# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2008 data_global _journal_coden_Cambridge 182 _journal_volume ? _journal_page_first ? _journal_year ? loop_ _publ_author_name 'Edwin Constable' 'Takeru Bessho' 'Michael Graetzel' 'Catherine E Housecroft' 'William Kylberg' 'Md. K. Nazeeruddin' 'Markus Neuburger' 'Ana Hernandez Redondo' 'Silvia Schaffner' _publ_contact_author_name 'Edwin Constable' _publ_contact_author_email EDWIN.CONSTABLE@UNIBAS.CH _publ_section_title ; An element of surprise - efficient copper-functionalized dye-sensitized solar cells ; # Attachment 'publish_new.cif' data_ah158-9 _database_code_depnum_ccdc_archive 'CCDC 688596' _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 10.8110(2) _cell_length_b 20.0824(4) _cell_length_c 16.3507(3) _cell_angle_alpha 90 _cell_angle_beta 98.6805(10) _cell_angle_gamma 90 _cell_volume 3509.25(12) _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' Cu 0.3201 1.2651 13.3380 3.5828 7.1676 0.2470 5.6158 11.3966 1.6735 64.8126 1.1910 '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' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 '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' 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' _cell_formula_units_Z 4 # Given Formula = C32 H32 Cu1 F6 N4 O8 P1 # Dc = 1.53 Fooo = 1656.00 Mu = 7.55 M = 809.14 # Found Formula = C32 H32 Cu1 F6 N4 O8 P1 # Dc = 1.53 FOOO = 1656.00 Mu = 7.55 M = 809.14 _chemical_formula_sum 'C32 H32 Cu1 F6 N4 O8 P1' _chemical_formula_moiety 'C32 H32 Cu N4 O8, F6 P' _chemical_compound_source ? _chemical_formula_weight 809.14 _cell_measurement_reflns_used 14486 _cell_measurement_theta_min 1 _cell_measurement_theta_max 27 _cell_measurement_temperature 173 _exptl_crystal_description plate _exptl_crystal_colour purple _exptl_crystal_size_min 0.02 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_max 0.49 _exptl_crystal_density_diffrn 1.531 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 1656 _exptl_absorpt_coefficient_mu 0.755 # Sheldrick geometric approximatio 0.95 0.99 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'DENZO/SCALEPACK (Otwinowski & Minor, 1997)' _exptl_absorpt_correction_T_min 0.95 _exptl_absorpt_correction_T_max 0.99 # 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 173 _diffrn_reflns_number 24693 _reflns_number_total 7729 _diffrn_reflns_av_R_equivalents 0.044 # Number of reflections with Friedels Law is 7729 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 7728 _diffrn_reflns_theta_min 