# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_080925a _database_code_depnum_ccdc_archive 'CCDC 767160' #TrackingRef '- 080925a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C52 H43 Cu2 Mn3 N8 O19 S2' _chemical_formula_weight 1439.96 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' 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 9.6676(17) _cell_length_b 12.039(2) _cell_length_c 12.914(2) _cell_angle_alpha 72.454(3) _cell_angle_beta 77.357(3) _cell_angle_gamma 68.565(2) _cell_volume 1324.0(4) _cell_formula_units_Z 1 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 3789 _cell_measurement_theta_min 2.18 _cell_measurement_theta_max 27.76 _exptl_crystal_description BLOCK _exptl_crystal_colour GREEN _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.22 _exptl_crystal_density_meas NONE _exptl_crystal_density_diffrn 1.807 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 729 _exptl_absorpt_coefficient_mu 1.653 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.704114 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 '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 6690 _diffrn_reflns_av_R_equivalents 0.0104 _diffrn_reflns_av_sigmaI/netI 0.0222 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 1.87 _diffrn_reflns_theta_max 25.02 _reflns_number_total 4643 _reflns_number_gt 3904 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0577P)^2^+3.8893P] 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 4643 _refine_ls_number_parameters 394 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0523 _refine_ls_R_factor_gt 0.0426 _refine_ls_wR_factor_ref 0.1229 _refine_ls_wR_factor_gt 0.1132 _refine_ls_goodness_of_fit_ref 1.048 _refine_ls_restrained_S_all 1.048 _refine_ls_shift/su_max 0.000 _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 Mn1 Mn 0.22499(7) 0.75456(6) 0.13569(5) 0.02793(17) Uani 1 1 d . . . Mn2 Mn 1.0000 1.0000 0.0000 0.01837(18) Uani 1 2 d S . . Cu1 Cu 0.21173(6) 0.70272(5) 0.57415(4) 0.03247(16) Uani 1 1 d . . . S1 S 0.48940(13) 0.73189(11) -0.08581(9) 0.0361(3) Uani 1 1 d . . . O1 O 0.3728(3) 0.6967(3) 0.2647(2) 0.0350(7) Uani 1 1 d . . . O2 O 0.0776(3) 0.7987(3) 0.2839(2) 0.0407(8) Uani 1 1 d . . . O3 O 0.4106(5) 0.7041(4) 