R . . C18 C 0.3071(5) 0.7095(3) 0.3730(3) 0.0441(12) Uani 1 1 d . . . H18 H 0.2375 0.7145 0.4037 0.053 Uiso 1 1 calc R . . C19 C 0.5214(4) 0.9922(3) 0.3809(2) 0.0315(10) Uani 1 1 d . . . C20 C 0.5608(5) 1.0580(3) 0.3678(3) 0.0383(11) Uani 1 1 d . . . C21 C 0.6374(5) 1.0592(3) 0.4120(3) 0.0392(11) Uani 1 1 d . . . C22 C 0.6732(4) 0.9953(3) 0.4694(3) 0.0365(11) Uani 1 1 d . . . C23 C 0.6348(4) 0.9291(3) 0.4827(2) 0.0341(10) Uani 1 1 d . . . C24 C 0.5613(4) 0.9254(2) 0.4398(2) 0.0299(9) Uani 1 1 d . . . C25 C 0.3269(5) 1.0737(3) 0.2774(3) 0.0358(10) Uani 1 1 d . . . C26 C 0.2244(6) 1.1088(3) 0.3058(3) 0.0520(15) Uani 1 1 d . . . H26 H 0.2015 1.0862 0.3537 0.062 Uiso 1 1 calc R . . C27 C 0.1562(7) 1.1766(4) 0.2637(3) 0.0657(19) Uani 1 1 d . . . H27 H 0.0860 1.2010 0.2829 0.079 Uiso 1 1 calc R . . C28 C 0.1882(6) 1.2098(3) 0.1940(3) 0.0554(15) Uani 1 1 d . . . H28 H 0.1398 1.2565 0.1655 0.067 Uiso 1 1 calc R . . C29 C 0.2896(5) 1.1755(3) 0.1659(3) 0.0479(13) Uani 1 1 d . . . H29 H 0.3120 1.1985 0.1179 0.057 Uiso 1 1 calc R . . C30 C 0.3596(5) 1.1071(3) 0.2077(3) 0.0413(11) Uani 1 1 d . . . H30 H 0.4302 1.0832 0.1883 0.050 Uiso 1 1 calc R . . C31 C 0.5066(4) 0.9417(2) 0.2753(2) 0.0313(9) Uani 1 1 d . . . C32 C 0.4485(5) 0.9074(3) 0.2468(3) 0.0419(12) Uani 1 1 d . . . H32 H 0.3629 0.9063 0.2572 0.050 Uiso 1 1 calc R . . C33 C 0.5171(6) 0.8752(3) 0.2038(3) 0.0482(13) Uani 1 1 d . . . H33 H 0.4784 0.8519 0.1844 0.058 Uiso 1 1 calc R . . C34 C 0.6410(6) 0.8766(3) 0.1886(3) 0.0554(16) Uani 1 1 d . . . H34 H 0.6872 0.8541 0.1588 0.066 Uiso 1 1 calc R . . C35 C 0.6986(5) 0.9101(3) 0.2160(3) 0.0557(15) Uani 1 1 d . . . H35 H 0.7841 0.9111 0.2051 0.067 Uiso 1 1 calc R . . C36 C 0.6318(5) 0.9426(3) 0.2597(3) 0.0441(12) Uani 1 1 d . . . H36 H 0.6717 0.9655 0.2790 0.053 Uiso 1 1 calc R . . C37 C 0.7651(5) 0.7373(3) 0.4470(3) 0.0425(12) Uani 1 1 d D . . C39 C 0.0933(5) 0.9467(3) 0.3359(3) 0.0553(15) Uani 1 1 d D . . Au3 Au 1.162750(15) 0.624671(9) 0.082344(9) 0.02796(6) Uani 1 1 d . . . Au4 Au 0.940522(16) 0.680343(9) 0.055264(8) 0.02725(5) Uani 1 1 d . . . P3 P 1.08301(11) 0.52353(6) 0.16988(6) 0.0290(2) Uani 1 1 d . . . P4 P 0.99110(11) 0.79162(6) 0.04551(6) 0.0308(2) Uani 1 1 d . . . F15 F 1.0041(3) 0.37551(16) 0.18793(17) 0.0543(8) Uani 1 1 d . . . F16 F 0.8683(3) 0.36316(18) 0.10283(18) 0.0605(9) Uani 1 1 d . . . F17 F 0.7636(3) 0.48721(18) -0.00342(16) 0.0533(8) Uani 1 1 d . . . F18 F 0.8034(3) 0.62385(16) -0.03022(15) 0.0447(7) Uani 1 1 d . . . F19 F 1.1140(3) 0.92715(17) -0.06004(19) 0.0618(10) Uani 1 1 d . . . F20 F 1.3172(4) 0.9154(2) -0.1437(2) 0.0902(15) Uani 1 1 d . . . F21 F 1.4437(4) 0.7785(2) -0.1358(2) 0.0758(12) Uani 1 1 d . . . F22 F 1.3745(3) 0.65176(17) -0.04316(16) 0.0502(8) Uani 1 1 d . . . C78A C 1.5290(6) 0.5487(5) 0.1596(7) 0.046(2) Uani 0.64 1 d PD C 5 F23A F 1.5682(6) 0.4857(5) 0.1422(5) 0.0884(19) Uani 0.64 1 d PU C 5 F24A F 1.5900(8) 0.5932(5) 0.1201(6) 0.111(3) Uani 0.64 1 d PU C 5 F25A F 1.5610(7) 0.5203(6) 0.2236(4) 0.104(2) Uani 0.64 1 d PU C 5 C78B C 1.5209(9) 0.5262(11) 0.1696(16) 0.046(2) Uani 0.36 1 d PD C 6 F23B F 1.5712(12) 0.5731(9) 0.1920(9) 0.0884(19) Uani 0.36 1 d P C 6 F24B F 1.5481(13) 0.4687(9) 0.1955(10) 0.111(3) Uani 0.36 1 d P C 6 F25B F 1.5871(15) 0.5643(12) 0.1018(8) 0.104(2) Uani 0.36 1 d P C 6 C80A C 0.5544(6) 0.7855(4) 0.0420(4) 0.0519(15) Uani 0.48 1 d PD D 7 F26A F 0.4822(4) 0.7907(8) 0.0943(5) 0.090(2) Uani 0.48 1 d PDU D 7 F27A F 0.5061(6) 0.7446(6) 0.0231(7) 0.097(2) Uani 0.48 1 d PDU D 7 F28A F 0.5384(6) 0.8518(6) -0.0098(7) 0.109(3) Uani 0.48 1 d PDU D 7 C80B C 0.5515(6) 0.7881(4) 0.0477(4) 0.0519(15) Uani 0.52 1 d PD D 8 F26B F 0.5317(7) 0.8003(8) -0.0148(4) 0.090(2) Uani 0.52 1 d PD D 8 F27B F 0.4747(5) 0.7462(6) 0.0887(6) 0.109(3) Uani 0.52 1 d PD D 8 F28B F 0.5192(5) 0.8544(5) 0.0497(7) 0.097(2) Uani 0.52 1 d PD D 8 O5 O 1.3516(3) 0.5803(2) 0.09867(19) 0.0436(9) Uani 1 1 d . C . O6 O 1.3235(4) 0.5831(3) 0.2030(2) 0.0608(11) Uani 1 1 d . C . O7 O 0.7557(3) 0.73113(19) 0.02525(17) 0.0360(8) Uani 1 1 d . D . O8 O 0.7057(4) 0.7370(3) 0.1281(2) 0.0642(12) Uani 1 1 d . D . C41 C 0.9792(4) 0.5087(3) 0.1224(2) 0.0316(10) Uani 1 1 d . . . C42 C 0.9571(5) 0.4382(3) 0.1351(3) 0.0379(11) Uani 1 1 d . . . C43 C 0.8859(5) 0.4312(3) 0.0924(3) 0.0437(12) Uani 1 1 d . . . C44 C 0.8344(5) 0.4943(3) 0.0377(3) 0.0393(11) Uani 1 1 d . . . C45 C 0.8537(4) 0.5650(3) 0.0258(2) 0.0346(10) Uani 1 1 d . . . C46 C 0.9240(4) 0.5740(2) 0.0671(2) 0.0297(9) Uani 1 1 d . . . C47 C 0.9905(4) 0.5433(3) 0.2388(2) 0.0340(10) Uani 1 1 d . . . C48 C 0.8660(5) 0.5435(3) 0.2491(3) 0.0444(12) Uani 1 1 d . . . H48 H 0.8261 0.5342 0.2186 0.053 Uiso 1 1 calc R . . C49 C 0.7975(6) 0.5572(4) 0.3045(3) 0.0577(16) Uani 1 1 d . . . H49 H 0.7108 0.5588 0.3107 0.069 Uiso 1 1 calc R . . C50 C 0.8571(6) 0.5683(4) 0.3502(3) 0.0621(17) Uani 1 1 d . . . H50 H 0.8120 0.5755 0.3889 0.075 Uiso 1 1 calc R . . C51 C 0.9814(6) 0.5687(4) 0.3393(3) 0.0602(16) Uani 1 1 d . . . H51 H 1.0215 0.5774 0.3700 0.072 Uiso 1 1 calc R . . C52 C 1.0488(5) 0.5566(3) 0.2837(3) 0.0487(13) Uani 1 1 d . . . H52 H 1.1347 0.5573 0.2764 0.058 Uiso 1 1 calc R . . C53 C 1.1948(4) 0.4366(3) 0.2092(3) 0.0347(10) Uani 1 1 d . . . C54 C 1.1852(5) 0.3903(3) 0.2792(3) 0.0428(12) Uani 1 1 d . . . H54 H 1.1211 0.4052 0.3082 0.051 Uiso 1 1 calc R . . C55 C 1.2673(6) 0.3234(3) 0.3064(3) 0.0546(15) Uani 1 1 d . . . H55 H 1.2609 0.2922 0.3545 0.065 Uiso 1 1 calc R . . C56 C 1.3595(7) 0.3009(3) 0.2643(4) 0.072(2) Uani 1 1 d . . . H56 H 1.4152 0.2536 0.2832 0.086 Uiso 1 1 calc R . . C57 C 1.3713(7) 0.3467(4) 0.1949(4) 