1.906 _diffrn_reflns_theta_max 27.084 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.084 _diffrn_measured_fraction_theta_full 1.000 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 23 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _reflns_limit_h_min -13 _reflns_limit_h_max 13 _reflns_limit_k_min 0 _reflns_limit_k_max 25 _reflns_limit_l_min 0 _reflns_limit_l_max 20 _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 -0.58 _refine_diff_density_max 0.80 # 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>1.5\s(I) _refine_ls_number_reflns 4831 _refine_ls_number_restraints 60 _refine_ls_number_parameters 469 _oxford_refine_ls_R_factor_ref 0.0505 _refine_ls_wR_factor_ref 0.0564 _refine_ls_goodness_of_fit_ref 1.2411 _refine_ls_shift/su_max 0.000546 # The values computed from all data _oxford_reflns_number_all 7639 _refine_ls_R_factor_all 0.0890 _refine_ls_wR_factor_all 0.0779 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 4457 _refine_ls_R_factor_gt 0.0473 _refine_ls_wR_factor_gt 0.0548 # 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: 0.798 0.657 0.533 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, G., 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 _refine_special_details ; Restraints have been used to control the refinement of the PF6 molecule. ; 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 Cu1 Cu 0.53654(4) 0.21086(2) 0.30055(2) 0.0394 1.0000 Uani . . . . . . . N1 N 0.6569(3) 0.24653(14) 0.39619(16) 0.0376 1.0000 Uani . . . . . . . N2 N 0.4843(2) 0.15501(13) 0.39192(15) 0.0346 1.0000 Uani . . . . . . . N3 N 0.5957(3) 0.16488(14) 0.20218(16) 0.0392 1.0000 Uani . . . . . . . N4 N 0.4159(3) 0.25193(14) 0.20956(16) 0.0389 1.0000 Uani . . . . . . . C1 C 0.7345(5) 0.3290(2) 0.3091(3) 0.0638 1.0000 Uani . . . . . . . C2 C 0.7437(4) 0.29362(18) 0.3900(2) 0.0468 1.0000 Uani . . . . . . . C3 C 0.8362(4) 0.30752(19) 0.4569(3) 0.0507 1.0000 Uani . . . . . . . C4 C 0.8378(3) 0.27319(18) 0.5303(2) 0.0455 1.0000 Uani . . . . . . . C5 C 0.9395(3) 0.2885(2) 0.6016(3) 0.0536 1.0000 Uani . . . . . . . C6 C 1.0120(4) 0.2753(3) 0.7439(3) 0.0751 1.0000 Uani . . . . . . . C7 C 0.7475(3) 0.22513(17) 0.5366(2) 0.0398 1.0000 Uani . . . . . . . C8 C 0.6577(3) 0.21258(17) 0.46750(19) 0.0374 1.0000 Uani . . . . . . . C9 C 0.5585(3) 0.16183(16) 0.46599(18) 0.0347 1.0000 Uani . . . . . . . C10 C 0.5396(3) 0.12433(17) 0.53403(19) 0.0393 1.0000 Uani . . . . . . . C11 C 0.4413(3) 0.07915(17) 0.5255(2) 0.0394 1.0000 Uani . . . . . . . C12 