0.0212(3) 0.0660(11) Uani 1 1 d . . . O4 O 0.3900(7) 0.8002(5) -0.1661(4) 0.109(2) Uani 1 1 d . . . O5 O 0.5989(5) 0.6236(5) -0.1092(6) 0.103(2) Uani 1 1 d . . . O6 O 0.9502(4) 0.6648(3) 0.0873(3) 0.0469(8) Uani 1 1 d . . . O7 O 1.0247(4) 0.8273(3) 0.0430(3) 0.0401(7) Uani 1 1 d . . . O8 O 0.8274(4) 1.0456(3) -0.0707(3) 0.0397(7) Uani 1 1 d . . . O9 O 0.2024(4) 0.5732(3) 0.1745(3) 0.0424(8) Uani 1 1 d . . . H9A H 0.2759 0.5265 0.1415 0.064 Uiso 1 1 d R . . H9B H 0.1192 0.6006 0.1489 0.064 Uiso 1 1 d R . . O10 O 0.8312(9) 0.9871(10) 0.1638(6) 0.079(3) Uani 0.50 1 d PD . . H10' H 0.7898 1.0553 0.1818 0.118 Uiso 0.50 1 d PRD . . N1 N 0.3695(4) 0.6915(3) 0.4468(3) 0.0313(8) Uani 1 1 d . . . N2 N 0.0817(4) 0.8051(3) 0.4603(3) 0.0342(8) Uani 1 1 d . . . N3 N 0.0292(4) 0.7003(4) 0.6832(3) 0.0421(9) Uani 1 1 d . . . N4 N 0.3598(4) 0.6035(3) 0.6790(3) 0.0355(8) Uani 1 1 d . . . C1 C 0.3099(5) 0.7136(4) 0.3566(3) 0.0297(9) Uani 1 1 d . . . C2 C 0.1402(5) 0.7767(4) 0.3659(3) 0.0315(9) Uani 1 1 d . . . C3 C -0.0655(5) 0.8865(4) 0.4734(4) 0.0375(10) Uani 1 1 d . . . C4 C -0.1240(6) 0.9873(5) 0.3894(5) 0.0536(13) Uani 1 1 d . . . H4 H -0.0649 1.0021 0.3228 0.064 Uiso 1 1 calc R . . C5 C -0.2674(6) 1.0647(5) 0.4037(5) 0.0564(14) Uani 1 1 d . . . H5 H -0.3046 1.1308 0.3461 0.068 Uiso 1 1 calc R . . C6 C -0.3576(6) 1.0470(5) 0.5013(5) 0.0568(14) Uani 1 1 d . . . H6 H -0.4559 1.0986 0.5096 0.068 Uiso 1 1 calc R . . C7 C -0.2995(6) 0.9516(6) 0.5857(5) 0.0561(14) Uani 1 1 d . . . H7 H -0.3585 0.9405 0.6529 0.067 Uiso 1 1 calc R . . C8 C -0.1529(5) 0.8699(5) 0.5740(4) 0.0425(11) Uani 1 1 d . . . C9 C -0.1033(6) 0.7733(5) 0.6689(4) 0.0494(12) Uani 1 1 d . . . H9 H -0.1771 0.7628 0.7272 0.059 Uiso 1 1 calc R . . C10 C 0.0452(6) 0.6099(5) 0.7896(4) 0.0551(14) Uani 1 1 d . . . H10A H 0.0683 0.5283 0.7790 0.066 Uiso 1 1 calc R . . H10B H -0.0489 0.6281 0.8369 0.066 Uiso 1 1 calc R . . C11 C 0.1673(6) 0.6117(5) 0.8438(4) 0.0511(13) Uani 1 1 d . . . H11A H 0.1593 0.6965 0.8362 0.061 Uiso 1 1 calc R . . H11B H 0.1533 0.5734 0.9213 0.061 Uiso 1 1 calc R . . C12 C 0.3202(6) 0.5460(5) 0.7959(4) 0.0458(12) Uani 1 1 d . . . H12A H 0.3932 0.5433 0.8384 0.055 Uiso 1 1 calc R . . H12B H 0.3268 0.4619 0.8024 0.055 Uiso 1 1 calc R . . C13 