# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Edwin Constable' 'Henk J. Bolink' 'Ruben D. Costa' 'Stefan Graber' 'Catherine E Housecroft' 'Markus Neuburger' 'Enrique Orti' 'Silvia Schaffner' _publ_contact_author_name 'Edwin Constable' _publ_contact_author_email EDWIN.CONSTABLE@UNIBAS.CH _publ_section_title ; Two are not always better than one: ligand optimisation for long-living light-emitting electrochemical cells ; # Attachment 'sg75-1_123k.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 711832' _publ_section_exptl_refinement # Some potentially useful phrases are donated by Bill Clegg: ; In the absence of significant anomalous scattering, Friedel pairs were merged. The absolute configuration was arbitrarily assigned. The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:nnn) reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (G\"orbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997). G\"orbitz, C. H. (1999). Acta Cryst. B55, 1090-1098. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularise their geometry (C---H in the range 0.93--0.98, N---H in the range 0.86--0.89 N---H to 0.86 O---H = 0.82 \%A) and U~iso~(H) (in the range 1.2-1.5 times U~eq~ of the parent atom), after which the positions were refined with riding constraints. ; _publ_section_exptl_prep # Brief details or a reference. Include solvent if known ; ? ; # Hand-made tables can be put in the cif. The number of columns # is set in the loop header. # The contants of each column can either be a piece of text # without any spaces (eg a number) or other text enclosed in " " # Remove the leading # in the following example #geom_extra_table_head_A #; #Table 2. #Molecular parameters deviating most from MOGUL averages #; # #loop_ #_geom_extra_tableA_col_1 #_geom_extra_tableA_col_2 #_geom_extra_tableA_col_3 #_geom_extra_tableA_col_4 # #Parameter "Observed Value" "MOGUL Value" "MOGUL e.s.d" #N5-C6-C4 129 124 "7 (\%)" #C3-O10-C2 105 109 "2 (\%)" #C6-O7 1.25 1.22 ".02 (\%A)" # # End of 'script/refcif-b.dat' #end of refcif _cell_length_a 13.6575(6) _cell_length_b 8.8865(4) _cell_length_c 29.8329(12) _cell_angle_alpha 90 _cell_angle_beta 95.286(2) _cell_angle_gamma 90 _cell_volume 3605.3(3) _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' 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' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 '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' Ir -1.4442 7.9887 27.3049 1.5928 16.7296 8.8655 15.6115 0.4179 5.8338 45.0011 11.4722 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C44 H32 F6 Ir1 N4 P1 # Dc = 1.76 Fooo = 1880.00 Mu = 38.19 M = 953.95 # Found Formula = C44 H32 F6 Ir1 N4 P1 # Dc = 1.76 FOOO = 1880.00 Mu = 38.19 M = 953.95 _chemical_formula_sum 'C44 H32 F6 Ir1 N4 P1' _chemical_formula_moiety 'C44 H32 Ir N4, F6 P' _chemical_compound_source ? _chemical_formula_weight 953.95 _cell_measurement_reflns_used 9306 _cell_measurement_theta_min 3.08 _cell_measurement_theta_max 36.81 _cell_measurement_temperature 123 