0.071(2) Uani 1 1 d . . . H57 H 1.4357 0.3314 0.1662 0.085 Uiso 1 1 calc R . . C58 C 1.2895(6) 0.4148(3) 0.1672(3) 0.0517(14) Uani 1 1 d . . . H58 H 1.2979 0.4467 0.1195 0.062 Uiso 1 1 calc R . . C59 C 1.1358(5) 0.7935(3) -0.0057(2) 0.0354(10) Uani 1 1 d . . . C60 C 1.1759(5) 0.8573(3) -0.0533(3) 0.0463(13) Uani 1 1 d . . . C61 C 1.2800(6) 0.8523(3) -0.0964(3) 0.0574(16) Uani 1 1 d . . . C62 C 1.3439(5) 0.7825(3) -0.0924(3) 0.0514(14) Uani 1 1 d . . . C63 C 1.3074(5) 0.7185(3) -0.0437(3) 0.0398(11) Uani 1 1 d . . . C64 C 1.2061(4) 0.7210(3) 0.0013(2) 0.0329(10) Uani 1 1 d . . . C65 C 1.0120(4) 0.7959(3) 0.1248(2) 0.0342(10) Uani 1 1 d . . . C66 C 0.9480(5) 0.7556(3) 0.1855(2) 0.0390(11) Uani 1 1 d . . . H66 H 0.9006 0.7220 0.1859 0.047 Uiso 1 1 calc R . . C67 C 0.9539(6) 0.7648(3) 0.2452(3) 0.0519(14) Uani 1 1 d . . . H67 H 0.9114 0.7372 0.2869 0.062 Uiso 1 1 calc R . . C68 C 1.0224(6) 0.8148(3) 0.2437(3) 0.0550(15) Uani 1 1 d . . . H68 H 1.0241 0.8225 0.2841 0.066 Uiso 1 1 calc R . . C69 C 1.0870(7) 0.8527(4) 0.1852(3) 0.0659(18) Uani 1 1 d . . . H69 H 1.1356 0.8854 0.1854 0.079 Uiso 1 1 calc R . . C70 C 1.0823(6) 0.8441(3) 0.1251(3) 0.0517(14) Uani 1 1 d . . . H70 H 1.1272 0.8712 0.0842 0.062 Uiso 1 1 calc R . . C71 C 0.8827(5) 0.8767(3) -0.0011(2) 0.0364(10) Uani 1 1 d . . . C72 C 0.8217(5) 0.9264(3) 0.0288(3) 0.0467(13) Uani 1 1 d . . . H72 H 0.8393 0.9169 0.0740 0.056 Uiso 1 1 calc R . . C73 C 0.7353(6) 0.9895(3) -0.0071(4) 0.0647(17) Uani 1 1 d . . . H73 H 0.6939 1.0234 0.0134 0.078 Uiso 1 1 calc R . . C74 C 0.7095(7) 1.0033(4) -0.0721(4) 0.074(2) Uani 1 1 d . . . H74 H 0.6491 1.0462 -0.0962 0.088 Uiso 1 1 calc R . . C75 C 0.7692(8) 0.9563(4) -0.1026(4) 0.080(2) Uani 1 1 d . . . H75 H 0.7521 0.9675 -0.1483 0.096 Uiso 1 1 calc R . . C76 C 0.8549(6) 0.8918(3) -0.0677(3) 0.0560(16) Uani 1 1 d . . . H76 H 0.8945 0.8583 -0.0888 0.067 Uiso 1 1 calc R . . C77 C 1.3853(5) 0.5719(3) 0.1560(3) 0.0446(12) Uani 1 1 d D . . C79 C 0.6844(5) 0.7462(3) 0.0710(3) 0.0392(11) Uani 1 1 d D . . Cl1A Cl 0.8159(4) 0.2064(3) 0.2277(3) 0.1139(14) Uani 0.61 1 d PD E 9 C81A C 0.6963(11) 0.2755(6) 0.2340(6) 0.081(3) Uani 0.61 1 d PDU E 9 H81A H 0.6727 0.3114 0.1867 0.097 Uiso 0.61 1 calc PR E 9 H81B H 0.6245 0.2519 0.2583 0.097 Uiso 0.61 1 calc PR E 9 Cl2A Cl 0.7228(16) 0.3259(5) 0.2754(5) 0.138(4) Uani 0.61 1 d PD E 9 Cl1B Cl 0.7486(10) 0.2132(7) 0.2226(7) 0.1139(14) Uani 0.28 1 d PD F 10 C81B C 0.813(2) 0.2428(15) 0.2706(13) 0.081(3) Uani 0.28 1 d PD F 10 H81C H 0.8823 0.2669 0.2433 0.097 Uiso 0.28 1 calc PR F 10 H81D H 0.8457 0.1986 0.3122 0.097 Uiso 0.28 1 calc PR F 10 Cl2B Cl 0.707(4) 0.3058(14) 0.2952(13) 0.138(4) Uani 0.28 1 d PD F 10 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Au1 0.02830(10) 0.02979(10) 0.02926(9) -0.01229(7) -0.00120(7) -0.00762(7) Au2 0.02580(10) 0.03534(10) 0.03456(10) -0.01870(8) 0.00101(7) -0.00705(7) P1 0.0360(6) 0.0293(6) 0.0308(6) -0.0093(5) -0.0028(5) -0.0108(5) P2 0.0285(6) 0.0305(6) 0.0330(6) -0.0144(5) -0.0026(5) -0.0051(5) F1 0.064(2) 0.0458(19) 0.075(2) -0.0073(17) 0.0043(19) -0.0291(17) F2 0.071(3) 0.091(3) 0.060(2) -0.005(2) 0.0137(19) -0.051(2) F3 0.063(2) 0.128(4) 0.071(2) -0.055(3) 0.040(2) -0.050(2) F4 0.054(2) 0.078(2) 0.083(3) -0.053(2) 0.0246(19) -0.0193(18) F5 0.065(2) 0.0332(16) 0.062(2) -0.0104(14) -0.0192(17) -0.0142(15) F6 0.067(2) 0.0432(18) 0.073(2) -0.0279(16) -0.0078(18) -0.0250(16) F7 0.0471(18) 0.0572(19) 0.0569(19) -0.0355(16) -0.0116(14) -0.0125(15) F8 0.0511(18) 0.0451(17) 0.0400(16) -0.0175(13) -0.0136(13) -0.0062(14) O2A 0.049(3) 0.121(19) 0.052(3) -0.047(6) -0.010(6) 0.004(13) C38A 0.058(4) 0.068(6) 0.058(4) -0.040(5) -0.007(4) 0.005(4) F9A 0.060(4) 0.106(5) 0.091(4) -0.022(4) -0.016(3) -0.002(4) F10A 0.085(4) 0.090(4) 0.129(5) -0.046(4) -0.024(3) -0.013(3) F11A 0.076(4) 0.120(5) 0.098(4) -0.074(4) -0.024(3) 0.026(4) O2B 0.049(3) 0.121(19) 0.052(3) -0.047(6) -0.010(6) 0.004(13) C38B 0.058(4) 0.068(6) 0.058(4) -0.040(5) -0.007(4) 0.005(4) F9B 0.076(4) 0.120(5) 0.098(4) -0.074(4) -0.024(3) 0.026(4) F10B 0.060(4) 0.106(5) 0.091(4) -0.022(4) -0.016(3) -0.002(4) F11B 0.085(4) 0.090(4) 0.129(5) -0.046(4) -0.024(3) -0.013(3) O4A 0.053(3) 0.139(14) 0.116(19) -0.101(16) -0.026(11) 0.014(12) C40A 0.037(4) 0.110(8) 0.094(8) -0.061(7) -0.018(4) -0.008(5) F12A 0.078(4) 0.124(5) 0.095(4) -0.036(4) -0.028(3) 0.001(4) F13A 0.064(3) 0.122(5) 0.136(6) -0.034(4) -0.015(4) -0.031(3) F14A 0.056(3) 0.084(5) 0.095(5) -0.031(4) -0.006(4) 0.012(4) O4B 0.053(3) 0.139(14) 0.116(19) -0.101(16) -0.026(11) 0.014(12) C40B 0.037(4) 0.110(8) 0.094(8) -0.061(7) -0.018(4) -0.008(5) F12B 0.078(4) 0.124(5) 0.095(4) -0.036(4) -0.028(3) 0.001(4) F13B 0.064(3) 0.122(5) 0.136(6) -0.034(4) -0.015(4) -0.031(3) F14B 0.056(3) 0.084(5) 0.095(5) -0.031(4) -0.006(4) 0.012(4) O1 0.040(2) 0.0359(18) 0.0428(19) -0.0210(15) -0.0091(16) 0.0017(15) O3 0.0292(19) 0.057(2) 0.063(2) -0.036(2) -0.0029(17) 0.0001(17) C1 0.036(3) 0.048(3) 0.036(3) -0.016(2) 0.001(2) -0.019(2) C2 0.050(3) 0.054(3) 0.043(3) -0.014(3) -0.001(2) -0.026(3) C3 0.054(4) 0.069(4) 0.042(3) -0.016(3) 0.010(3) -0.041(3) C4 0.048(3) 0.096(5) 0.042(3) -0.036(3) 0.020(3) -0.039(3) C5 0.048(3) 0.060(4) 0.050(3) -0.034(3) 0.014(3) -0.021(3) C6 0.040(3) 0.050(3) 0.035(2) -0.020(2) 0.005(2) -0.022(2) C7 0.047(3) 0.033(2) 0.032(2) -0.0024(19) -0.008(2) -0.017(2) C8 0.062(4) 0.034(3) 0.057(3) -0.015(2) -0.017(3) -0.006(3) C9 0.088(5) 0.036(3) 0.086(5) -0.016(3) -0.044(4) -0.002(3) C10 0.098(6) 0.038(3) 0.087(5) 0.004(3) -0.061(4) -0.016(3) C11 0.096(6) 0.053(4) 0.058(4) 0.000(3) -0.038(4) -0.026(4) C12 