C 0.5007(5) 0.5863(4) 0.6523(4) 0.0375(10) Uani 1 1 d . . . H13 H 0.5584 0.5467 0.7099 0.045 Uiso 1 1 calc R . . C14 C 0.5834(5) 0.6189(4) 0.5465(4) 0.0365(10) Uani 1 1 d . . . C15 C 0.7349(5) 0.5991(5) 0.5481(4) 0.0492(12) Uani 1 1 d . . . H15 H 0.7748 0.5642 0.6143 0.059 Uiso 1 1 calc R . . C16 C 0.8261(6) 0.6301(5) 0.4540(5) 0.0554(14) Uani 1 1 d . . . H16 H 0.9261 0.6183 0.4565 0.066 Uiso 1 1 calc R . . C17 C 0.7668(6) 0.6791(5) 0.3560(4) 0.0525(13) Uani 1 1 d . . . H17 H 0.8272 0.7012 0.2920 0.063 Uiso 1 1 calc R . . C18 C 0.6189(5) 0.6959(5) 0.3515(4) 0.0429(11) Uani 1 1 d . . . H18 H 0.5821 0.7274 0.2841 0.052 Uiso 1 1 calc R . . C19 C 0.5237(5) 0.6665(4) 0.4458(3) 0.0316(9) Uani 1 1 d . . . C20 C 0.5881(5) 0.8268(4) -0.0803(3) 0.0321(9) Uani 1 1 d . . . C21 C 0.7128(5) 0.7748(4) -0.0257(3) 0.0323(9) Uani 1 1 d . . . H21 H 0.7408 0.6913 0.0085 0.039 Uiso 1 1 calc R . . C22 C 0.7986(5) 0.8443(4) -0.0201(3) 0.0294(9) Uani 1 1 d . . . C23 C 0.7553(5) 0.9707(4) -0.0713(3) 0.0309(9) Uani 1 1 d . . . C24 C 0.6258(5) 1.0221(4) -0.1249(4) 0.0364(10) Uani 1 1 d . . . H24 H 0.5951 1.1058 -0.1582 0.044 Uiso 1 1 calc R . . C25 C 0.5432(5) 0.9520(4) -0.1295(4) 0.0361(10) Uani 1 1 d . . . H25 H 0.4579 0.9882 -0.1652 0.043 Uiso 1 1 calc R . . C26 C 0.9312(5) 0.7738(4) 0.0412(3) 0.0319(9) Uani 1 1 d . . . 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 Mn1 0.0306(3) 0.0280(3) 0.0258(3) -0.0049(2) -0.0073(2) -0.0093(3) Mn2 0.0222(4) 0.0148(4) 0.0209(4) 0.0007(3) -0.0125(3) -0.0076(3) Cu1 0.0315(3) 0.0370(3) 0.0261(3) -0.0064(2) -0.0043(2) -0.0084(2) S1 0.0389(6) 0.0411(6) 0.0361(6) -0.0133(5) -0.0039(5) -0.0189(5) O1 0.0311(15) 0.0424(17) 0.0293(16) -0.0113(13) -0.0046(12) -0.0068(13) O2 0.0319(16) 0.055(2) 0.0311(16) -0.0103(14) -0.0080(13) -0.0071(14) O3 0.067(3) 0.082(3) 0.065(3) -0.033(2) 0.026(2) -0.049(2) O4 0.166(5) 0.093(4) 0.104(4) 0.033(3) -0.100(4) -0.084(4) O5 0.057(3) 0.090(3) 0.196(6) -0.105(4) 0.021(3) -0.028(2) O6 0.0461(19) 0.0300(17) 0.062(2) 0.0097(15) -0.0221(16) -0.0169(15) O7 0.0435(18) 0.0325(16) 0.0494(19) -0.0001(14) -0.0223(15) -0.0165(14) O8 0.0463(18) 0.0297(16) 0.0478(18) 0.0005(14) -0.0219(15) -0.0166(14) O9 0.0395(17) 0.0355(17) 0.0495(19) -0.0054(15) -0.0131(15) -0.0084(14) O10 