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_max 0.44 _exptl_crystal_density_diffrn 1.757 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 1880 _exptl_absorpt_coefficient_mu 3.819 # Sheldrick geometric approximatio 0.40 0.47 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.40 _exptl_absorpt_correction_T_max 0.47 # 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 'Nonius KappaCCD' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius, 1997-2001).' _computing_cell_refinement 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 123 _diffrn_reflns_number 207215 _reflns_number_total 20603 _diffrn_reflns_av_R_equivalents 0.044 # Number of reflections with Friedels Law is 20603 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 20672 _diffrn_reflns_theta_min 2.122 _diffrn_reflns_theta_max 38.790 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 38.790 _diffrn_measured_fraction_theta_full 0.996 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -52 _diffrn_reflns_limit_l_max 52 _reflns_limit_h_min -24 _reflns_limit_h_max 23 _reflns_limit_k_min 0 _reflns_limit_k_max 15 _reflns_limit_l_min 0 _reflns_limit_l_max 52 _oxford_diffrn_Wilson_B_factor 0.00 _oxford_diffrn_Wilson_scale 0.00 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.90 _refine_diff_density_max 2.13 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>3.0\s(I) _refine_ls_number_reflns 12996 _refine_ls_number_restraints 120 _refine_ls_number_parameters 559 _oxford_refine_ls_R_factor_ref 0.0263 _refine_ls_wR_factor_ref 0.0254 _refine_ls_goodness_of_fit_ref 1.1122 _refine_ls_shift/su_max 0.002519 # The values computed from all data _oxford_reflns_number_all 20589 _refine_ls_R_factor_all 0.0543 _refine_ls_wR_factor_all 0.0293 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 14344 _refine_ls_R_factor_gt 0.0299 _refine_ls_wR_factor_gt 0.0262 # 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 constr # 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: 0.510 -0.721 0.279 -0.330 ; _refine_special_details ; The PF6 molecule is disordered and has been refined using a overlay model. In order to keep the refinement stable restraints have been applied to keep equivalent distances equal and adp's of bonded atoms similar. ; # Insert your own references if required - in alphabetical order _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Nonius (1997-2001). COLLECT. Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326. New York: 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. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # 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 _oxford_atom_site_special_shape _atom_site_attached_hydrogens Ir1 Ir 0.164234(5) 0.462357(8) 0.387062(2) 0.0215 1.0000 Uani . . . . . . . N1 N 0.22255(13) 0.6429(2) 0.42307(7) 0.0263 1.0000 Uani . . . . . . . N2 N 0.09941(13) 0.2983(2) 0.34709(5) 0.0237 1.0000 Uani . . . . . . . N3 N 0.12312(18) 0.3323(2) 0.44529(6) 0.0329 1.0000 Uani . . . . . . . N4 N 0.30398(15) 0.3519(2) 0.41356(6) 0.0293 1.0000 Uani . . . . . . . C1 C 