C 0.4131(4) 0.03627(18) 0.5957(2) 0.0445 1.0000 Uani . . . . . . . C13 C 0.4528(5) 0.0170(2) 0.7386(2) 0.0686 1.0000 Uani . . . . . . . C14 C 0.3657(3) 0.07224(18) 0.4500(2) 0.0423 1.0000 Uani . . . . . . . C15 C 0.3880(3) 0.11135(17) 0.3841(2) 0.0387 1.0000 Uani . . . . . . . C16 C 0.3062(4) 0.1082(2) 0.3019(2) 0.0515 1.0000 Uani . . . . . . . C17 C 0.7746(3) 0.11599(19) 0.2864(2) 0.0452 1.0000 Uani . . . . . . . C18 C 0.6921(3) 0.12256(17) 0.2052(2) 0.0401 1.0000 Uani . . . . . . . C19 C 0.7118(4) 0.08584(19) 0.1359(2) 0.0457 1.0000 Uani . . . . . . . C20 C 0.6303(4) 0.09362(19) 0.0631(2) 0.0461 1.0000 Uani . . . . . . . C21 C 0.6433(4) 0.0532(2) -0.0127(2) 0.0571 1.0000 Uani . . . . . . . C22 C 0.7650(6) -0.0254(3) -0.0718(3) 0.0915 1.0000 Uani . . . . . . . C23 C 0.5332(4) 0.1387(2) 0.0594(2) 0.0468 1.0000 Uani . . . . . . . C24 C 0.5179(3) 0.17458(17) 0.13026(19) 0.0395 1.0000 Uani . . . . . . . C25 C 0.4193(3) 0.22499(17) 0.13350(19) 0.0388 1.0000 Uani . . . . . . . C26 C 0.3353(3) 0.24491(18) 0.0651(2) 0.0435 1.0000 Uani . . . . . . . C27 C 0.2482(3) 0.29287(19) 0.0755(2) 0.0443 1.0000 Uani . . . . . . . C28 C 0.1550(4) 0.3135(2) 0.0009(2) 0.0511 1.0000 Uani . . . . . . . C29 C -0.0167(5) 0.3838(3) -0.0429(3) 0.0801 1.0000 Uani . . . . . . . C30 C 0.2457(3) 0.3208(2) 0.1519(2) 0.0457 1.0000 Uani . . . . . . . C31 C 0.3307(3) 0.29883(17) 0.2191(2) 0.0426 1.0000 Uani . . . . . . . C32 C 0.3291(4) 0.3239(2) 0.3051(2) 0.0523 1.0000 Uani . . . . . . . O1 O 1.0334(3) 0.3180(2) 0.5923(2) 0.0789 1.0000 Uani . . . . . . . O2 O 0.9142(3) 0.26546(15) 0.67265(17) 0.0576 1.0000 Uani . . . . . . . O3 O 0.3400(3) -0.00884(14) 0.58731(17) 0.0572 1.0000 Uani . . . . . . . O4 O 0.4788(3) 0.05524(14) 0.66733(15) 0.0547 1.0000 Uani . . . . . . . O5 O 0.5687(4) 0.0559(2) -0.07450(19) 0.0878 1.0000 Uani . . . . . . . O6 O 0.7437(3) 0.01613(17) -0.0021(2) 0.0737 1.0000 Uani . . . . . . . O7 O 0.1548(3) 0.29175(17) -0.06735(17) 0.0658 1.0000 Uani . . . . . . . O8 O 0.0778(3) 0.35860(17) 0.02278(17) 0.0681 1.0000 Uani . . . . . . . P1 P 0.97274(14) 0.45735(6) 0.23086(13) 0.0899 1.0000 Uani D U . . . . . F1 F 0.8245(3) 0.45682(16) 0.2246(3) 0.1107 1.0000 Uani D U . . . . . F2 F 1.1177(3) 0.45870(18) 0.2371(4) 0.1600 1.0000 Uani D U . . . . . F3 F 0.9756(3) 0.53187(15) 0.2610(3) 0.1244 1.0000 Uani D U . . . . . F4 F 0.9692(4) 0.38338(15) 0.2017(3) 0.1349 1.0000 Uani D U . . . . . F5 F 0.9596(6) 0.4843(2) 0.1406(3) 0.1789 1.0000 Uani D U . . . . . F6 F 0.9796(4) 0.4317(2) 0.3225(3) 