0.056(5) 0.114(8) 0.045(4) -0.030(5) -0.011(4) 0.008(5) N1 0.0292(18) 0.037(2) 0.0263(17) -0.0081(15) -0.0049(14) -0.0079(15) N2 0.0285(18) 0.039(2) 0.0293(18) -0.0065(15) -0.0041(14) -0.0059(16) N3 0.040(2) 0.048(2) 0.033(2) -0.0070(17) 0.0006(17) -0.0130(19) N4 0.044(2) 0.035(2) 0.0275(18) -0.0057(15) -0.0099(16) -0.0111(17) C1 0.031(2) 0.028(2) 0.029(2) -0.0060(17) -0.0060(17) -0.0073(17) C2 0.031(2) 0.034(2) 0.027(2) -0.0024(17) -0.0076(17) -0.0094(18) C3 0.033(2) 0.037(2) 0.043(3) -0.015(2) -0.0045(19) -0.0072(19) C4 0.044(3) 0.049(3) 0.052(3) -0.006(2) -0.009(2) 0.000(2) C5 0.052(3) 0.040(3) 0.070(4) -0.012(3) -0.021(3) 0.001(2) C6 0.038(3) 0.054(3) 0.080(4) -0.034(3) -0.012(3) 0.000(2) C7 0.036(3) 0.073(4) 0.055(3) -0.032(3) -0.001(2) -0.002(3) C8 0.035(2) 0.049(3) 0.041(3) -0.019(2) -0.003(2) -0.006(2) C9 0.039(3) 0.065(3) 0.038(3) -0.015(2) 0.005(2) -0.013(2) C10 0.055(3) 0.056(3) 0.040(3) 0.003(2) 0.006(2) -0.021(3) C11 0.066(3) 0.054(3) 0.028(2) -0.005(2) -0.004(2) -0.018(3) C12 0.055(3) 0.048(3) 0.028(2) -0.001(2) -0.008(2) -0.015(2) C13 0.042(3) 0.034(2) 0.033(2) -0.0039(19) -0.0150(19) -0.007(2) C14 0.036(2) 0.035(2) 0.038(2) -0.0060(19) -0.0130(19) -0.0068(19) C15 0.037(3) 0.055(3) 0.054(3) -0.005(2) -0.021(2) -0.010(2) C16 0.032(3) 0.070(4) 0.064(3) -0.011(3) -0.012(2) -0.017(2) C17 0.035(3) 0.069(4) 0.052(3) -0.013(3) 0.002(2) -0.019(2) C18 0.037(2) 0.056(3) 0.035(2) -0.012(2) -0.007(2) -0.012(2) C19 0.028(2) 0.031(2) 0.035(2) -0.0098(18) -0.0059(17) -0.0073(17) C20 0.034(2) 0.039(2) 0.028(2) -0.0114(18) -0.0011(17) -0.0153(19) C21 0.035(2) 0.031(2) 0.030(2) -0.0059(17) -0.0038(17) -0.0119(18) C22 0.032(2) 0.030(2) 0.027(2) -0.0060(17) -0.0046(17) -0.0118(17) C23 0.034(2) 0.030(2) 0.030(2) -0.0052(17) -0.0041(17) -0.0140(18) C24 0.039(2) 0.031(2) 0.039(2) -0.0024(19) -0.0152(19) -0.0109(19) C25 0.035(2) 0.039(2) 0.036(2) -0.0079(19) -0.0085(18) -0.0115(19) C26 0.030(2) 0.034(2) 0.033(2) -0.0073(18) -0.0046(17) -0.0133(18) _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 Mn1 O3 2.087(4) . ? Mn1 O9 2.169(3) . ? Mn1 O8 2.197(3) 2_675 ? Mn1 O2 2.201(3) . ? Mn1 O1 2.217(3) . ? Mn1 O7 2.256(3) 1_455 ? Mn1 Mn2 3.2221(7) 1_455 ? Mn2 O8 1.901(3) 2_775 ? Mn2 O8 