0.21926(14) 0.5786(2) 0.33723(7) 0.0250 1.0000 Uani . . . . . . . C2 C 0.21431(15) 0.5419(3) 0.29170(7) 0.0331 1.0000 Uani . . . . . . . C3 C 0.25700(19) 0.6342(4) 0.26109(9) 0.0451 1.0000 Uani . . . . . . . C4 C 0.30326(19) 0.7662(4) 0.27523(12) 0.0512 1.0000 Uani . . . . . . . C5 C 0.30945(18) 0.8065(3) 0.32014(12) 0.0436 1.0000 Uani . . . . . . . C6 C 0.26738(15) 0.7131(3) 0.35110(9) 0.0310 1.0000 Uani . . . . . . . C7 C 0.27094(15) 0.7457(2) 0.39920(9) 0.0314 1.0000 Uani . . . . . . . C8 C 0.31894(18) 0.8672(3) 0.42154(12) 0.0444 1.0000 Uani . . . . . . . C9 C 0.3158(2) 0.8844(4) 0.46731(13) 0.0520 1.0000 Uani . . . . . . . C10 C 0.2636(2) 0.7825(4) 0.49082(12) 0.0464 1.0000 Uani . . . . . . . C11 C 0.2186(2) 0.6636(3) 0.46768(9) 0.0358 1.0000 Uani . . . . . . . C12 C 0.04100(14) 0.5709(2) 0.36323(7) 0.0232 1.0000 Uani . . . . . . . C13 C 0.01024(17) 0.7154(3) 0.37401(9) 0.0308 1.0000 Uani . . . . . . . C14 C -0.07502(18) 0.7778(3) 0.35226(10) 0.0379 1.0000 Uani . . . . . . . C15 C -0.13067(19) 0.6998(3) 0.31881(10) 0.0401 1.0000 Uani . . . . . . . C16 C -0.10158(16) 0.5571(3) 0.30703(8) 0.0338 1.0000 Uani . . . . . . . C17 C -0.01608(15) 0.4933(3) 0.32895(7) 0.0264 1.0000 Uani . . . . . . . C18 C 0.01674(15) 0.3408(3) 0.32057(7) 0.0256 1.0000 Uani . . . . . . . C19 C -0.03045(17) 0.2376(3) 0.29051(7) 0.0310 1.0000 Uani . . . . . . . C20 C 0.00326(19) 0.0906(3) 0.28923(8) 0.0355 1.0000 Uani . . . . . . . C21 C 0.08381(18) 0.0481(3) 0.31814(8) 0.0333 1.0000 Uani . . . . . . . C22 C 0.12952(17) 0.1540(2) 0.34636(7) 0.0275 1.0000 Uani . . . . . . . C23 C 0.0332(2) 0.2877(3) 0.45569(8) 0.0404 1.0000 Uani . . . . . . . C24 C 0.0225(3) 0.1987(3) 0.49355(11) 0.0584 1.0000 Uani . . . . . . . C25 C 0.1032(4) 0.1544(4) 0.52118(11) 0.0676 1.0000 Uani . . . . . . . C26 C 0.1943(3) 0.1971(3) 0.51043(9) 0.0552 1.0000 Uani . . . . . . . C27 C 0.2033(3) 0.2854(3) 0.47230(8) 0.0406 1.0000 Uani . . . . . . . C28 C 0.3005(2) 0.3206(3) 0.45807(8) 0.0393 1.0000 Uani . . . . . . . C29 C 0.3841(3) 0.3158(5) 0.48812(11) 0.0637 1.0000 Uani . . . . . . . C30 C 0.4737(3) 0.3382(6) 0.47205(14) 0.0788 1.0000 Uani . . . . . . . C31 C 0.4790(2) 0.3587(5) 0.42706(13) 0.0615 1.0000 Uani . . . . . . . C32 C 0.39317(18) 0.3637(3) 0.39777(10) 0.0369 1.0000 Uani . . . . . . . C33 C -0.0584(2) 0.3296(3) 0.42750(9) 0.0424 1.0000 Uani . . . . . . . C34 C -0.1047(3) 0.2218(4) 0.39934(11) 0.0611 1.0000 Uani . . . . . . . C35 C -0.1945(3) 0.2506(6) 0.37606(12) 0.0763 1.0000 Uani . . . . . . . C36 C -0.2392(3) 0.3869(7) 0.38131(12) 0.0786 1.0000 Uani . . . . . . . C37 C -0.1934(3) 0.4968(6) 0.40937(11) 0.0623 1.0000 Uani . . . . . . . C38 C -0.1032(2) 0.4666(4) 0.43242(9) 0.0457 1.0000 Uani . . . . . . . C39 C 0.40202(17) 0.3686(3) 0.34877(10) 0.0357 1.0000 Uani . . . . . . . C40 C 0.36025(19) 0.2548(3) 0.32131(9) 0.0372 1.0000 Uani . . . . . . . C41 C 0.3747(3) 0.2474(5) 0.27626(11) 0.0619 1.0000 Uani . . . . . . . C42 C 0.4318(4) 0.3560(8) 0.25817(16) 0.0918 1.0000 Uani . . . . . . . C43 C 0.4735(3) 0.4696(7) 0.2845(2) 