0.071(4) 0.045(3) 0.040(3) -0.004(2) -0.019(3) -0.017(3) C13 0.043(3) 0.028(2) 0.034(2) -0.0082(19) -0.011(2) -0.008(2) C14 0.051(3) 0.046(3) 0.043(3) -0.016(2) 0.000(2) -0.008(3) C15 0.079(5) 0.052(3) 0.043(3) -0.023(3) 0.002(3) -0.013(3) C16 0.097(5) 0.043(3) 0.050(3) -0.022(3) -0.024(4) -0.006(3) C17 0.074(4) 0.045(3) 0.067(4) -0.025(3) -0.035(3) -0.005(3) C18 0.043(3) 0.038(3) 0.050(3) -0.015(2) -0.017(2) -0.003(2) C19 0.030(2) 0.030(2) 0.038(2) -0.0177(19) -0.0009(19) -0.0056(18) C20 0.042(3) 0.032(2) 0.042(3) -0.017(2) -0.001(2) -0.006(2) C21 0.037(3) 0.043(3) 0.051(3) -0.029(2) 0.002(2) -0.014(2) C22 0.029(2) 0.049(3) 0.045(3) -0.032(2) 0.002(2) -0.012(2) C23 0.032(2) 0.039(3) 0.033(2) -0.019(2) -0.0021(19) -0.003(2) C24 0.028(2) 0.032(2) 0.034(2) -0.0177(19) -0.0008(18) -0.0064(18) C25 0.036(3) 0.032(2) 0.041(3) -0.014(2) -0.009(2) -0.007(2) C26 0.056(4) 0.056(3) 0.040(3) -0.026(3) -0.006(3) 0.011(3) C27 0.070(4) 0.059(4) 0.060(4) -0.033(3) -0.011(3) 0.023(3) C28 0.066(4) 0.041(3) 0.057(4) -0.019(3) -0.020(3) 0.004(3) C29 0.054(3) 0.034(3) 0.044(3) -0.006(2) -0.007(3) -0.005(2) C30 0.036(3) 0.037(3) 0.045(3) -0.015(2) 0.002(2) -0.004(2) C31 0.030(2) 0.029(2) 0.030(2) -0.0088(18) -0.0041(18) -0.0013(18) C32 0.047(3) 0.038(3) 0.042(3) -0.017(2) -0.003(2) -0.007(2) C33 0.065(4) 0.044(3) 0.040(3) -0.022(2) -0.008(3) -0.006(3) C34 0.072(4) 0.040(3) 0.046(3) -0.022(2) 0.010(3) 0.003(3) C35 0.041(3) 0.053(3) 0.068(4) -0.030(3) 0.014(3) -0.002(3) C36 0.035(3) 0.040(3) 0.056(3) -0.022(2) -0.001(2) -0.004(2) C37 0.035(3) 0.044(3) 0.050(3) -0.019(2) -0.007(2) -0.006(2) C39 0.027(3) 0.074(4) 0.077(4) -0.046(4) -0.008(3) 0.001(3) Au3 0.02484(9) 0.02916(9) 0.03098(10) -0.01335(7) -0.00064(7) -0.00602(7) Au4 0.02587(10) 0.02803(9) 0.02857(9) -0.01228(7) -0.00179(7) -0.00527(7) P3 0.0284(6) 0.0268(5) 0.0307(6) -0.0109(4) -0.0017(5) -0.0053(4) P4 0.0337(6) 0.0280(6) 0.0314(6) -0.0126(5) -0.0029(5) -0.0061(5) F15 0.065(2) 0.0278(15) 0.066(2) -0.0080(14) -0.0207(17) -0.0120(14) F16 0.079(2) 0.0439(18) 0.074(2) -0.0284(17) -0.0107(19) -0.0275(17) F17 0.063(2) 0.062(2) 0.0559(19) -0.0338(16) -0.0125(16) -0.0236(17) F18 0.0503(18) 0.0464(17) 0.0404(16) -0.0169(13) -0.0141(13) -0.0092(14) F19 0.068(2) 0.0318(16) 0.079(2) -0.0185(16) 0.0128(19) -0.0163(15) F20 0.093(3) 0.050(2) 0.104(3) -0.014(2) 0.045(3) -0.038(2) F21 0.071(3) 0.069(2) 0.078(2) -0.030(2) 0.048(2) -0.032(2) F22 0.0468(18) 0.0470(18) 0.0575(19) -0.0272(15) 0.0151(15) -0.0115(14) C78A 0.043(4) 0.027(6) 0.059(6) -0.002(6) -0.011(3) -0.017(3) F23A 0.053(3) 0.097(4) 0.112(4) -0.050(3) -0.017(3) 0.011(3) F24A 0.064(4) 0.101(4) 0.152(6) -0.030(4) -0.004(4) -0.031(3) F25A 0.062(3) 0.150(5) 0.091(4) -0.042(4) -0.034(3) 0.000(4) C78B 0.043(4) 0.027(6) 0.059(6) -0.002(6) -0.011(3) -0.017(3) F23B 0.053(3) 0.097(4) 0.112(4) -0.050(3) -0.017(3) 0.011(3) F24B 0.064(4) 0.101(4) 0.152(6) -0.030(4) -0.004(4) -0.031(3) F25B 0.062(3) 0.150(5) 0.091(4) -0.042(4) -0.034(3) 0.000(4) C80A 0.043(3) 0.075(4) 0.043(3) -0.032(3) -0.007(3) -0.001(3) F26A 0.054(3) 0.132(5) 0.072(4) -0.050(4) -0.014(3) 0.027(3) F27A 0.087(4) 0.083(4) 0.131(5) -0.052(4) -0.061(3) 0.015(3) F28A 0.067(4) 0.105(4) 0.117(5) -0.004(4) -0.010(3) -0.028(3) C80B 0.043(3) 0.075(4) 0.043(3) -0.032(3) -0.007(3) -0.001(3) F26B 0.054(3) 0.132(5) 0.072(4) -0.050(4) -0.014(3) 0.027(3) F27B 0.067(4) 0.105(4) 0.117(5) -0.004(4) -0.010(3) -0.028(3) F28B 0.087(4) 0.083(4) 0.131(5) -0.052(4) -0.061(3) 0.015(3) O5 0.0297(18) 0.054(2) 0.049(2) -0.0261(18) -0.0006(16) -0.0039(16) O6 0.053(3) 0.088(3) 0.060(3) -0.046(2) -0.005(2) -0.016(2) O7 0.0284(17) 0.0420(19) 0.0394(18) -0.0212(15) -0.0037(14) -0.0007(14) O8 0.039(2) 0.112(4) 0.052(2) -0.048(3) -0.0083(19) -0.003(2) C41 0.030(2) 0.033(2) 0.035(2) -0.0159(19) 0.0000(19) -0.0088(19) C42 0.042(3) 0.029(2) 0.042(3) -0.013(2) -0.003(2) -0.008(2) C43 0.048(3) 0.040(3) 0.055(3) -0.028(2) 0.003(3) -0.018(2) C44 0.038(3) 0.047(3) 0.044(3) -0.026(2) -0.003(2) -0.014(2) C45 0.035(3) 0.038(3) 0.034(2) -0.017(2) -0.003(2) -0.009(2) C46 0.029(2) 0.030(2) 0.033(2) -0.0159(18) 0.0033(18) -0.0097(18) C47 0.032(2) 0.031(2) 0.034(2) -0.0097(19) 0.0018(19) -0.0066(19) C48 0.034(3) 0.053(3) 0.045(3) -0.022(2) -0.001(2) -0.003(2) C49 0.040(3) 0.067(4) 0.058(4) -0.026(3) 0.010(3) -0.006(3) C50 0.065(4) 0.071(4) 0.052(4) -0.036(3) 0.017(3) -0.010(3) C51 0.064(4) 0.082(5) 0.047(3) -0.040(3) 0.003(3) -0.016(3) C52 0.043(3) 0.064(4) 0.048(3) -0.031(3) 0.001(2) -0.014(3) C53 0.034(2) 0.030(2) 0.042(3) -0.015(2) -0.004(2) -0.0069(19) C54 0.039(3) 0.039(3) 0.043(3) -0.009(2) -0.002(2) -0.010(2) C55 0.050(3) 0.038(3) 0.062(4) -0.002(3) -0.012(3) -0.012(3) C56 0.068(5) 0.036(3) 0.097(6) -0.019(3) -0.012(4) 0.007(3) C57 0.066(4) 0.056(4) 0.078(5) -0.035(4) 0.006(4) 0.017(3) C58 0.056(4) 0.045(3) 0.049(3) -0.023(3) -0.001(3) 0.005(3) C59 0.035(3) 0.035(2) 0.038(3) -0.016(2) 0.000(2) -0.010(2) C60 0.054(3) 0.037(3) 0.051(3) -0.019(2) 0.008(3) -0.019(2) C61 0.062(4) 0.041(3) 0.062(4) -0.011(3) 0.015(3) -0.030(3) C62 0.050(3) 0.053(3) 0.049(3) -0.022(3) 0.021(3) -0.021(3) C63 0.041(3) 0.042(3) 0.040(3) -0.020(2) 0.011(2) -0.016(2) C64 0.034(3) 0.034(2) 0.031(2) -0.0102(19) -0.0025(19) -0.014(2) C65 0.035(3) 0.034(2) 0.036(2) -0.016(2) -0.010(2) -0.0012(19) C66 0.041(3) 0.038(3) 0.038(3) -0.016(2) -0.008(2) -0.003(2) C67 0.059(4) 0.057(3) 0.041(3) -0.026(3) -0.004(3) -0.003(3) C68 0.062(4) 0.062(4) 0.051(3) -0.034(3) -0.019(3) 0.001(3) C69 0.078(5) 0.072(4) 0.066(4) -0.036(4) -0.018(4) -0.023(4) C70 0.055(4) 0.061(4) 0.051(3) -0.027(3) 0.000(3) -0.026(3) C71 