1.901(3) . ? Mn2 O7 1.920(3) 2_775 ? Mn2 O7 1.920(3) . ? Mn2 O10 2.374(8) 2_775 ? Mn2 O10 2.374(8) . ? Mn2 Mn1 3.2222(7) 2_675 ? Mn2 Mn1 3.2222(7) 1_655 ? Cu1 N2 1.961(3) . ? Cu1 N4 1.983(4) . ? Cu1 N1 1.984(3) . ? Cu1 N3 2.006(4) . ? S1 O5 1.414(4) . ? S1 O4 1.421(4) . ? S1 O3 1.432(4) . ? S1 C20 1.760(4) . ? O1 C1 1.248(5) . ? O2 C2 1.245(5) . ? O6 C26 1.229(5) . ? O7 C26 1.295(5) . ? O7 Mn1 2.256(3) 1_655 ? O8 C23 1.329(5) . ? O8 Mn1 2.197(3) 2_675 ? O9 H9A 0.8504 . ? O9 H9B 0.8502 . ? O10 H10' 0.8500 . ? N1 C1 1.324(5) . ? N1 C19 1.407(5) . ? N2 C2 1.317(5) . ? N2 C3 1.410(6) . ? N3 C9 1.277(6) . ? N3 C10 1.471(6) . ? N4 C13 1.283(6) . ? N4 C12 1.489(6) . ? C1 C2 1.530(6) . ? C3 C8 1.388(7) . ? C3 C4 1.394(7) . ? C4 C5 1.368(7) . ? C4 H4 0.9300 . ? C5 C6 1.374(8) . ? C5 H5 0.9300 . ? C6 C7 1.366(8) . ? C6 H6 0.9300 . ? C7 C8 1.406(7) . ? C7 H7 0.9300 . ? C8 C9 1.441(7) . ? C9 H9 0.9300 . ? C10 C11 1.508(8) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 C12 1.494(7) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 C14 1.445(6) . ? C13 H13 0.9300 . ? C14 C15 1.400(6) . ? C14 C19 1.411(6) . ? C15 C16 1.375(8) . ? C15 H15 0.9300 . ? C16 C17 1.378(8) . ? C16 H16 0.9300 . ? C17 C18 1.381(7) . ? C17 H17 0.9300 . ? C18 C19 1.394(6) . ? C18 H18 0.9300 . ? C20 C21 1.378(6) . ? C20 C25 1.389(6) . ? C21 C22 1.401(6) . ? C21 H21 0.9300 . ? C22 C23 1.406(6) . ? C22 C26 1.495(6) . ? C23 C24 1.409(6) . ? C24 C25 1.377(6) . ? C24 H24 0.9300 . ? C25 H25 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 O3 Mn1 O9 90.51(14) . . ? O3 Mn1 O8 96.56(15) . 2_675 ? O9 Mn1 O8 159.02(12) . 2_675 ? O3 Mn1 O2 164.15(15) . . ? O9 Mn1 O2 92.65(13) . . ? O8 Mn1 O2 85.92(13) 2_675 . ? O3 Mn1 O1 90.63(15) . . ? O9 Mn1 O1 91.95(12) . . ? O8 Mn1 O1 107.64(11) 2_675 . ? O2 Mn1 O1 73.74(11) . . ? O3 Mn1 O7 105.37(16) . 1_455 ? O9 Mn1 O7 88.26(11) . 1_455 ? O8 Mn1 O7 70.82(11) 2_675 1_455 ? O2 Mn1 O7 90.26(12) . 1_455 ? O1 Mn1 O7 163.99(12) . 1_455 ? O3 Mn1 Mn2 104.37(13) . 1_455 ? O9 Mn1 Mn2 124.03(9) . 1_455 ? O8 Mn1 Mn2 35.01(8) 2_675 1_455 ? O2 Mn1 Mn2 86.65(8) . 1_455 ? O1 Mn1 Mn2 140.06(8) . 1_455 ? O7 Mn1 Mn2 35.84(8) 1_455 1_455 ? O8 Mn2 O8 179.999(1) 2_775 . ? O8 Mn2 O7 95.03(12) 2_775 2_775 ? O8 Mn2 O7 84.97(12) . 