0.0936 1.0000 Uani . . . . . . . C44 C 0.4602(2) 0.4766(4) 0.33041(16) 0.0623 1.0000 Uani . . . . . . . P1 P 0.39462(6) 0.05859(11) 0.61434(3) 0.0482 1.0000 Uani D U . . . . . F1 F 0.4830(3) 0.1209(7) 0.64426(17) 0.0828 0.6500 Uani D U . . . . . F2 F 0.2986(3) 0.0011(4) 0.58143(10) 0.0643 0.6500 Uani D U . . . . . F3 F 0.3605(4) 0.2302(4) 0.59893(13) 0.0798 0.6500 Uani D U . . . . . F4 F 0.4162(3) -0.1060(5) 0.62732(15) 0.0879 0.6500 Uani D U . . . . . F5 F 0.3234(2) 0.0704(4) 0.65318(10) 0.0596 0.6500 Uani D U . . . . . F6 F 0.4519(4) 0.0514(7) 0.57082(14) 0.1081 0.6500 Uani D U . . . . . F11 F 0.4355(5) 0.1658(8) 0.5786(2) 0.0810 0.3500 Uani D U . . . . . F12 F 0.3742(4) -0.0537(7) 0.65395(17) 0.0652 0.3500 Uani D U . . . . . F13 F 0.2957(4) 0.1301(8) 0.6136(2) 0.0842 0.3500 Uani D U . . . . . F14 F 0.5058(3) -0.0251(7) 0.6170(2) 0.0734 0.3500 Uani D U . . . . . F15 F 0.3613(4) -0.0600(8) 0.57800(19) 0.0838 0.3500 Uani D U . . . . . F16 F 0.4440(6) 0.1711(9) 0.6529(3) 0.1055 0.3500 Uani D U . . . . . H21 H 0.1827 0.4537 0.2816 0.0412 1.0000 Uiso R . . . . . . H31 H 0.2540 0.6064 0.2309 0.0557 1.0000 Uiso R . . . . . . H41 H 0.3308 0.8314 0.2544 0.0614 1.0000 Uiso R . . . . . . H51 H 0.3409 0.8951 0.3296 0.0530 1.0000 Uiso R . . . . . . H81 H 0.3541 0.9355 0.4053 0.0549 1.0000 Uiso R . . . . . . H91 H 0.3491 0.9636 0.4819 0.0636 1.0000 Uiso R . . . . . . H101 H 0.2584 0.7923 0.5217 0.0559 1.0000 Uiso R . . . . . . H111 H 0.1844 0.5929 0.4828 0.0433 1.0000 Uiso R . . . . . . H131 H 0.0464 0.7700 0.3958 0.0386 1.0000 Uiso R . . . . . . H141 H -0.0954 0.8733 0.3601 0.0473 1.0000 Uiso R . . . . . . H151 H -0.1890 0.7425 0.3046 0.0499 1.0000 Uiso R . . . . . . H161 H -0.1386 0.5031 0.2848 0.0434 1.0000 Uiso R . . . . . . H191 H -0.0832 0.2654 0.2715 0.0394 1.0000 Uiso R . . . . . . H201 H -0.0290 0.0208 0.2694 0.0438 1.0000 Uiso R . . . . . . H211 H 0.1069 -0.0484 0.3187 0.0406 1.0000 Uiso R . . . . . . H221 H 0.1815 0.1241 0.3663 0.0334 1.0000 Uiso R . . . . . . H241 H -0.0398 0.1672 0.5006 0.0708 1.0000 Uiso R . . . . . . H251 H 0.0962 0.0971 0.5465 0.0868 1.0000 Uiso R . . . . . . H261 H 0.2502 0.1677 0.5282 0.0648 1.0000 Uiso R . . . . . . H291 H 0.3788 0.2987 0.5188 0.0759 1.0000 Uiso R . . . . . . H301 H 0.5311 0.3375 0.4916 0.0928 1.0000 Uiso R . . . . . . H311 H 0.5372 0.3693 0.4151 0.0712 1.0000 Uiso R . . . . . . H341 H -0.0746 0.1296 0.3963 0.0786 1.0000 Uiso R . . . . . . H351 H -0.2263 0.1765 0.3572 0.0957 1.0000 Uiso R . . . . . . H361 H -0.2995 0.4043 0.3658 0.0946 1.0000 Uiso R . . . . . . H371 H -0.2220 0.5905 0.4128 0.0781 1.0000 Uiso R . . . . . . H381 H -0.0724 0.5391 0.4508 0.0573 1.0000 Uiso R . . . . . . H401 H 0.3228 0.1812 0.3333 0.0457 1.0000 Uiso R . . . . . . H411 H 0.3473 0.1691 0.2579 0.0742 1.0000 Uiso R . . . . . . H421 H 0.4416 0.3520 0.2282 0.1198 1.0000 Uiso R . . . . . . H431 H 0.5119 0.5433 0.2722 0.1114 1.0000 Uiso R . . . . . . H441 H 0.4878 0.5510 0.3488 0.0769 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 Ir1 0.02353(3) 0.02071(2) 0.02064(2) 