0.1338 1.0000 Uani D U . . . . . H11 H 0.7963 0.3640 0.3117 0.0991 1.0000 Uiso R . . . . . . H12 H 0.6524 0.3466 0.2946 0.0993 1.0000 Uiso R . . . . . . H13 H 0.7497 0.2975 0.2678 0.0991 1.0000 Uiso R . . . . . . H31 H 0.8963 0.3400 0.4524 0.0614 1.0000 Uiso R . . . . . . H61 H 0.9864 0.2565 0.7928 0.1103 1.0000 Uiso R . . . . . . H62 H 1.0267 0.3228 0.7515 0.1099 1.0000 Uiso R . . . . . . H63 H 1.0878 0.2543 0.7330 0.1101 1.0000 Uiso R . . . . . . H71 H 0.7464 0.2021 0.5855 0.0480 1.0000 Uiso R . . . . . . H101 H 0.5916 0.1294 0.5843 0.0476 1.0000 Uiso R . . . . . . H131 H 0.5081 0.0335 0.7863 0.1026 1.0000 Uiso R . . . . . . H132 H 0.4669 -0.0301 0.7315 0.1027 1.0000 Uiso R . . . . . . H133 H 0.3659 0.0245 0.7462 0.1027 1.0000 Uiso R . . . . . . H141 H 0.3000 0.0424 0.4431 0.0496 1.0000 Uiso R . . . . . . H161 H 0.2520 0.0708 0.2995 0.0763 1.0000 Uiso R . . . . . . H162 H 0.2587 0.1480 0.2947 0.0763 1.0000 Uiso R . . . . . . H163 H 0.3560 0.1055 0.2583 0.0761 1.0000 Uiso R . . . . . . H171 H 0.8441 0.0877 0.2819 0.0700 1.0000 Uiso R . . . . . . H172 H 0.8063 0.1593 0.3055 0.0698 1.0000 Uiso R . . . . . . H173 H 0.7277 0.0980 0.3269 0.0698 1.0000 Uiso R . . . . . . H191 H 0.7769 0.0559 0.1393 0.0556 1.0000 Uiso R . . . . . . H221 H 0.8355 -0.0539 -0.0559 0.1441 1.0000 Uiso R . . . . . . H222 H 0.7811 0.0017 -0.1174 0.1439 1.0000 Uiso R . . . . . . H223 H 0.6921 -0.0525 -0.0893 0.1439 1.0000 Uiso R . . . . . . H231 H 0.4789 0.1449 0.0112 0.0547 1.0000 Uiso R . . . . . . H261 H 0.3381 0.2250 0.0140 0.0505 1.0000 Uiso R . . . . . . H291 H -0.0690 0.4159 -0.0205 0.1168 1.0000 Uiso R . . . . . . H292 H 0.0233 0.4051 -0.0842 0.1169 1.0000 Uiso R . . . . . . H293 H -0.0680 0.3484 -0.0684 0.1171 1.0000 Uiso R . . . . . . H301 H 0.1888 0.3533 0.1600 0.0538 1.0000 Uiso R . . . . . . H321 H 0.2626 0.3572 0.3059 0.0765 1.0000 Uiso R . . . . . . H322 H 0.4105 0.3413 0.3275 0.0778 1.0000 Uiso R . . . . . . H323 H 0.3147 0.2872 0.3405 0.0782 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 Cu1 0.0422(2) 0.0465(2) 0.02816(19) 0.00398(18) 0.00137(14) -0.0042(2) N1 0.0381(15) 0.0394(15) 0.0346(13) -0.0013(11) 0.0034(11) -0.0037(12) N2 0.0359(14) 0.0374(14) 0.0303(12) 0.0025(11) 0.0038(10) -0.0015(11) N3 0.0408(15) 0.0451(15) 0.0308(12) 0.0025(11) 0.0027(11) -0.0085(12) N4 0.0393(14) 0.0440(16) 0.0323(13) 0.0069(11) 0.0020(11) -0.0035(12) C1 0.071(3) 0.066(3) 0.057(2) 0.007(2) 0.015(2) -0.023(2) C2 0.049(2) 0.0441(19) 0.0483(19) -0.0041(16) 0.0093(15) -0.0092(17) C3 0.0405(19) 