0.041(3) 0.032(2) 0.036(2) -0.0111(19) -0.009(2) -0.007(2) C72 0.047(3) 0.041(3) 0.047(3) -0.017(2) -0.006(2) -0.003(2) C73 0.064(4) 0.042(3) 0.086(5) -0.027(3) -0.023(4) 0.007(3) C74 0.073(5) 0.041(3) 0.097(5) -0.016(3) -0.047(4) 0.009(3) C75 0.113(7) 0.052(4) 0.075(5) -0.014(3) -0.058(5) -0.005(4) C76 0.082(5) 0.043(3) 0.048(3) -0.019(3) -0.026(3) -0.006(3) C77 0.036(3) 0.042(3) 0.056(3) -0.018(2) -0.009(2) -0.008(2) C79 0.034(3) 0.044(3) 0.041(3) -0.020(2) -0.002(2) -0.006(2) Cl1A 0.087(3) 0.089(2) 0.125(3) -0.012(2) -0.020(3) 0.001(3) C81A 0.065(5) 0.086(5) 0.078(5) -0.017(4) -0.011(4) -0.019(4) Cl2A 0.174(6) 0.135(6) 0.104(7) -0.049(6) -0.057(6) 0.001(6) Cl1B 0.087(3) 0.089(2) 0.125(3) -0.012(2) -0.020(3) 0.001(3) C81B 0.065(5) 0.086(5) 0.078(5) -0.017(4) -0.011(4) -0.019(4) Cl2B 0.174(6) 0.135(6) 0.104(7) -0.049(6) -0.057(6) 0.001(6) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Au1 C24 2.077(4) . ? Au1 O1 2.108(4) . ? Au1 P1 2.3384(12) . ? Au1 Au2 2.5093(2) . ? Au2 C6 2.071(5) . ? Au2 O3 2.110(4) . ? Au2 P2 2.3394(12) . ? P1 C7 1.804(5) . ? P1 C13 1.806(5) . ? P1 C1 1.806(5) . ? P2 C31 1.798(4) . ? P2 C19 1.808(5) . ? P2 C25 1.811(5) . ? F1 C2 1.350(7) . ? F2 C3 1.336(6) . ? F3 C4 1.360(6) . ? F4 C5 1.346(6) . ? F5 C20 1.335(6) . ? F6 C21 1.333(5) . ? F7 C22 1.344(5) . ? F8 C23 1.348(5) . ? O2A C37 1.205(9) . ? C38A F10A 1.312(5) . ? C38A F9A 1.313(5) . ? C38A F11A 1.313(5) . ? C38A C37 1.557(9) . ? O2B C37 1.205(9) . ? C38B F10B 1.311(5) . ? C38B F9B 1.311(5) . ? C38B F11B 1.311(5) . ? C38B C37 1.557(9) . ? O4A C39 1.207(10) . ? C40A F14A 1.316(5) . ? C40A F12A 1.317(4) . ? C40A F13A 1.318(5) . ? C40A C39 1.540(9) . ? O4B C39 1.207(10) . ? C40B F14B 1.316(5) . ? C40B F12B 1.316(5) . ? C40B F13B 1.317(5) . ? C40B C39 1.540(9) . ? O1 C37 1.259(6) . ? O3 C39 1.260(7) . ? C1 C2 1.379(7) . ? C1 C6 1.407(7) . ? C2 C3 1.374(8) . ? C3 C4 1.355(9) . ? C4 C5 1.395(8) . ? C5 C6 1.365(7) . ? C7 C8 1.396(7) . ? C7 C12 1.397(7) . ? C8 C9 1.393(8) . ? C8 H8 0.9500 . ? C9 C10 1.378(9) . ? C9 H9 0.9500 . ? C10 C11 1.393(10) . ? C10 H10 0.9500 . ? C11 C12 1.380(8) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? C13 C14 1.383(7) . ? C13 C18 1.393(7) . ? C14 C15 1.382(8) . ? C14 H14 0.9500 . ? C15 C16 1.381(9) . ? C15 H15 0.9500 . ? C16 C17 1.362(9) . ? C16 H16 0.9500 . ? C17 C18 1.390(7) . ? C17 H17 0.9500 . ? C18 H18 0.9500 . ? C19 C20 1.389(6) . ? C19 C24 1.419(6) . ? C20 C21 1.387(7) . ? C21 C22 1.363(7) . ? C22 C23 1.391(7) . ? C23 C24 1.363(6) . ? C25 C30 1.382(7) . ? C25 C26 1.386(7) . ? C26 C27 1.373(8) . ? C26 H26 0.9500 . ? C27 C28 1.380(9) . ? C27 H27 0.9500 . ? C28 C29 1.367(8) . ? C28 H28 0.9500 . ? C29 C30 1.388(7) . ? C29 H29 0.9500 . ? C30 H30 0.9500 . ? C31 C36 1.388(7) . ? C31 C32 1.406(7) . ? C32 C33 1.377(7) . ? C32 H32 0.9500 . ? C33 C34 1.375(9) . ? C33 H33 0.9500 . ? C34 C35 1.374(9) . ? C34 H34 0.9500 . ? C35 C36 1.387(7) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? Au3 C64 2.069(4) . ? Au3 O5 2.097(4) . ? Au3 P3 2.3455(11) . ? Au3 Au4 2.5048(2) . ? Au4 C46 2.081(4) . ? Au4 O7 2.129(3) . ? Au4 P4 2.3437(12) . ? P3 C47 1.798(5) . ? P3 C41 1.812(5) . ? P3 C53 1.813(5) . ? P4 C65 1.797(5) . ? P4 C59 1.804(5) . ? P4 C71 1.805(5) . ? F15 C42 1.332(6) . ? F16 C43 1.339(5) . ? F17 C44 1.345(6) . ? F18 C45 1.348(5) . ? F19 C60 1.351(6) . ? F20 C61 1.349(6) . ? F21 C62 1.344(6) . ? F22 C63 1.355(6) . ? C78A F24A 1.200(13) . ? C78A F25A 1.313(16) . ? C78A F23A 1.415(14) . ? C78A C77 1.562(8) . ? C78B F24B 1.03(2) . ? C78B F23B 1.47(3) . ? C78B F25B 1.49(3) . ? C78B C77 1.562(8) . ? C80A F26A 1.302(4) . ? C80A F27A 1.304(4) . ? C80A F28A 1.305(4) . ? C80A C79 1.554(8) . ? C80B F27B 1.301(4) . ? C80B F28B 1.303(4) . ? C80B F26B 1.305(4) . ? C80B C79 1.554(8) . ? O5 C77 1.274(7) . ? O6 C77 1.201(7) . ? O7 C79 1.256(6) . ? O8 C79 1.214(6) . ? C41 C42 1.393(6) . ? C41 C46 1.412(6) . ? C42 C43 1.375(7) . ? C43 C44 1.372(8) . ? C44 C45 1.391(7) . ? C45 C46 1.365(6) . ? C47 C48 1.373(7) . ? C47 C52 1.390(7) . ? C48 C49 1.400(7) . ? C48 H48 0.9500 . ? C49 C50 1.388(9) . ? C49 H49 0.9500 . ? C50 C51 1.372(9) . ? C50 H50 0.9500 . ? C51 C52 1.386(7) . ? C51 H51 0.9500 . ? C52 H52 0.9500 . ? C53 C58 1.389(7) . ? C53 C54 1.390(7) . ? C54 C55 1.364(7) . ? C54 H54 0.9500 . ? C55 C56 1.381(9) . ? C55 H55 0.9500 . ? C56 C57 1.379(9) . ? C56 H56 0.9500 . ? C57 C58 1.379(8) . ? C57 H57 0.9500 . ? C58 H58 0.9500 . ? C59 C60 1.374(7) . ? C59 C64 1.422(6) . ? C60 C61 1.377(8) . ? C61 C62 1.372(8) . ? C62 C63 1.367(7) . ? C63 C64 1.372(6) . ? C65 C70 1.390(7) . ? C65 C66 1.394(7) . ? C66 C67 1.388(7) . ? C66 H66 0.9500 . ? C67 C68 1.388(8) . ? C67 H67 0.9500 . ? C68 C69 1.354(9) . ? C68 H68 0.9500 . ? C69 C70 1.384(8) . ? C69 H69 0.9500 . ? C70 H70 0.9500 . ? C71 C72 1.392(7) . ? C71 C76 1.400(7) . ? C72 C73 1.384(8) . ? C72 H72 0.9500 . ? C73 C74 1.367(9) . ? C73 H73 0.9500 . ? C74 C75 1.354(10) . ? C74 H74 0.9500 . ? C75 C76 1.387(9) . ? C75 H75 0.9500 . ? C76 H76 0.9500 . ? Cl1A C81A 1.702(9) . ? C81A Cl2A 1.702(9) . ? C81A H81A 0.9900 . ? C81A H81B 0.9900 . ? Cl1B C81B 1.702(9) . ? C81B Cl2B 1.702(9) . ? C81B H81C 0.9900 . ? C81B H81D 0.9900 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C24 Au1 O1 91.28(16) . . ? C24 Au1 P1 172.74(13) . . ? O1 Au1 P1 95.94(10) . . ? C24 Au1 Au2 88.85(13) . . ? O1 Au1 Au2 178.19(9) . . ? P1 Au1 Au2 83.91(3) . . ? C6 Au2 O3 91.35(19) . . ? C6 Au2 P2 170.93(15) . . ? O3 Au2 P2 97.60(12) . . ? C6 Au2 Au1 88.85(15) . . ? O3 Au2 Au1 179.80(15) . . ? P2 Au2 Au1 82.21(3) . . ? C7 P1 C13 108.9(2) . . ? C7 P1 C1 107.0(2) . . ? C13 