0.00140(3) 0.004131(18) -0.00112(3) N1 0.0231(7) 0.0219(7) 0.0341(8) -0.0037(6) 0.0029(6) -0.0013(6) N2 0.0257(7) 0.0254(7) 0.0206(6) -0.0020(5) 0.0056(5) -0.0011(6) N3 0.0538(12) 0.0226(7) 0.0236(7) -0.0020(6) 0.0099(8) -0.0068(8) N4 0.0362(9) 0.0223(7) 0.0279(8) -0.0004(6) -0.0041(7) 0.0043(7) C1 0.0184(7) 0.0265(8) 0.0310(9) 0.0104(7) 0.0073(6) 0.0051(6) C2 0.0243(8) 0.0469(12) 0.0291(9) 0.0151(10) 0.0075(7) 0.0100(9) C3 0.0293(10) 0.0681(19) 0.0399(12) 0.0304(13) 0.0136(9) 0.0156(12) C4 0.0282(11) 0.0619(19) 0.0662(18) 0.0428(16) 0.0189(11) 0.0122(11) C5 0.0240(10) 0.0359(12) 0.0721(19) 0.0266(13) 0.0116(11) 0.0030(9) C6 0.0184(7) 0.0255(9) 0.0500(13) 0.0135(9) 0.0077(8) 0.0040(7) C7 0.0188(8) 0.0226(8) 0.0531(14) 0.0019(9) 0.0044(8) 0.0025(7) C8 0.0235(9) 0.0256(10) 0.084(2) -0.0069(12) 0.0050(11) -0.0027(8) C9 0.0283(11) 0.0390(13) 0.088(2) -0.0310(16) 0.0018(13) -0.0038(10) C10 0.0358(12) 0.0445(15) 0.0582(17) -0.0280(13) 0.0004(11) 0.0005(11) C11 0.0365(11) 0.0333(11) 0.0375(12) -0.0111(9) 0.0041(9) -0.0008(9) C12 0.0218(7) 0.0230(7) 0.0261(8) 0.0001(6) 0.0089(6) -0.0004(6) C13 0.0260(9) 0.0272(9) 0.0402(11) -0.0029(8) 0.0088(8) 0.0015(7) C14 0.0284(10) 0.0351(12) 0.0512(14) -0.0030(10) 0.0088(10) 0.0065(9) C15 0.0274(10) 0.0449(14) 0.0481(14) 0.0002(12) 0.0042(9) 0.0098(10) C16 0.0244(8) 0.0454(14) 0.0318(9) -0.0014(9) 0.0033(7) 0.0036(9) C17 0.0241(8) 0.0323(9) 0.0237(8) 0.0002(7) 0.0066(6) 0.0018(7) C18 0.0241(8) 0.0318(9) 0.0218(7) -0.0011(7) 0.0057(6) -0.0013(7) C19 0.0282(9) 0.0405(12) 0.0242(8) -0.0070(8) 0.0019(7) -0.0022(8) C20 0.0357(11) 0.0395(12) 0.0317(10) -0.0140(9) 0.0052(8) -0.0047(10) C21 0.0358(10) 0.0305(10) 0.0340(10) -0.0094(9) 0.0054(8) -0.0008(9) C22 0.0306(9) 0.0260(9) 0.0261(8) -0.0026(7) 0.0036(7) 0.0009(7) C23 0.0694(18) 0.0269(10) 0.0285(10) -0.0060(8) 0.0233(11) -0.0167(11) C24 0.106(3) 0.0332(13) 0.0415(14) -0.0005(11) 0.0386(17) -0.0194(16) C25 0.138(4) 0.0339(14) 0.0360(14) 0.0096(11) 0.0346(19) -0.0010(19) C26 0.106(3) 0.0343(13) 0.0257(10) 0.0051(10) 0.0102(14) 0.0134(16) C27 0.0737(19) 0.0265(10) 0.0217(9) 0.0011(7) 0.0047(10) 0.0039(11) C28 0.0575(16) 0.0327(11) 0.0255(9) -0.0017(8) -0.0081(10) 0.0111(11) C29 0.078(2) 0.071(2) 0.0371(14) -0.0083(15) -0.0237(15) 0.028(2) C30 0.060(2) 0.108(4) 0.062(2) -0.028(2) -0.0337(18) 0.035(2) C31 0.0357(14) 0.080(3) 0.065(2) -0.0203(19) -0.0139(13) 0.0211(16) C32 0.0307(10) 0.0317(11) 0.0466(13) -0.0043(10) -0.0054(9) 0.0077(9) C33 0.0563(16) 0.0430(13) 0.0314(10) -0.0122(10) 0.0229(11) -0.0264(12) C34 0.088(3) 0.0574(19) 0.0421(14) -0.0212(14) 0.0302(16) -0.0477(19) C35 0.083(3) 0.104(3) 0.0460(17) -0.027(2) 0.0253(18) -0.065(3) C36 0.0492(18) 0.146(5) 0.0437(16) -0.021(2) 0.0198(14) -0.046(3) C37 0.0464(16) 0.098(3) 0.0458(16) -0.0168(18) 0.0220(13) -0.0143(18) C38 0.0461(14) 0.0565(17) 0.0371(12) -0.0153(13) 0.0171(10) -0.0174(14) C39 0.0236(9) 0.0321(11) 0.0519(14) 0.0101(10) 0.0074(9) 0.0107(8) C40 0.0341(11) 0.0433(13) 0.0352(11) 0.0022(10) 0.0092(9) 0.0134(10) C41 0.0508(17) 0.097(3) 0.0401(14) 