0.050(2) 0.062(2) -0.0129(17) 0.0090(17) -0.0102(16) C4 0.0349(17) 0.050(2) 0.051(2) -0.0143(16) 0.0020(15) 0.0020(15) C5 0.0364(18) 0.060(2) 0.062(2) -0.024(2) -0.0005(16) 0.0041(18) C6 0.048(2) 0.106(4) 0.063(3) -0.036(3) -0.0173(19) 0.013(2) C7 0.0363(17) 0.0463(19) 0.0357(15) -0.0054(13) 0.0016(13) 0.0035(14) C8 0.0369(16) 0.0413(16) 0.0335(14) -0.0019(14) 0.0039(12) 0.0047(15) C9 0.0355(16) 0.0382(16) 0.0303(14) -0.0005(12) 0.0050(12) 0.0026(13) C10 0.0438(18) 0.0434(18) 0.0307(15) 0.0001(13) 0.0059(13) 0.0044(14) C11 0.0423(18) 0.0404(17) 0.0377(16) 0.0025(13) 0.0129(14) 0.0045(14) C12 0.053(2) 0.0443(19) 0.0379(17) 0.0046(15) 0.0142(15) 0.0069(17) C13 0.104(4) 0.068(3) 0.0352(19) 0.0105(19) 0.016(2) -0.003(3) C14 0.0382(17) 0.0454(18) 0.0431(17) 0.0048(15) 0.0058(14) -0.0018(15) C15 0.0362(17) 0.0415(17) 0.0377(16) 0.0014(14) 0.0039(13) -0.0021(14) C16 0.046(2) 0.061(2) 0.0435(18) 0.0067(17) -0.0061(15) -0.0145(18) C17 0.0424(19) 0.053(2) 0.0388(17) 0.0005(15) 0.0020(14) 0.0022(16) C18 0.0387(17) 0.0435(18) 0.0383(16) 0.0007(14) 0.0066(13) -0.0065(14) C19 0.047(2) 0.050(2) 0.0407(18) 0.0012(15) 0.0096(15) 0.0002(16) C20 0.054(2) 0.051(2) 0.0347(16) -0.0029(15) 0.0109(15) -0.0099(17) C21 0.066(3) 0.068(3) 0.040(2) -0.0068(18) 0.0161(19) -0.006(2) C22 0.104(4) 0.103(4) 0.073(3) -0.033(3) 0.032(3) 0.011(3) C23 0.049(2) 0.060(2) 0.0306(15) 0.0042(15) 0.0029(14) -0.0100(18) C24 0.0427(18) 0.0441(18) 0.0316(15) 0.0032(14) 0.0048(13) -0.0079(15) C25 0.0410(17) 0.0455(19) 0.0296(14) 0.0065(13) 0.0042(13) -0.0072(14) C26 0.0430(19) 0.052(2) 0.0334(16) 0.0089(14) 0.0003(14) -0.0081(16) C27 0.0397(17) 0.056(2) 0.0344(15) 0.0119(15) -0.0032(13) -0.0117(17) C28 0.047(2) 0.059(2) 0.044(2) 0.0138(17) -0.0051(16) -0.0090(18) C29 0.067(3) 0.100(4) 0.064(3) 0.028(3) -0.022(2) 0.011(3) C30 0.0409(18) 0.051(2) 0.0446(18) 0.0094(16) 0.0038(15) -0.0011(16) C31 0.0424(18) 0.0455(19) 0.0389(16) 0.0070(14) 0.0030(13) -0.0065(15) C32 0.058(2) 0.056(2) 0.0415(18) 0.0020(17) 0.0008(16) 0.0083(19) O1 0.0460(17) 0.105(3) 0.084(2) -0.0253(19) 0.0019(15) -0.0208(17) O2 0.0447(14) 0.0707(18) 0.0516(15) -0.0185(13) -0.0112(12) 0.0047(13) O3 0.0677(18) 0.0565(16) 0.0490(15) 0.0074(12) 0.0143(13) -0.0140(14) O4 0.0731(18) 0.0571(16) 0.0344(12) 0.0080(11) 0.0098(12) -0.0059(14) O5 0.098(3) 0.118(3) 0.0440(17) -0.0264(18) -0.0005(17) 0.018(2) O6 0.078(2) 0.088(2) 0.0569(17) -0.0213(16) 0.0166(15) 0.0145(18) O7 0.0670(18) 0.086(2) 0.0384(13) 0.0076(14) -0.0100(12) 0.0019(16) O8 0.0613(18) 