P1 C1 107.3(2) . . ? C7 P1 Au1 111.84(17) . . ? C13 P1 Au1 118.29(16) . . ? C1 P1 Au1 102.61(17) . . ? C31 P2 C19 106.7(2) . . ? C31 P2 C25 107.2(2) . . ? C19 P2 C25 111.9(2) . . ? C31 P2 Au2 109.74(15) . . ? C19 P2 Au2 102.99(15) . . ? C25 P2 Au2 117.77(17) . . ? F10A C38A F9A 111.0(9) . . ? F10A C38A F11A 103.9(9) . . ? F9A C38A F11A 106.0(9) . . ? F10A C38A C37 112.3(7) . . ? F9A C38A C37 112.1(8) . . ? F11A C38A C37 111.0(7) . . ? F10B C38B F9B 101.7(12) . . ? F10B C38B F11B 108.1(11) . . ? F9B C38B F11B 110.6(10) . . ? F10B C38B C37 109.5(8) . . ? F9B C38B C37 113.3(10) . . ? F11B C38B C37 112.9(8) . . ? F14A C40A F12A 115.6(9) . . ? F14A C40A F13A 95.3(8) . . ? F12A C40A F13A 106.9(8) . . ? F14A C40A C39 113.7(8) . . ? F12A C40A C39 110.8(7) . . ? F13A C40A C39 113.6(7) . . ? F14B C40B F12B 88.7(12) . . ? F14B C40B F13B 114.6(15) . . ? F12B C40B F13B 107.7(13) . . ? F14B C40B C39 118.5(12) . . ? F12B C40B C39 118.3(10) . . ? F13B C40B C39 107.9(10) . . ? C37 O1 Au1 115.7(3) . . ? C39 O3 Au2 113.9(3) . . ? C2 C1 C6 120.1(5) . . ? C2 C1 P1 123.8(4) . . ? C6 C1 P1 116.0(4) . . ? F1 C2 C3 116.9(5) . . ? F1 C2 C1 122.0(5) . . ? C3 C2 C1 121.1(6) . . ? F2 C3 C4 119.9(5) . . ? F2 C3 C2 121.5(6) . . ? C4 C3 C2 118.6(5) . . ? C3 C4 F3 120.2(5) . . ? C3 C4 C5 121.5(5) . . ? F3 C4 C5 118.3(6) . . ? F4 C5 C6 121.8(5) . . ? F4 C5 C4 117.8(5) . . ? C6 C5 C4 120.4(5) . . ? C5 C6 C1 118.1(5) . . ? C5 C6 Au2 122.2(4) . . ? C1 C6 Au2 119.6(3) . . ? C8 C7 C12 120.6(5) . . ? C8 C7 P1 122.4(4) . . ? C12 C7 P1 117.0(4) . . ? C9 C8 C7 118.6(6) . . ? C9 C8 H8 120.7 . . ? C7 C8 H8 120.7 . . ? C10 C9 C8 121.0(6) . . ? C10 C9 H9 119.5 . . ? C8 C9 H9 119.5 . . ? C9 C10 C11 120.1(6) . . ? C9 C10 H10 120.0 . . ? C11 C10 H10 120.0 . . ? C12 C11 C10 120.0(6) . . ? C12 C11 H11 120.0 . . ? C10 C11 H11 120.0 . . ? C11 C12 C7 119.8(6) . . ? C11 C12 H12 120.1 . . ? C7 C12 H12 120.1 . . ? C14 C13 C18 119.9(5) . . ? C14 C13 P1 120.1(4) . . ? C18 C13 P1 120.0(4) . . ? C15 C14 C13 119.8(6) . . ? C15 C14 H14 120.1 . . ? C13 C14 H14 120.1 . . ? C16 C15 C14 120.7(6) . . ? C16 C15 H15 119.6 . . ? C14 C15 H15 119.6 . . ? C17 C16 C15 119.3(6) . . ? C17 C16 H16 120.4 . . ? C15 C16 H16 120.4 . . ? C16 C17 C18 121.5(6) . . ? C16 C17 H17 119.2 . . ? C18 C17 H17 119.2 . . ? C17 C18 C13 118.8(6) . . ? C17 C18 H18 120.6 . . ? C13 C18 H18 120.6 . . ? C20 C19 C24 119.4(4) . . ? C20 C19 P2 126.2(4) . . ? C24 C19 P2 114.3(3) . . ? F5 C20 C21 118.0(4) . . ? F5 C20 C19 121.2(5) . . ? C21 C20 C19 120.8(5) . . ? F6 C21 C22 120.0(5) . . ? F6 C21 C20 120.3(5) . . ? C22 C21 C20 119.6(4) . . ? F7 C22 C21 120.0(4) . . ? F7 C22 C23 120.0(5) . . ? C21 C22 C23 120.0(5) . . ? F8 C23 C24 121.6(4) . . ? F8 C23 C22 116.3(4) . . ? C24 C23 C22 122.0(5) . . ? C23 C24 C19 118.2(4) . . ? C23 C24 Au1 122.6(3) . . ? C19 C24 Au1 119.0(3) . . ? C30 C25 C26 120.0(5) . . ? C30 C25 P2 120.3(4) . . ? C26 C25 P2 119.7(4) . . ? C27 C26 C25 119.2(5) . . ? C27 C26 H26 120.4 . . ? C25 C26 H26 120.4 . . ? C26 C27 C28 120.9(5) . . ? C26 C27 H27 119.5 . . ? C28 C27 H27 119.5 . . ? C29 C28 C27 120.0(5) . . ? C29 C28 H28 120.0 . . ? C27 C28 H28 120.0 . . ? C28 C29 C30 119.7(5) . . ? C28 C29 H29 120.1 . . ? C30 C29 H29 120.1 . . ? C25 C30 C29 120.1(5) . . ? C25 C30 H30 120.0 . . ? C29 C30 H30 120.0 . . ? C36 C31 C32 119.7(4) . . ? C36 C31 P2 122.2(4) . . ? C32 C31 P2 118.2(4) . . ? C33 C32 C31 119.2(5) . . ? C33 C32 H32 120.4 . . ? C31 C32 H32 120.4 . . ? C34 C33 C32 120.7(5) . . ? C34 C33 H33 119.6 . . ? C32 C33 H33 119.6 . . ? C35 C34 C33 120.5(5) . . ? C35 C34 H34 119.8 . . ? C33 C34 H34 119.8 . . ? C34 C35 C36 120.0(5) . . ? C34 C35 H35 120.0 . . ? C36 C35 H35 120.0 . . ? C35 C36 C31 119.9(5) . . ? C35 C36 H36 120.1 . . ? C31 C36 H36 120.1 . . ? O2B C37 O1 127(6) . . ? O2A C37 O1 131(5) . . ? O2B C37 C38B 119(6) . . ? O2A C37 C38B 114(4) . . ? O1 C37 C38B 113.6(6) . . ? O2B C37 C38A 120(6) . . ? O2A C37 C38A 117(5) . . ? O1 C37 C38A 111.3(5) . . ? O4B C39 O3 126(6) . . ? O4A C39 O3 132(4) . . ? O4B C39 C40B 121(6) . . ? O4A C39 C40B 112(4) . . ? O3 C39 C40B 113.3(7) . . ? O4B C39 C40A 120(6) . . ? O4A C39 C40A 116(4) . . ? O3 C39 C40A 111.8(5) . . ? C64 Au3 O5 89.99(17) . . ? C64 Au3 P3 171.48(14) . . ? O5 Au3 P3 98.51(11) . . ? C64 Au3 Au4 87.45(13) . . ? O5 Au3 Au4 176.58(10) . . ? P3 Au3 Au4 84.03(3) . . ? C46 Au4 O7 93.38(16) . . ? C46 Au4 P4 171.19(13) . . ? O7 Au4 P4 95.39(10) . . ? C46 Au4 Au3 87.52(13) . . ? O7 Au4 Au3 176.21(9) . . ? P4 Au4 Au3 83.67(3) . . ? C47 P3 C41 106.7(2) . . ? C47 P3 C53 107.2(2) . . ? C41 P3 C53 109.4(2) . . ? C47 P3 Au3 115.98(15) . . ? C41 P3 Au3 100.90(15) . . ? C53 P3 Au3 115.90(16) . . ? C65 P4 C59 109.4(2) . . ? C65 P4 C71 106.6(2) . . ? C59 P4 C71 107.7(2) . . ? C65 P4 Au4 116.43(16) . . ? C59 P4 Au4 102.46(16) . . ? C71 P4 Au4 113.90(16) . . ? F24A C78A F25A 112.8(10) . . ? F24A C78A F23A 103.7(11) . . ? F25A C78A F23A 102.3(8) . . ? F24A C78A C77 118.1(8) . . ? F25A C78A C77 111.2(9) . . ? F23A C78A C77 107.0(8) . . ? F24B C78B F23B 116(2) . . ? F24B C78B F25B 118(2) . . ? F23B C78B F25B 84.7(15) . . ? F24B C78B C77 126.7(17) . . ? F23B C78B C77 100.9(13) . . ? F25B C78B C77 101.6(14) . . ? F26A C80A F27A 104.2(9) . . ? F26A C80A F28A 108.5(9) . . ? F27A C80A F28A 103.8(9) . . ? F26A C80A C79 105.2(4) . . ? F27A C80A C79 113.7(5) . . ? F28A C80A C79 120.4(5) . . ? F27B C80B F28B 108.5(9) . . ? F27B C80B F26B 106.2(9) . . ? F28B C80B F26B 104.9(8) . . ? F27B C80B C79 107.8(4) . . ? F28B C80B C79 113.6(4) . . ? F26B C80B C79 115.4(5) . . ? C77 O5 Au3 115.4(3) . . ? C79 O7 Au4 113.5(3) . . ? C42 C41 C46 