0.0023(17) 0.0149(13) 0.0386(19) C42 0.071(3) 0.143(5) 0.070(3) 0.056(3) 0.047(2) 0.062(3) C43 0.054(2) 0.097(3) 0.140(5) 0.077(4) 0.061(3) 0.038(2) C44 0.0273(11) 0.0450(17) 0.117(3) 0.0300(19) 0.0202(15) 0.0109(12) P1 0.0435(4) 0.0679(6) 0.0327(3) 0.0023(3) 0.0007(3) -0.0168(4) F1 0.0360(17) 0.131(5) 0.079(3) -0.020(3) -0.0069(17) -0.024(2) F2 0.082(2) 0.060(2) 0.0453(16) 0.0113(14) -0.0262(16) -0.0254(18) F3 0.114(3) 0.058(2) 0.064(2) 0.0025(18) -0.012(2) -0.027(2) F4 0.076(3) 0.087(3) 0.097(3) -0.001(3) -0.015(2) 0.035(2) F5 0.0484(16) 0.085(3) 0.0476(16) -0.0055(16) 0.0143(13) -0.0003(16) F6 0.098(3) 0.171(6) 0.062(2) -0.034(3) 0.042(2) -0.038(4) F11 0.064(4) 0.094(6) 0.081(5) 0.058(5) -0.011(4) -0.007(4) F12 0.059(4) 0.085(5) 0.048(3) 0.031(3) -0.012(3) -0.028(4) F13 0.073(5) 0.090(6) 0.093(6) 0.012(5) 0.024(4) 0.033(4) F14 0.041(3) 0.061(4) 0.114(6) 0.041(4) -0.013(3) -0.009(3) F15 0.042(3) 0.145(8) 0.064(4) -0.051(5) -0.001(3) -0.006(4) F16 0.116(9) 0.097(7) 0.095(7) -0.005(6) -0.040(7) -0.057(7) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.19815(8) 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 Ir1 . N1 . 2.0504(18) yes Ir1 . N2 . 2.0341(17) yes Ir1 . N3 . 2.2017(18) yes Ir1 . N4 . 2.2254(19) yes Ir1 . C1 . 2.0120(19) yes Ir1 . C12 . 2.012(2) yes N1 . C7 . 1.366(3) yes N1 . C11 . 1.350(3) yes N2 . C18 . 1.371(3) yes N2 . C22 . 1.347(3) yes N3 . C23 . 1.354(4) yes N3 . C27 . 1.364(4) yes N4 . C28 . 1.362(3) yes N4 . C32 . 1.350(3) yes C1 . C2 . 1.393(3) yes C1 . C6 . 1.408(3) yes C2 . C3 . 1.395(3) yes C2 . H21 . 0.931 no C3 . C4 . 1.379(5) yes C3 . H31 . 0.931 no C4 . C5 . 1.382(5) yes C4 . H41 . 0.952 no C5 . C6 . 1.403(3) yes C5 . H51 . 0.929 no C6 . C7 . 1.460(4) yes C7 . C8 . 1.400(4) yes C8 . C9 . 1.378(5) yes C8 . H81 . 0.936 no C9 . C10 . 1.383(5) yes C9 . H91 . 0.925 no C10 . C11 . 1.376(4) yes C10 . H101 . 0.936 no C11 . H111 . 0.925 no C12 . C13 . 1.398(3) yes C12 . C17 . 1.408(3) yes C13 . C14 . 1.395(4) yes C13 . H131 . 0.918 no C14 . C15 . 1.384(4) yes C14 . H141 . 0.930 no C15 . C16 . 1.384(4) yes C15 . H151 . 0.947 no C16 . C17 . 1.404(3) yes C16 . H161 . 0.930 no C17 . C18 . 1.456(3) yes C18 . C19 . 1.398(3) yes C19 . C20 . 1.387(4) yes C19 . H191 . 0.908 no C20 . C21 . 1.386(4) yes C20 . H201 . 0.938 no C21 . C22 . 1.374(3) yes C21 . H211 . 0.913 no C22 . H221 . 0.923 no C23 . C24 . 1.398(4) yes C23 . C33 . 1.488(5) yes C24 . C25 . 1.372(6) yes C24 . H241 . 0.937 no C25 . C26 . 1.366(6) yes C25 . H251 . 0.924 no C26 . C27 . 1.397(4) yes C26 . H261 . 0.925 no C27 . C28 . 1.464(5) yes C28 . C29 . 1.386(4) yes C29 . C30 . 1.369(7) yes C29 . H291 . 0.938 no C30 . C31 . 1.363(6) yes C30 . H301 . 0.933 no C31 . C32 . 1.397(4) yes C31 . H311 . 0.907 no C32 . C39 . 1.478(4) yes C33 . C34 . 1.387(4) yes C33 . C38 . 1.376(5) yes C34 . C35 . 1.377(7) yes C34 . H341 . 0.925 no C35 . C36 . 1.372(8) yes C35 . H351 . 0.945 no C36 . C37 . 1.396(6) yes C36 . H361 . 0.921 no C37 . C38 . 1.381(5) yes C37 . H371 . 0.929 no C38 . H381 . 0.923 no C39 . C40 . 