0.086(2) 0.0501(15) 0.0123(15) -0.0135(13) 0.0141(17) P1 0.0760(9) 0.0466(6) 0.1619(14) 0.0245(8) 0.0657(10) 0.0065(6) F1 0.0743(19) 0.0745(19) 0.184(4) 0.042(2) 0.021(2) 0.0032(16) F2 0.079(2) 0.074(2) 0.345(6) 0.012(3) 0.090(3) 0.0045(18) F3 0.079(2) 0.0618(17) 0.243(5) -0.011(2) 0.059(3) 0.0011(16) F4 0.141(3) 0.0617(18) 0.227(5) -0.009(2) 0.107(3) -0.011(2) F5 0.239(6) 0.146(4) 0.167(4) 0.050(3) 0.078(4) -0.040(4) F6 0.121(3) 0.126(3) 0.150(3) 0.041(3) 0.004(3) -0.027(3) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.2170(5) 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 Cu1 . N1 . 2.009(3) yes Cu1 . N2 . 2.016(2) yes Cu1 . N3 . 2.039(3) yes Cu1 . N4 . 2.003(3) yes N1 . C2 . 1.347(4) yes N1 . C8 . 1.350(4) yes N2 . C9 . 1.355(4) yes N2 . C15 . 1.353(4) yes N3 . C18 . 1.340(5) yes N3 . C24 . 1.353(4) yes N4 . C25 . 1.362(4) yes N4 . C31 . 1.343(5) yes C1 . C2 . 1.490(5) yes C1 . H11 . 0.966 no C1 . H12 . 0.952 no C1 . H13 . 0.956 no C2 . C3 . 1.395(5) yes C3 . C4 . 1.381(6) yes C3 . H31 . 0.932 no C4 . C5 . 1.508(5) yes C4 . C7 . 1.388(5) yes C5 . O1 . 1.204(5) yes C5 . O2 . 1.317(5) yes C6 . O2 . 1.464(5) yes C6 . H61 . 0.963 no C6 . H62 . 0.970 no C6 . H63 . 0.962 no C7 . C8 . 1.397(4) yes C7 . H71 . 0.926 no C8 . C9 . 1.477(5) yes C9 . C10 . 1.384(4) yes C10 . C11 . 1.388(5) yes C10 . H101 . 0.928 no C11 . C12 . 1.503(5) yes C11 . C14 . 1.381(5) yes C12 . O3 . 1.197(5) yes C12 . O4 . 1.330(5) yes C13 . O4 . 1.459(5) yes C13 . H131 . 0.967 no C13 . H132 . 0.966 no C13 . H133 . 0.977 no C14 . C15 . 1.384(5) yes C14 . H141 . 0.923 no C15 . C16 . 1.495(5) yes C16 . H161 . 0.949 no C16 . H162 . 0.947 no C16 . H163 . 0.958 no C17 . C18 . 1.490(5) yes C17 . H171 . 0.954 no C17 . H172 . 0.970 no C17 . H173 . 0.963 no C18 . C19 . 1.395(5) yes C19 . C20 . 1.379(5) yes C19 . H191 . 0.921 no C20 . C21 . 1.506(5) yes C20 . C23 . 1.381(6) yes C21 . O5 . 1.195(5) yes C21 . O6 . 1.306(6) yes C22 . O6 . 1.459(5) yes C22 . H221 . 0.957 no C22 . H222 . 0.959 no C22 . H223 . 0.964 no C23 . C24 . 1.395(5) yes C23 . H231 . 0.917 no C24 . C25 . 1.476(5) yes C25 . C26 . 1.389(4) yes C26 . C27 . 1.375(5) yes C26 . H261 . 0.932 no C27 . C28 . 1.518(5) yes C27 . C30 . 1.373(5) yes C28 . O7 . 1.198(5) yes C28 . O8 . 1.317(5) yes C29 . O8 . 1.457(5) yes C29 . H291 . 0.966 no C29 . H292 . 0.957 no C29 . H293 . 0.958 no C30 . C31 . 1.393(5) yes C30 . H301 . 0.920 no C31 . C32 . 1.496(5) yes C32 . H321 . 0.983 no C32 . H322 . 0.967 no C32 . H323 . 0.964 no P1 . F1 . 1.591(3) yes P1 . F2 . 