119.9(4) . . ? C42 C41 P3 124.3(4) . . ? C46 C41 P3 115.7(3) . . ? F15 C42 C43 117.7(4) . . ? F15 C42 C41 121.9(5) . . ? C43 C42 C41 120.5(5) . . ? F16 C43 C44 119.5(5) . . ? F16 C43 C42 120.7(5) . . ? C44 C43 C42 119.8(4) . . ? F17 C44 C43 119.5(4) . . ? F17 C44 C45 120.5(5) . . ? C43 C44 C45 119.9(5) . . ? F18 C45 C46 121.8(4) . . ? F18 C45 C44 116.4(4) . . ? C46 C45 C44 121.8(5) . . ? C45 C46 C41 118.1(4) . . ? C45 C46 Au4 122.1(3) . . ? C41 C46 Au4 119.7(3) . . ? C48 C47 C52 119.8(5) . . ? C48 C47 P3 121.8(4) . . ? C52 C47 P3 118.3(4) . . ? C47 C48 C49 120.3(5) . . ? C47 C48 H48 119.9 . . ? C49 C48 H48 119.9 . . ? C50 C49 C48 119.5(6) . . ? C50 C49 H49 120.3 . . ? C48 C49 H49 120.3 . . ? C51 C50 C49 119.9(5) . . ? C51 C50 H50 120.1 . . ? C49 C50 H50 120.1 . . ? C50 C51 C52 120.6(6) . . ? C50 C51 H51 119.7 . . ? C52 C51 H51 119.7 . . ? C51 C52 C47 119.8(5) . . ? C51 C52 H52 120.1 . . ? C47 C52 H52 120.1 . . ? C58 C53 C54 119.6(5) . . ? C58 C53 P3 118.6(4) . . ? C54 C53 P3 121.8(4) . . ? C55 C54 C53 120.3(5) . . ? C55 C54 H54 119.9 . . ? C53 C54 H54 119.9 . . ? C54 C55 C56 120.1(6) . . ? C54 C55 H55 120.0 . . ? C56 C55 H55 120.0 . . ? C57 C56 C55 120.3(6) . . ? C57 C56 H56 119.9 . . ? C55 C56 H56 119.9 . . ? C56 C57 C58 119.9(6) . . ? C56 C57 H57 120.0 . . ? C58 C57 H57 120.0 . . ? C57 C58 C53 119.8(6) . . ? C57 C58 H58 120.1 . . ? C53 C58 H58 120.1 . . ? C60 C59 C64 119.4(5) . . ? C60 C59 P4 125.8(4) . . ? C64 C59 P4 114.5(3) . . ? F19 C60 C59 121.3(5) . . ? F19 C60 C61 117.7(5) . . ? C59 C60 C61 121.0(5) . . ? F20 C61 C62 119.9(5) . . ? F20 C61 C60 120.5(5) . . ? C62 C61 C60 119.6(5) . . ? F21 C62 C63 121.1(5) . . ? F21 C62 C61 119.0(5) . . ? C63 C62 C61 119.9(5) . . ? F22 C63 C62 116.5(4) . . ? F22 C63 C64 121.2(4) . . ? C62 C63 C64 122.3(5) . . ? C63 C64 C59 117.6(4) . . ? C63 C64 Au3 122.3(4) . . ? C59 C64 Au3 119.9(3) . . ? C70 C65 C66 119.5(5) . . ? C70 C65 P4 120.6(4) . . ? C66 C65 P4 119.6(4) . . ? C67 C66 C65 119.7(5) . . ? C67 C66 H66 120.2 . . ? C65 C66 H66 120.2 . . ? C68 C67 C66 119.5(6) . . ? C68 C67 H67 120.2 . . ? C66 C67 H67 120.2 . . ? C69 C68 C67 120.9(5) . . ? C69 C68 H68 119.6 . . ? C67 C68 H68 119.6 . . ? C68 C69 C70 120.3(6) . . ? C68 C69 H69 119.8 . . ? C70 C69 H69 119.8 . . ? C69 C70 C65 120.0(6) . . ? C69 C70 H70 120.0 . . ? C65 C70 H70 120.0 . . ? C72 C71 C76 118.8(5) . . ? C72 C71 P4 121.5(4) . . ? C76 C71 P4 119.7(4) . . ? C73 C72 C71 120.2(5) . . ? C73 C72 H72 119.9 . . ? C71 C72 H72 119.9 . . ? C74 C73 C72 120.0(6) . . ? C74 C73 H73 120.0 . . ? C72 C73 H73 120.0 . . ? C75 C74 C73 120.7(6) . . ? C75 C74 H74 119.6 . . ? C73 C74 H74 119.6 . . ? C74 C75 C76 120.8(6) . . ? C74 C75 H75 119.6 . . ? C76 C75 H75 119.6 . . ? C75 C76 C71 119.5(6) . . ? C75 C76 H76 120.3 . . ? C71 C76 H76 120.3 . . ? O6 C77 O5 129.2(5) . . ? O6 C77 C78A 118.9(8) . . ? O5 C77 C78A 111.8(7) . . ? O6 C77 C78B 117.6(13) . . ? O5 C77 C78B 112.1(12) . . ? O8 C79 O7 129.9(5) . . ? O8 C79 C80B 116.2(5) . . ? O7 C79 C80B 113.7(5) . . ? O8 C79 C80A 121.5(5) . . ? O7 C79 C80A 108.5(5) . . ? Cl2A C81A Cl1A 116.4(10) . . ? Cl2A C81A H81A 108.2 . . ? Cl1A C81A H81A 108.2 . . ? Cl2A C81A H81B 108.2 . . ? Cl1A C81A H81B 108.2 . . ? H81A C81A H81B 107.3 . . ? Cl1B C81B Cl2B 111.2(17) . . ? Cl1B C81B H81C 109.4 . . ? Cl2B C81B H81C 109.4 . . ? Cl1B C81B H81D 109.4 . . ? Cl2B C81B H81D 109.4 . . ? H81C C81B H81D 108.0 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C24 Au1 Au2 C6 -137.42(18) . . . . ? P1 Au1 Au2 C6 42.05(13) . . . . ? C24 Au1 Au2 P2 44.09(12) . . . . ? P1 Au1 Au2 P2 -136.44(4) . . . . ? O1 Au1 P1 C7 19.3(2) . . . . ? Au2 Au1 P1 C7 -158.89(18) . . . . ? O1 Au1 P1 C13 -108.5(2) . . . . ? Au2 Au1 P1 C13 73.31(19) . . . . ? O1 Au1 P1 C1 133.6(2) . . . . ? Au2 Au1 P1 C1 -44.54(17) . . . . ? O3 Au2 P2 C31 -114.44(19) . . . . ? Au1 Au2 P2 C31 65.58(16) . . . . ? O3 Au2 P2 C19 132.17(18) . . . . ? Au1 Au2 P2 C19 -47.81(15) . . . . ? O3 Au2 P2 C25 8.5(2) . . . . ? Au1 Au2 P2 C25 -171.50(18) . . . . ? C24 Au1 O1 C37 -112.7(4) . . . . ? P1 Au1 O1 C37 68.1(3) . . . . ? C6 Au2 O3 C39 -96.6(4) . . . . ? P2 Au2 O3 C39 81.9(4) . . . . ? C7 P1 C1 C2 -29.7(5) . . . . ? C13 P1 C1 C2 87.1(5) . . . . ? Au1 P1 C1 C2 -147.5(4) . . . . ? C7 P1 C1 C6 147.1(4) . . . . ? C13 P1 C1 C6 -96.1(4) . . . . ? Au1 P1 C1 C6 29.3(4) . . . . ? C6 C1 C2 F1 177.2(5) . . . . ? P1 C1 C2 F1 -6.1(8) . . . . ? C6 C1 C2 C3 -4.5(8) . . . . ? P1 C1 C2 C3 172.2(4) . . . . ? F1 C2 C3 F2 0.8(9) . . . . ? C1 C2 C3 F2 -177.6(5) . . . . ? F1 C2 C3 C4 -179.2(5) . . . . ? C1 C2 C3 C4 2.3(9) . . . . ? F2 C3 C4 F3 -1.5(9) . . . . ? C2 C3 C4 F3 178.5(5) . . . . ? F2 C3 C4 C5 179.4(5) . . . . ? C2 C3 C4 C5 -0.6(9) . . . . ? C3 C4 C5 F4 -179.1(6) . . . . ? F3 C4 C5 F4 1.7(8) . . . . ? C3 C4 C5 C6 0.9(9) . . . . ? F3 C4 C5 C6 -178.2(5) . . . . ? F4 C5 C6 C1 177.1(5) . . . . ? C4 C5 C6 C1 -3.0(8) . . . . ? F4 C5 C6 Au2 -6.4(8) . . . . ? C4 C5 C6 Au2 173.6(4) . . . . ? C2 C1 C6 C5 4.7(8) . . . . ? P1 C1 C6 C5 -172.2(4) . . . . ? C2 C1 C6 Au2 -171.9(4) . . . . ? P1 C1 C6 Au2 11.2(5) . . . . ? O3 Au2 C6 C5 -38.1(5) . . . . ? Au1 Au2 C6 C5 141.9(4) . . . . ? O3 Au2 C6 C1 138.4(4) . . . . ? Au1 Au2 C6 C1 -41.6(4) . . . . ? C13 P1 C7 C8 1.1(5) . . . . ? C1 P1 C7 C8 116.9(5) . . . . ? Au1 P1 C7 C8 -131.5(4) . . . . ? C13 P1 C7 C12 -177.4(4) . . . . ? C1 P1 C7 C12 -61.7(5) . . . . ? Au1 P1 C7 C12 49.9(5) . . . . ? C12 C7 C8 C9 1.3(9) . . . . ? P1 C7 C8 C9 -177.2(5) . . . . ? C7 C8 C9 C10 -0.2(11) . . . . ? C8 C9 C10 C11 -0.6(12) . . . . ? C9 C10 C11 C12 0.3(12) . . . . ? C10 C11 C12 C7 0.9(11) . . . . ? C8 C7 C12 C11 -1.7(9) . . . . ? P1 