1.390(4) yes C39 . C44 . 1.390(4) yes C40 . C41 . 1.378(4) yes C40 . H401 . 0.922 no C41 . C42 . 1.382(7) yes C41 . H411 . 0.942 no C42 . C43 . 1.371(8) yes C42 . H421 . 0.916 no C43 . C44 . 1.398(7) yes C43 . H431 . 0.935 no C44 . H441 . 0.918 no P1 . F1 . 1.537(4) yes P1 . F2 . 1.645(3) yes P1 . F3 . 1.647(4) yes P1 . F4 . 1.534(4) yes P1 . F5 . 1.583(3) yes P1 . F6 . 1.578(3) yes P1 . F11 . 1.570(5) yes P1 . F12 . 1.591(4) yes P1 . F13 . 1.492(5) yes P1 . F14 . 1.686(5) yes P1 . F15 . 1.550(5) yes P1 . F16 . 1.624(6) yes 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 N1 . Ir1 . N2 . 174.32(7) yes N1 . Ir1 . N3 . 96.44(7) yes N2 . Ir1 . N3 . 87.56(7) yes N1 . Ir1 . N4 . 83.10(7) yes N2 . Ir1 . N4 . 101.82(7) yes N3 . Ir1 . N4 . 76.18(8) yes N1 . Ir1 . C1 . 80.32(9) yes N2 . Ir1 . C1 . 96.15(8) yes N3 . Ir1 . C1 . 172.84(8) yes N4 . Ir1 . C1 . 97.03(8) yes N1 . Ir1 . C12 . 94.71(8) yes N2 . Ir1 . C12 . 80.31(8) yes N3 . Ir1 . C12 . 105.34(8) yes N4 . Ir1 . C12 . 177.49(7) yes C1 . Ir1 . C12 . 81.37(7) yes Ir1 . N1 . C7 . 115.69(16) yes Ir1 . N1 . C11 . 125.06(16) yes C7 . N1 . C11 . 119.2(2) yes Ir1 . N2 . C18 . 115.56(14) yes Ir1 . N2 . C22 . 125.08(15) yes C18 . N2 . C22 . 119.31(19) yes Ir1 . N3 . C23 . 129.58(19) yes Ir1 . N3 . C27 . 112.16(18) yes C23 . N3 . C27 . 118.1(2) yes Ir1 . N4 . C28 . 109.30(17) yes Ir1 . N4 . C32 . 127.85(16) yes C28 . N4 . C32 . 118.0(2) yes Ir1 . C1 . C2 . 127.75(18) yes Ir1 . C1 . C6 . 114.52(16) yes C2 . C1 . C6 . 117.7(2) yes C1 . C2 . C3 . 121.0(3) yes C1 . C2 . H21 . 119.6 no C3 . C2 . H21 . 119.4 no C2 . C3 . C4 . 120.5(3) yes C2 . C3 . H31 . 119.5 no C4 . C3 . H31 . 120.0 no C3 . C4 . C5 . 120.1(2) yes C3 . C4 . H41 . 121.1 no C5 . C4 . H41 . 118.8 no C4 . C5 . C6 . 119.5(3) yes C4 . C5 . H51 . 120.1 no C6 . C5 . H51 . 120.4 no C1 . C6 . C5 . 121.1(3) yes C1 . C6 . C7 . 115.44(19) yes C5 . C6 . C7 . 123.4(2) yes C6 . C7 . N1 . 113.9(2) yes C6 . C7 . C8 . 126.4(2) yes N1 . C7 . C8 . 119.7(3) yes C7 . C8 . C9 . 120.1(3) yes C7 . C8 . H81 . 119.5 no C9 . C8 . H81 . 120.4 no C8 . C9 . C10 . 119.7(3) yes C8 . C9 . H91 . 119.3 no C10 . C9 . H91 . 121.0 no C9 . C10 . C11 . 118.4(3) yes C9 . C10 . H101 . 121.9 no C11 . C10 . H101 . 119.7 no C10 . C11 . N1 . 122.9(3) yes C10 . C11 . H111 . 119.9 no N1 . C11 . H111 . 117.2 no Ir1 . C12 . C13 . 128.20(17) yes Ir1 . C12 . C17 . 114.29(14) yes C13 . C12 . C17 . 117.3(2) yes C12 . C13 . C14 . 120.9(2) yes C12 . C13 . H131 . 119.7 no C14 . C13 . H131 . 119.4 no C13 . C14 . C15 . 121.1(2) yes C13 . C14 . H141 . 120.1 no C15 . C14 . H141 . 118.8 no C14 . C15 . C16 . 119.4(2) yes C14 . C15 . H151 . 120.4 no C16 . C15 . H151 . 120.2 no C15 . C16 . C17 . 119.8(2) yes C15 . C16 . H161 . 120.3 no C17 . C16 . H161 . 119.9 no C12 . C17 . C16 . 121.5(2) yes C12 . C17 . C18 . 114.94(19) yes C16 . C17 . C18 . 123.5(2) yes C17 . C18 . N2 . 114.06(18) yes C17 . C18 . C19 . 126.1(2) yes N2 . C18 . C19 . 119.7(2) yes C18 . C19 . C20 . 120.1(2) yes C18 . C19 . H191 . 120.9 no C20 . C19 . H191 . 119.0 no C19 . C20 . C21 . 