1.555(3) yes P1 . F3 . 1.574(3) yes P1 . F4 . 1.559(3) yes P1 . F5 . 1.558(5) yes P1 . F6 . 1.576(4) 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 . Cu1 . N2 . 80.93(11) yes N1 . Cu1 . N3 . 122.14(11) yes N2 . Cu1 . N3 . 119.26(11) yes N1 . Cu1 . N4 . 134.76(11) yes N2 . Cu1 . N4 . 123.77(11) yes N3 . Cu1 . N4 . 81.21(12) yes Cu1 . N1 . C2 . 124.6(2) yes Cu1 . N1 . C8 . 114.3(2) yes C2 . N1 . C8 . 120.4(3) yes Cu1 . N2 . C9 . 114.3(2) yes Cu1 . N2 . C15 . 126.1(2) yes C9 . N2 . C15 . 119.6(3) yes Cu1 . N3 . C18 . 126.3(2) yes Cu1 . N3 . C24 . 113.1(2) yes C18 . N3 . C24 . 120.1(3) yes Cu1 . N4 . C25 . 114.2(2) yes Cu1 . N4 . C31 . 125.7(2) yes C25 . N4 . C31 . 119.9(3) yes C2 . C1 . H11 . 110.8 no C2 . C1 . H12 . 109.4 no H11 . C1 . H12 . 110.7 no C2 . C1 . H13 . 108.5 no H11 . C1 . H13 . 108.7 no H12 . C1 . H13 . 108.8 no C1 . C2 . N1 . 116.6(3) yes C1 . C2 . C3 . 123.0(3) yes N1 . C2 . C3 . 120.4(3) yes C2 . C3 . C4 . 119.7(3) yes C2 . C3 . H31 . 120.2 no C4 . C3 . H31 . 120.1 no C3 . C4 . C5 . 118.8(3) yes C3 . C4 . C7 . 119.6(3) yes C5 . C4 . C7 . 121.6(3) yes C4 . C5 . O1 . 122.2(4) yes C4 . C5 . O2 . 112.7(3) yes O1 . C5 . O2 . 125.1(4) yes O2 . C6 . H61 . 110.1 no O2 . C6 . H62 . 108.6 no H61 . C6 . H62 . 110.0 no O2 . C6 . H63 . 109.1 no H61 . C6 . H63 . 109.9 no H62 . C6 . H63 . 109.1 no C4 . C7 . C8 . 118.4(3) yes C4 . C7 . H71 . 120.9 no C8 . C7 . H71 . 120.7 no C7 . C8 . N1 . 121.4(3) yes C7 . C8 . C9 . 123.5(3) yes N1 . C8 . C9 . 115.1(3) yes C8 . C9 . N2 . 114.5(3) yes C8 . C9 . C10 . 123.9(3) yes N2 . C9 . C10 . 121.6(3) yes C9 . C10 . C11 . 118.6(3) yes C9 . C10 . H101 . 120.6 no C11 . C10 . H101 . 120.8 no C10 . C11 . C12 . 122.6(3) yes C10 . C11 . C14 . 119.8(3) yes C12 . C11 . C14 . 117.7(3) yes C11 . C12 . O3 . 123.6(3) yes C11 . C12 . O4 . 111.4(3) yes O3 . C12 . O4 . 125.0(3) yes O4 . C13 . H131 . 107.0 no O4 . C13 . H132 . 111.4 no H131 . C13 . H132 . 110.1 no O4 . C13 . H133 . 108.9 no H131 . C13 . H133 . 109.6 no H132 . C13 . H133 . 109.8 no C11 . C14 . C15 . 119.3(3) yes C11 . C14 . H141 . 121.1 no C15 . C14 . H141 . 119.6 no C14 . C15 . N2 . 121.1(3) yes C14 . C15 . C16 . 121.8(3) yes N2 . C15 . C16 . 117.1(3) yes C15 . C16 . H161 . 110.4 no C15 . C16 . H162 . 108.2 no H161 . C16 . H162 . 110.0 no C15 . C16 . H163 . 110.4 no H161 . C16 . H163 . 109.7 no H162 . C16 . H163 . 108.1 no C18 . C17 . H171 . 110.9 no C18 . C17 . H172 . 110.0 no H171 . C17 . H172 . 108.3 no C18 . C17 . H173 . 109.8 no H171 . C17 . H173 . 