C7 C12 C11 176.9(5) . . . . ? C7 P1 C13 C14 -67.4(4) . . . . ? C1 P1 C13 C14 177.1(4) . . . . ? Au1 P1 C13 C14 61.8(4) . . . . ? C7 P1 C13 C18 111.0(4) . . . . ? C1 P1 C13 C18 -4.5(5) . . . . ? Au1 P1 C13 C18 -119.8(4) . . . . ? C18 C13 C14 C15 -1.2(8) . . . . ? P1 C13 C14 C15 177.2(4) . . . . ? C13 C14 C15 C16 0.9(9) . . . . ? C14 C15 C16 C17 -0.1(9) . . . . ? C15 C16 C17 C18 -0.3(9) . . . . ? C16 C17 C18 C13 0.0(8) . . . . ? C14 C13 C18 C17 0.8(7) . . . . ? P1 C13 C18 C17 -177.6(4) . . . . ? C31 P2 C19 C20 99.9(4) . . . . ? C25 P2 C19 C20 -17.1(5) . . . . ? Au2 P2 C19 C20 -144.6(4) . . . . ? C31 P2 C19 C24 -83.2(4) . . . . ? C25 P2 C19 C24 159.8(3) . . . . ? Au2 P2 C19 C24 32.3(3) . . . . ? C24 C19 C20 F5 178.5(4) . . . . ? P2 C19 C20 F5 -4.8(7) . . . . ? C24 C19 C20 C21 -0.7(7) . . . . ? P2 C19 C20 C21 176.0(4) . . . . ? F5 C20 C21 F6 2.5(7) . . . . ? C19 C20 C21 F6 -178.3(4) . . . . ? F5 C20 C21 C22 180.0(4) . . . . ? C19 C20 C21 C22 -0.8(7) . . . . ? F6 C21 C22 F7 -2.9(7) . . . . ? C20 C21 C22 F7 179.6(4) . . . . ? F6 C21 C22 C23 178.8(4) . . . . ? C20 C21 C22 C23 1.2(7) . . . . ? F7 C22 C23 F8 3.3(6) . . . . ? C21 C22 C23 F8 -178.3(4) . . . . ? F7 C22 C23 C24 -178.5(4) . . . . ? C21 C22 C23 C24 -0.1(7) . . . . ? F8 C23 C24 C19 176.7(4) . . . . ? C22 C23 C24 C19 -1.3(7) . . . . ? F8 C23 C24 Au1 -8.8(6) . . . . ? C22 C23 C24 Au1 173.1(3) . . . . ? C20 C19 C24 C23 1.7(7) . . . . ? P2 C19 C24 C23 -175.4(3) . . . . ? C20 C19 C24 Au1 -172.9(3) . . . . ? P2 C19 C24 Au1 10.0(5) . . . . ? O1 Au1 C24 C23 -35.5(4) . . . . ? Au2 Au1 C24 C23 142.7(4) . . . . ? O1 Au1 C24 C19 138.9(3) . . . . ? Au2 Au1 C24 C19 -42.9(3) . . . . ? C31 P2 C25 C30 -15.8(5) . . . . ? C19 P2 C25 C30 100.9(4) . . . . ? Au2 P2 C25 C30 -140.0(4) . . . . ? C31 P2 C25 C26 162.4(5) . . . . ? C19 P2 C25 C26 -80.9(5) . . . . ? Au2 P2 C25 C26 38.2(5) . . . . ? C30 C25 C26 C27 0.2(9) . . . . ? P2 C25 C26 C27 -178.0(5) . . . . ? C25 C26 C27 C28 0.2(11) . . . . ? C26 C27 C28 C29 -0.5(11) . . . . ? C27 C28 C29 C30 0.4(10) . . . . ? C26 C25 C30 C29 -0.4(8) . . . . ? P2 C25 C30 C29 177.8(4) . . . . ? C28 C29 C30 C25 0.1(9) . . . . ? C19 P2 C31 C36 -18.6(5) . . . . ? C25 P2 C31 C36 101.5(4) . . . . ? Au2 P2 C31 C36 -129.5(4) . . . . ? C19 P2 C31 C32 161.0(4) . . . . ? C25 P2 C31 C32 -78.9(4) . . . . ? Au2 P2 C31 C32 50.1(4) . . . . ? C36 C31 C32 C33 -0.1(7) . . . . ? P2 C31 C32 C33 -179.7(4) . . . . ? C31 C32 C33 C34 0.0(8) . . . . ? C32 C33 C34 C35 -0.1(9) . . . . ? C33 C34 C35 C36 0.4(9) . . . . ? C34 C35 C36 C31 -0.5(9) . . . . ? C32 C31 C36 C35 0.4(8) . . . . ? P2 C31 C36 C35 180.0(4) . . . . ? Au1 O1 C37 O2B 7(3) . . . . ? Au1 O1 C37 O2A -7(2) . . . . ? Au1 O1 C37 C38B -172.9(5) . . . . ? Au1 O1 C37 C38A 172.9(4) . . . . ? F10B C38B C37 O2B 59(3) . . . . ? F9B C38B C37 O2B 172(3) . . . . ? F11B C38B C37 O2B -61(3) . . . . ? F10B C38B C37 O2A 71(2) . . . . ? F9B C38B C37 O2A -176(2) . . . . ? F11B C38B C37 O2A -49(2) . . . . ? F10B C38B C37 O1 -120.4(10) . . . . ? F9B C38B C37 O1 -7.7(13) . . . . ? F11B C38B C37 O1 119.1(10) . . . . ? F10B C38B C37 C38A -38(2) . . . . ? F9B C38B C37 C38A 75(3) . . . . ? F11B C38B C37 C38A -158(3) . . . . ? F10A C38A C37 O2B 87(3) . . . . ? F9A C38A C37 O2B -147(3) . . . . ? F11A C38A C37 O2B -29(3) . . . . ? F10A C38A C37 O2A 101(2) . . . . ? F9A C38A C37 O2A -133(2) . . . . ? F11A C38A C37 O2A -15(2) . . . . ? F10A C38A C37 O1 -79.5(8) . . . . ? F9A C38A C37 O1 46.3(9) . . . . ? F11A C38A C37 O1 164.6(8) . . . . ? F10A C38A C37 C38B 178(3) . . . . ? F9A C38A C37 C38B -56(3) . . . . ? F11A C38A C37 C38B 62(3) . . . . ? Au2 O3 C39 O4B 7(3) . . . . ? Au2 O3 C39 O4A -13(2) . . . . ? Au2 O3 C39 C40B -173.1(6) . . . . ? Au2 O3 C39 C40A 169.2(5) . . . . ? F14B C40B C39 O4B -167(3) . . . . ? F12B C40B C39 O4B -62(3) . . . . ? F13B C40B C39 O4B 60(3) . . . . ? F14B C40B C39 O4A -151(2) . . . . ? F12B C40B C39 O4A -46(2) . . . . ? F13B C40B C39 O4A 76(2) . . . . ? F14B C40B C39 O3 12.9(15) . . . . ? F12B C40B C39 O3 118.2(13) . . . . ? F13B C40B C39 O3 -119.4(12) . . . . ? F14B C40B C39 C40A 101(3) . . . . ? F12B C40B C39 C40A -154(4) . . . . ? F13B C40B C39 C40A -31(2) . . . . ? F14A C40A C39 O4B -176(3) . . . . ? F12A C40A C39 O4B -44(3) . . . . ? F13A C40A C39 O4B 77(3) . . . . ? F14A C40A C39 O4A -157.4(18) . . . . ? F12A C40A C39 O4A -25.3(19) . . . . ? F13A C40A C39 O4A 95.1(18) . . . . ? F14A C40A C39 O3 21.1(9) . . . . ? F12A C40A C39 O3 153.2(8) . . . . ? F13A C40A C39 O3 -86.5(9) . . . . ? F14A C40A C39 C40B -77(3) . . . . ? F12A C40A C39 C40B 55(3) . . . . ? F13A C40A C39 C40B 175(3) . . . . ? C64 Au3 Au4 C46 135.87(17) . . . . ? P3 Au3 Au4 C46 -44.01(12) . . . . ? C64 Au3 Au4 P4 -43.93(13) . . . . ? P3 Au3 Au4 P4 136.19(4) . . . . ? O5 Au3 P3 C47 114.6(2) . . . . ? Au4 Au3 P3 C47 -67.70(18) . . . . ? O5 Au3 P3 C41 -130.55(18) . . . . ? Au4 Au3 P3 C41 47.15(15) . . . . ? O5 Au3 P3 C53 -12.5(2) . . . . ? Au4 Au3 P3 C53 165.20(18) . . . . ? O7 Au4 P4 C65 110.3(2) . . . . ? Au3 Au4 P4 C65 -73.36(18) . . . . ? O7 Au4 P4 C59 -130.40(19) . . . . ? Au3 Au4 P4 C59 45.91(17) . . . . ? O7 Au4 P4 C71 -14.4(2) . . . . ? Au3 Au4 P4 C71 161.90(18) . . . . ? C64 Au3 O5 C77 114.5(4) . . . . ? P3 Au3 O5 C77 -65.9(4) . . . . ? C46 Au4 O7 C79 107.1(4) . . . . ? P4 Au4 O7 C79 -73.7(3) . . . . ? C47 P3 C41 C42 -93.2(4) . . . . ? C53 P3 C41 C42 22.5(5) . . . . ? Au3 P3 C41 C42 145.2(4) . . . . ? C47 P3 C41 C46 90.1(4) . . . . ? C53 P3 C41 C46 -154.1(3) . . . . ? Au3 P3 C41 C46 -31.5(3) . . . . ? C46 C41 C42 F15 -177.9(4) . . . . ? P3 C41 C42 F15 5.6(7) . . . . ? C46 C41 C42 C43 