2_775 ? O8 Mn2 O7 84.97(12) 2_775 . ? O8 Mn2 O7 95.03(12) . . ? O7 Mn2 O7 179.999(1) 2_775 . ? O8 Mn2 O10 84.6(2) 2_775 2_775 ? O8 Mn2 O10 95.4(2) . 2_775 ? O7 Mn2 O10 78.7(3) 2_775 2_775 ? O7 Mn2 O10 101.3(3) . 2_775 ? O8 Mn2 O10 95.4(2) 2_775 . ? O8 Mn2 O10 84.6(2) . . ? O7 Mn2 O10 101.3(3) 2_775 . ? O7 Mn2 O10 78.7(3) . . ? O10 Mn2 O10 179.999(1) 2_775 . ? O8 Mn2 Mn1 138.47(9) 2_775 2_675 ? O8 Mn2 Mn1 41.53(9) . 2_675 ? O7 Mn2 Mn1 43.47(9) 2_775 2_675 ? O7 Mn2 Mn1 136.53(9) . 2_675 ? O10 Mn2 Mn1 85.0(2) 2_775 2_675 ? O10 Mn2 Mn1 95.0(2) . 2_675 ? O8 Mn2 Mn1 41.53(9) 2_775 1_655 ? O8 Mn2 Mn1 138.47(9) . 1_655 ? O7 Mn2 Mn1 136.53(9) 2_775 1_655 ? O7 Mn2 Mn1 43.47(9) . 1_655 ? O10 Mn2 Mn1 95.0(2) 2_775 1_655 ? O10 Mn2 Mn1 85.0(2) . 1_655 ? Mn1 Mn2 Mn1 179.998(1) 2_675 1_655 ? N2 Cu1 N4 174.29(15) . . ? N2 Cu1 N1 82.70(14) . . ? N4 Cu1 N1 92.11(15) . . ? N2 Cu1 N3 89.32(15) . . ? N4 Cu1 N3 96.23(16) . . ? N1 Cu1 N3 166.58(16) . . ? O5 S1 O4 114.8(4) . . ? O5 S1 O3 110.1(3) . . ? O4 S1 O3 111.9(3) . . ? O5 S1 C20 106.2(2) . . ? O4 S1 C20 107.1(2) . . ? O3 S1 C20 106.1(2) . . ? C1 O1 Mn1 116.4(3) . . ? C2 O2 Mn1 116.4(3) . . ? S1 O3 Mn1 149.4(3) . . ? C26 O7 Mn2 128.2(3) . . ? C26 O7 Mn1 129.4(3) . 1_655 ? Mn2 O7 Mn1 100.69(12) . 1_655 ? C23 O8 Mn2 125.7(3) . . ? C23 O8 Mn1 130.7(3) . 2_675 ? Mn2 O8 Mn1 103.46(13) . 2_675 ? Mn1 O9 H9A 110.0 . . ? Mn1 O9 H9B 93.2 . . ? H9A O9 H9B 116.9 . . ? Mn2 O10 H10' 113.2 . . ? C1 N1 C19 122.1(4) . . ? C1 N1 Cu1 110.3(3) . . ? C19 N1 Cu1 127.6(3) . . ? C2 N2 C3 120.5(4) . . ? C2 N2 Cu1 111.0(3) . . ? C3 N2 Cu1 127.9(3) . . ? C9 N3 C10 115.7(4) . . ? C9 N3 Cu1 125.1(3) . . ? C10 N3 Cu1 119.1(3) . . ? C13 N4 C12 113.4(4) . . ? C13 N4 Cu1 122.4(3) . . ? C12 N4 Cu1 124.2(3) . . ? O1 C1 N1 129.5(4) . . ? O1 C1 C2 116.1(3) . . ? N1 C1 C2 114.3(4) . . ? O2 C2 N2 129.0(4) . . ? O2 C2 C1 117.2(4) . . ? N2 C2 C1 113.7(3) . . ? C8 C3 C4 118.6(4) . . ? C8 C3 N2 119.6(4) . . ? C4 C3 N2 121.8(4) . . ? C5 C4 C3 120.8(5) . . ? C5 C4 H4 119.6 . . ? C3 C4 H4 119.6 . . ? C4 C5 C6 121.3(5) . . ? C4 C5 H5 119.3 . . ? C6 C5 H5 119.3 . . ? C7 C6 C5 118.4(5) . . ? C7 C6 H6 120.8 . . ? C5 C6 H6 120.8 . . ? C6 C7 C8 121.8(5) . . ? C6 C7 H7 119.1 . . ? C8 C7 H7 119.1 . . ? C3 C8 C7 