109.5 no H172 . C17 . H173 . 108.3 no C17 . C18 . N3 . 116.6(3) yes C17 . C18 . C19 . 122.2(3) yes N3 . C18 . C19 . 121.2(3) yes C18 . C19 . C20 . 119.0(4) yes C18 . C19 . H191 . 120.4 no C20 . C19 . H191 . 120.5 no C19 . C20 . C21 . 121.5(4) yes C19 . C20 . C23 . 119.6(3) yes C21 . C20 . C23 . 118.9(3) yes C20 . C21 . O5 . 122.4(4) yes C20 . C21 . O6 . 112.1(4) yes O5 . C21 . O6 . 125.4(4) yes O6 . C22 . H221 . 110.0 no O6 . C22 . H222 . 110.6 no H221 . C22 . H222 . 108.7 no O6 . C22 . H223 . 109.6 no H221 . C22 . H223 . 108.9 no H222 . C22 . H223 . 109.0 no C20 . C23 . C24 . 119.1(3) yes C20 . C23 . H231 . 120.6 no C24 . C23 . H231 . 120.2 no C23 . C24 . N3 . 120.8(3) yes C23 . C24 . C25 . 124.1(3) yes N3 . C24 . C25 . 115.2(3) yes C24 . C25 . N4 . 115.1(3) yes C24 . C25 . C26 . 123.8(3) yes N4 . C25 . C26 . 121.0(3) yes C25 . C26 . C27 . 118.6(3) yes C25 . C26 . H261 . 119.5 no C27 . C26 . H261 . 121.8 no C26 . C27 . C28 . 118.4(3) yes C26 . C27 . C30 . 120.4(3) yes C28 . C27 . C30 . 121.2(4) yes C27 . C28 . O7 . 123.9(4) yes C27 . C28 . O8 . 109.9(3) yes O7 . C28 . O8 . 126.2(4) yes O8 . C29 . H291 . 109.8 no O8 . C29 . H292 . 109.5 no H291 . C29 . H292 . 108.8 no O8 . C29 . H293 . 111.1 no H291 . C29 . H293 . 109.2 no H292 . C29 . H293 . 108.5 no C27 . C30 . C31 . 119.1(4) yes C27 . C30 . H301 . 121.7 no C31 . C30 . H301 . 119.1 no C30 . C31 . N4 . 120.9(3) yes C30 . C31 . C32 . 122.3(3) yes N4 . C31 . C32 . 116.8(3) yes C31 . C32 . H321 . 110.7 no C31 . C32 . H322 . 109.8 no H321 . C32 . H322 . 111.9 no C31 . C32 . H323 . 109.5 no H321 . C32 . H323 . 109.1 no H322 . C32 . H323 . 105.6 no C6 . O2 . C5 . 115.7(4) yes C13 . O4 . C12 . 114.2(3) yes C22 . O6 . C21 . 116.6(4) yes C29 . O8 . C28 . 116.2(4) yes F1 . P1 . F2 . 179.4(2) yes F1 . P1 . F3 . 89.92(19) yes F2 . P1 . F3 . 89.5(2) yes F1 . P1 . F4 . 89.8(2) yes F2 . P1 . F4 . 90.8(2) yes F3 . P1 . F4 . 179.5(2) yes F1 . P1 . F5 . 89.7(3) yes F2 . P1 . F5 . 90.2(3) yes F3 . P1 . F5 . 87.7(3) yes F4 . P1 . F5 . 92.7(3) yes F1 . P1 . F6 . 87.8(2) yes F2 . P1 . F6 . 92.4(3) yes F3 . P1 . F6 . 91.0(3) yes F4 . P1 . F6 . 88.5(2) yes F5 . P1 . F6 . 177.2(3) yes loop_ _geom_hbond_atom_site_label_D _geom_hbond_site_symmetry_D _geom_hbond_atom_site_label_H _geom_hbond_site_symmetry_H _geom_hbond_atom_site_label_A _geom_hbond_site_symmetry_A _geom_hbond_angle_DHA _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_publ_flag C13 . H131 . O5 1_556 155 0.97 2.32 3.219(5) yes C17 . H173 . O3 2_656 154 0.96 2.45 3.346(5) yes