119.1(2) yes C19 . C20 . H201 . 120.2 no C21 . C20 . H201 . 120.7 no C20 . C21 . C22 . 119.0(2) yes C20 . C21 . H211 . 121.3 no C22 . C21 . H211 . 119.7 no C21 . C22 . N2 . 122.7(2) yes C21 . C22 . H221 . 118.5 no N2 . C22 . H221 . 118.8 no N3 . C23 . C24 . 121.0(3) yes N3 . C23 . C33 . 122.0(2) yes C24 . C23 . C33 . 116.9(3) yes C23 . C24 . C25 . 120.7(3) yes C23 . C24 . H241 . 120.9 no C25 . C24 . H241 . 118.4 no C24 . C25 . C26 . 118.5(3) yes C24 . C25 . H251 . 120.8 no C26 . C25 . H251 . 120.7 no C25 . C26 . C27 . 119.9(4) yes C25 . C26 . H261 . 120.6 no C27 . C26 . H261 . 119.6 no C26 . C27 . N3 . 121.8(3) yes C26 . C27 . C28 . 120.5(3) yes N3 . C27 . C28 . 117.6(2) yes C27 . C28 . N4 . 116.1(2) yes C27 . C28 . C29 . 121.4(3) yes N4 . C28 . C29 . 122.4(3) yes C28 . C29 . C30 . 118.6(3) yes C28 . C29 . H291 . 120.2 no C30 . C29 . H291 . 121.2 no C29 . C30 . C31 . 119.6(3) yes C29 . C30 . H301 . 120.4 no C31 . C30 . H301 . 120.0 no C30 . C31 . C32 . 120.2(4) yes C30 . C31 . H311 . 122.0 no C32 . C31 . H311 . 117.8 no C31 . C32 . N4 . 120.7(3) yes C31 . C32 . C39 . 118.6(3) yes N4 . C32 . C39 . 120.4(2) yes C23 . C33 . C34 . 118.8(3) yes C23 . C33 . C38 . 121.3(2) yes C34 . C33 . C38 . 119.5(3) yes C33 . C34 . C35 . 120.8(4) yes C33 . C34 . H341 . 119.2 no C35 . C34 . H341 . 119.9 no C34 . C35 . C36 . 119.5(3) yes C34 . C35 . H351 . 120.6 no C36 . C35 . H351 . 119.9 no C35 . C36 . C37 . 120.4(4) yes C35 . C36 . H361 . 118.6 no C37 . C36 . H361 . 121.0 no C36 . C37 . C38 . 119.5(4) yes C36 . C37 . H371 . 121.6 no C38 . C37 . H371 . 118.9 no C37 . C38 . C33 . 120.3(3) yes C37 . C38 . H381 . 119.8 no C33 . C38 . H381 . 119.9 no C32 . C39 . C40 . 119.7(2) yes C32 . C39 . C44 . 120.8(3) yes C40 . C39 . C44 . 119.2(3) yes C39 . C40 . C41 . 121.5(3) yes C39 . C40 . H401 . 120.0 no C41 . C40 . H401 . 118.5 no C40 . C41 . C42 . 119.0(4) yes C40 . C41 . H411 . 121.2 no C42 . C41 . H411 . 119.8 no C41 . C42 . C43 . 120.7(4) yes C41 . C42 . H421 . 119.5 no C43 . C42 . H421 . 119.9 no C42 . C43 . C44 . 120.6(4) yes C42 . C43 . H431 . 120.6 no C44 . C43 . H431 . 118.8 no C43 . C44 . C39 . 119.1(4) yes C43 . C44 . H441 . 122.3 no C39 . C44 . H441 . 118.6 no F1 . P1 . F2 . 177.0(3) yes F1 . P1 . F3 . 90.9(3) yes F2 . P1 . F3 . 86.07(18) yes F1 . P1 . F4 . 94.3(3) yes F2 . P1 . F4 . 88.8(2) yes F3 . P1 . F4 . 174.5(2) yes F1 . P1 . F5 . 93.1(2) yes F2 . P1 . F5 . 87.01(18) yes F3 . P1 . F5 . 88.0(2) yes F4 . P1 . F5 . 89.7(2) yes F1 . P1 . F6 . 94.0(2) yes F2 . P1 . F6 . 85.7(2) yes F3 . P1 . F6 . 87.5(3) yes F4 . P1 . F6 . 94.1(3) yes F5 . P1 . F6 . 171.7(2) yes F11 . P1 . F12 . 169.3(3) yes F11 . P1 . F13 . 96.3(3) yes F12 . P1 . F13 . 93.3(3) yes F11 . P1 . F14 . 85.7(3) yes F12 . P1 . F14 . 84.7(3) yes F13 . P1 . F14 . 177.9(3) yes F11 . P1 . F15 . 92.2(4) yes F12 . P1 . F15 . 91.9(3) yes F13 . P1 . F15 . 94.1(3) yes F14 . P1 . F15 . 86.5(3) yes F11 . P1 . F16 . 87.5(4) yes F12 . P1 . F16 . 87.1(3) yes F13 . P1 . F16 . 93.7(4) yes F14 . P1 . F16 . 85.7(3) yes F15 . P1 . F16 . 172.1(4) yes