118.9(5) . . ? C3 C8 C9 124.2(4) . . ? C7 C8 C9 116.9(5) . . ? N3 C9 C8 128.2(5) . . ? N3 C9 H9 115.9 . . ? C8 C9 H9 115.9 . . ? N3 C10 C11 111.4(4) . . ? N3 C10 H10A 109.3 . . ? C11 C10 H10A 109.3 . . ? N3 C10 H10B 109.3 . . ? C11 C10 H10B 109.3 . . ? H10A C10 H10B 108.0 . . ? C12 C11 C10 112.4(4) . . ? C12 C11 H11A 109.1 . . ? C10 C11 H11A 109.1 . . ? C12 C11 H11B 109.1 . . ? C10 C11 H11B 109.1 . . ? H11A C11 H11B 107.8 . . ? N4 C12 C11 114.1(4) . . ? N4 C12 H12A 108.7 . . ? C11 C12 H12A 108.7 . . ? N4 C12 H12B 108.7 . . ? C11 C12 H12B 108.7 . . ? H12A C12 H12B 107.6 . . ? N4 C13 C14 129.9(4) . . ? N4 C13 H13 115.0 . . ? C14 C13 H13 115.0 . . ? C15 C14 C19 119.6(4) . . ? C15 C14 C13 115.1(4) . . ? C19 C14 C13 125.4(4) . . ? C16 C15 C14 121.5(5) . . ? C16 C15 H15 119.3 . . ? C14 C15 H15 119.3 . . ? C15 C16 C17 118.8(5) . . ? C15 C16 H16 120.6 . . ? C17 C16 H16 120.6 . . ? C16 C17 C18 121.0(5) . . ? C16 C17 H17 119.5 . . ? C18 C17 H17 119.5 . . ? C17 C18 C19 121.3(4) . . ? C17 C18 H18 119.3 . . ? C19 C18 H18 119.3 . . ? C18 C19 N1 123.5(4) . . ? C18 C19 C14 117.8(4) . . ? N1 C19 C14 118.5(4) . . ? C21 C20 C25 119.6(4) . . ? C21 C20 S1 118.7(3) . . ? C25 C20 S1 121.6(3) . . ? C20 C21 C22 121.8(4) . . ? C20 C21 H21 119.1 . . ? C22 C21 H21 119.1 . . ? C21 C22 C23 118.9(4) . . ? C21 C22 C26 115.2(4) . . ? C23 C22 C26 126.0(4) . . ? O8 C23 C22 124.1(4) . . ? O8 C23 C24 117.7(4) . . ? C22 C23 C24 118.2(4) . . ? C25 C24 C23 122.0(4) . . ? C25 C24 H24 119.0 . . ? C23 C24 H24 119.0 . . ? C24 C25 C20 119.5(4) . . ? C24 C25 H25 120.2 . . ? C20 C25 H25 120.2 . . ? O6 C26 O7 121.5(4) . . ? O6 C26 C22 118.7(4) . . ? O7 C26 C22 119.8(4) . . ? 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 O3 Mn1 O1 C1 177.6(3) . . . . ? O9 Mn1 O1 C1 -91.9(3) . . . . ? O8 Mn1 O1 C1 80.5(3) 2_675 . . . ? O2 Mn1 O1 C1 0.3(3) . . . . ? O7 Mn1 O1 C1 -1.4(6) 1_455 . . . ? Mn2 Mn1 O1 C1 64.0(3) 1_455 . . . ? O3 Mn1 O2 C2 -7.7(7) . . . . ? O9 Mn1 O2 C2 93.6(3) . . . . ? O8 Mn1 O2 C2 -107.4(3) 2_675 . . . ? O1 Mn1 O2 C2 2.3(3) . . . . ? O7 Mn1 O2 C2 -178.1(3) 1_455 . . . ? Mn2 Mn1 O2 C2 -142.5(3) 1_455 . . . ? O5 S1 O3 Mn1 -162.9(5) . . . . ? O4 S1 O3 Mn1 -33.9(6) . . . . ? C20 S1 O3 Mn1 82.6(5) . . . . ? O9 Mn1 O3 S1 133.6(5) . . . . ? O8 