2.7(7) . . . . ? P3 C41 C42 C43 -173.8(4) . . . . ? F15 C42 C43 F16 -2.0(7) . . . . ? C41 C42 C43 F16 177.5(4) . . . . ? F15 C42 C43 C44 179.3(5) . . . . ? C41 C42 C43 C44 -1.3(8) . . . . ? F16 C43 C44 F17 2.1(8) . . . . ? C42 C43 C44 F17 -179.2(5) . . . . ? F16 C43 C44 C45 -179.1(4) . . . . ? C42 C43 C44 C45 -0.4(8) . . . . ? F17 C44 C45 F18 -3.3(7) . . . . ? C43 C44 C45 F18 177.9(4) . . . . ? F17 C44 C45 C46 179.3(4) . . . . ? C43 C44 C45 C46 0.5(8) . . . . ? F18 C45 C46 C41 -176.3(4) . . . . ? C44 C45 C46 C41 0.9(7) . . . . ? F18 C45 C46 Au4 8.4(6) . . . . ? C44 C45 C46 Au4 -174.4(4) . . . . ? C42 C41 C46 C45 -2.5(7) . . . . ? P3 C41 C46 C45 174.3(3) . . . . ? C42 C41 C46 Au4 172.9(3) . . . . ? P3 C41 C46 Au4 -10.2(5) . . . . ? O7 Au4 C46 C45 34.2(4) . . . . ? Au3 Au4 C46 C45 -142.1(4) . . . . ? O7 Au4 C46 C41 -141.0(3) . . . . ? Au3 Au4 C46 C41 42.7(3) . . . . ? C41 P3 C47 C48 1.6(5) . . . . ? C53 P3 C47 C48 -115.6(4) . . . . ? Au3 P3 C47 C48 113.1(4) . . . . ? C41 P3 C47 C52 179.6(4) . . . . ? C53 P3 C47 C52 62.4(4) . . . . ? Au3 P3 C47 C52 -68.9(4) . . . . ? C52 C47 C48 C49 0.3(8) . . . . ? P3 C47 C48 C49 178.3(4) . . . . ? C47 C48 C49 C50 -2.0(9) . . . . ? C48 C49 C50 C51 2.6(10) . . . . ? C49 C50 C51 C52 -1.4(10) . . . . ? C50 C51 C52 C47 -0.4(10) . . . . ? C48 C47 C52 C51 0.9(8) . . . . ? P3 C47 C52 C51 -177.2(5) . . . . ? C47 P3 C53 C58 -170.5(4) . . . . ? C41 P3 C53 C58 74.0(5) . . . . ? Au3 P3 C53 C58 -39.2(5) . . . . ? C47 P3 C53 C54 12.1(5) . . . . ? C41 P3 C53 C54 -103.4(4) . . . . ? Au3 P3 C53 C54 143.4(4) . . . . ? C58 C53 C54 C55 -0.7(8) . . . . ? P3 C53 C54 C55 176.6(4) . . . . ? C53 C54 C55 C56 -0.8(9) . . . . ? C54 C55 C56 C57 1.7(11) . . . . ? C55 C56 C57 C58 -1.0(12) . . . . ? C56 C57 C58 C53 -0.6(11) . . . . ? C54 C53 C58 C57 1.5(9) . . . . ? P3 C53 C58 C57 -176.0(5) . . . . ? C65 P4 C59 C60 -89.5(5) . . . . ? C71 P4 C59 C60 26.0(5) . . . . ? Au4 P4 C59 C60 146.4(5) . . . . ? C65 P4 C59 C64 96.1(4) . . . . ? C71 P4 C59 C64 -148.4(4) . . . . ? Au4 P4 C59 C64 -28.0(4) . . . . ? C64 C59 C60 F19 -177.8(5) . . . . ? P4 C59 C60 F19 8.1(8) . . . . ? C64 C59 C60 C61 3.0(9) . . . . ? P4 C59 C60 C61 -171.1(5) . . . . ? F19 C60 C61 F20 -0.5(10) . . . . ? C59 C60 C61 F20 178.8(6) . . . . ? F19 C60 C61 C62 -178.4(6) . . . . ? C59 C60 C61 C62 0.8(10) . . . . ? F20 C61 C62 F21 0.5(10) . . . . ? C60 C61 C62 F21 178.4(6) . . . . ? F20 C61 C62 C63 179.0(6) . . . . ? C60 C61 C62 C63 -3.1(10) . . . . ? F21 C62 C63 F22 -1.9(9) . . . . ? C61 C62 C63 F22 179.7(6) . . . . ? F21 C62 C63 C64 179.9(5) . . . . ? C61 C62 C63 C64 1.4(10) . . . . ? F22 C63 C64 C59 -175.8(5) . . . . ? C62 C63 C64 C59 2.3(8) . . . . ? F22 C63 C64 Au3 9.3(7) . . . . ? C62 C63 C64 Au3 -172.6(4) . . . . ? C60 C59 C64 C63 -4.5(7) . . . . ? P4 C59 C64 C63 170.2(4) . . . . ? C60 C59 C64 Au3 170.5(4) . . . . ? P4 C59 C64 Au3 -14.7(5) . . . . ? O5 Au3 C64 C63 38.1(4) . . . . ? Au4 Au3 C64 C63 -139.7(4) . . . . ? O5 Au3 C64 C59 -136.7(4) . . . . ? Au4 Au3 C64 C59 45.6(4) . . . . ? C59 P4 C65 C70 41.6(5) . . . . ? C71 P4 C65 C70 -74.6(5) . . . . ? Au4 P4 C65 C70 157.1(4) . . . . ? C59 P4 C65 C66 -144.3(4) . . . . ? C71 P4 C65 C66 99.6(4) . . . . ? Au4 P4 C65 C66 -28.8(4) . . . . ? C70 C65 C66 C67 0.8(8) . . . . ? P4 C65 C66 C67 -173.4(4) . . . . ? C65 C66 C67 C68 0.7(8) . . . . ? C66 C67 C68 C69 -2.3(9) . . . . ? C67 C68 C69 C70 2.1(10) . . . . ? C68 C69 C70 C65 -0.5(10) . . . . ? C66 C65 C70 C69 -0.9(9) . . . . ? P4 C65 C70 C69 173.2(5) . . . . ? C65 P4 C71 C72 -7.3(5) . . . . ? C59 P4 C71 C72 -124.6(4) . . . . ? Au4 P4 C71 C72 122.5(4) . . . . ? C65 P4 C71 C76 175.4(5) . . . . ? C59 P4 C71 C76 58.2(5) . . . . ? Au4 P4 C71 C76 -54.7(5) . . . . ? C76 C71 C72 C73 -0.1(9) . . . . ? P4 C71 C72 C73 -177.4(5) . . . . ? C71 C72 C73 C74 0.1(10) . . . . ? C72 C73 C74 C75 -1.1(12) . . . . ? C73 C74 C75 C76 2.0(13) . . . . ? C74 C75 C76 C71 -2.0(12) . . . . ? C72 C71 C76 C75 1.0(9) . . . . ? P4 C71 C76 C75 178.3(6) . . . . ? Au3 O5 C77 O6 3.0(8) . . . . ? Au3 O5 C77 C78A -172.6(4) . . . . ? Au3 O5 C77 C78B 170.2(9) . . . . ? F24A C78A C77 O6 -111.5(14) . . . . ? F25A C78A C77 O6 21.2(11) . . . . ? F23A C78A C77 O6 132.2(9) . . . . ? F24A C78A C77 O5 64.7(15) . . . . ? F25A C78A C77 O5 -162.6(8) . . . . ? F23A C78A C77 O5 -51.7(9) . . . . ? F24A C78A C77 C78B 159(7) . . . . ? F25A C78A C77 C78B -68(6) . . . . ? F23A C78A C77 C78B 43(5) . . . . ? F24B C78B C77 O6 78(3) . . . . ? F23B C78B C77 O6 -57.5(18) . . . . ? F25B C78B C77 O6 -144.3(13) . . . . ? F24B C78B C77 O5 -91(4) . . . . ? F23B C78B C77 O5 133.6(14) . . . . ? F25B C78B C77 O5 46.9(16) . . . . ? F24B C78B C77 C78A 177(9) . . . . ? F23B C78B C77 C78A 42(5) . . . . ? F25B C78B C77 C78A -45(5) . . . . ? Au4 O7 C79 O8 1.1(8) . . . . ? Au4 O7 C79 C80B 176.2(4) . . . . ? Au4 O7 C79 C80A 177.9(4) . . . . ? F27B C80B C79 O8 -64.2(10) . . . . ? F28B C80B C79 O8 56.1(10) . . . . ? F26B C80B C79 O8 177.3(9) . . . . ? F27B C80B C79 O7 120.0(9) . . . . ? F28B C80B C79 O7 -119.7(8) . . . . ? F26B C80B C79 O7 1.4(11) . . . . ? F27B C80B C79 C80A 103(5) . . . . ? F28B C80B C79 C80A -137(5) . . . . ? F26B C80B C79 C80A -16(5) . . . . ? F26A C80A C79 O8 -10.6(11) . . . . ? F27A C80A C79 O8 -124.0(9) . . . . ? F28A C80A C79 O8 112.0(11) . . . . ? F26A C80A C79 O7 172.2(8) . . . . ? F27A C80A C79 O7 58.9(10) . . . . ? F28A C80A C79 O7 -65.1(11) . . . . ? F26A C80A C79 C80B -25(5) . . . . ? F27A C80A C79 C80B -138(5) . . . . ? F28A C80A C79 C80B 98(5) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 1.596 _refine_diff_density_min -1.617 _refine_diff_density_rms 0.142