Mn1 O3 S1 -26.6(5) 2_675 . . . ? O2 Mn1 O3 S1 -124.8(6) . . . . ? O1 Mn1 O3 S1 -134.4(5) . . . . ? O7 Mn1 O3 S1 45.3(5) 1_455 . . . ? Mn2 Mn1 O3 S1 8.1(5) 1_455 . . . ? O8 Mn2 O7 C26 167.6(4) 2_775 . . . ? O8 Mn2 O7 C26 -12.4(4) . . . . ? O7 Mn2 O7 C26 114(35) 2_775 . . . ? O10 Mn2 O7 C26 -108.9(4) 2_775 . . . ? O10 Mn2 O7 C26 71.1(4) . . . . ? Mn1 Mn2 O7 C26 -14.3(4) 2_675 . . . ? Mn1 Mn2 O7 C26 165.7(4) 1_655 . . . ? O8 Mn2 O7 Mn1 1.83(14) 2_775 . . 1_655 ? O8 Mn2 O7 Mn1 -178.17(14) . . . 1_655 ? O7 Mn2 O7 Mn1 -52(35) 2_775 . . 1_655 ? O10 Mn2 O7 Mn1 85.3(2) 2_775 . . 1_655 ? O10 Mn2 O7 Mn1 -94.7(2) . . . 1_655 ? Mn1 Mn2 O7 Mn1 180.0 2_675 . . 1_655 ? O8 Mn2 O8 C23 55(28) 2_775 . . . ? O7 Mn2 O8 C23 -174.3(4) 2_775 . . . ? O7 Mn2 O8 C23 5.7(4) . . . . ? O10 Mn2 O8 C23 107.6(4) 2_775 . . . ? O10 Mn2 O8 C23 -72.4(4) . . . . ? Mn1 Mn2 O8 C23 -176.2(4) 2_675 . . . ? Mn1 Mn2 O8 C23 3.8(4) 1_655 . . . ? O8 Mn2 O8 Mn1 -129(28) 2_775 . . 2_675 ? O7 Mn2 O8 Mn1 1.89(15) 2_775 . . 2_675 ? O7 Mn2 O8 Mn1 -178.11(15) . . . 2_675 ? O10 Mn2 O8 Mn1 -76.2(3) 2_775 . . 2_675 ? O10 Mn2 O8 Mn1 103.8(3) . . . 2_675 ? Mn1 Mn2 O8 Mn1 180.0 1_655 . . 2_675 ? N2 Cu1 N1 C1 -23.0(3) . . . . ? N4 Cu1 N1 C1 159.3(3) . . . . ? N3 Cu1 N1 C1 30.9(8) . . . . ? N2 Cu1 N1 C19 155.8(4) . . . . ? N4 Cu1 N1 C19 -21.8(4) . . . . ? N3 Cu1 N1 C19 -150.3(6) . . . . ? N4 Cu1 N2 C2 49.8(17) . . . . ? N1 Cu1 N2 C2 25.3(3) . . . . ? N3 Cu1 N2 C2 -143.9(3) . . . . ? N4 Cu1 N2 C3 -139.5(14) . . . . ? N1 Cu1 N2 C3 -164.1(4) . . . . ? N3 Cu1 N2 C3 26.7(4) . . . . ? N2 Cu1 N3 C9 -15.6(5) . . . . ? N4 Cu1 N3 C9 163.0(4) . . . . ? N1 Cu1 N3 C9 -68.9(9) . . . . ? N2 Cu1 N3 C10 165.4(4) . . . . ? N4 Cu1 N3 C10 -16.0(4) . . . . ? N1 Cu1 N3 C10 112.1(7) . . . . ? N2 Cu1 N4 C13 -6.9(17) . . . . ? N1 Cu1 N4 C13 17.4(4) . . . . ? N3 Cu1 N4 C13 -173.1(4) . . . . ? N2 Cu1 N4 C12 170.7(14) . . . . ? N1 Cu1 N4 C12 -165.0(4) . . . . ? N3 Cu1 N4 C12 4.5(4) . . . . ? Mn1 O1 C1 N1 -177.9(4) . . . . ? Mn1 O1 C1 C2 -2.4(5) . . . . ? C19 N1 C1 O1 13.6(7) . . . . ? Cu1 N1 C1 O1 -167.5(4) . . . . ? C19 N1 C1 C2 -162.0(4) . . . . ? Cu1 N1 C1 C2 16.9(4) . . . . ? Mn1 O2 C2 N2 172.4(4) . . . . ? Mn1 O2 C2 C1 -4.3(5) . . . . ? C3 N2 C2 O2 -10.7(7) . . . . ? Cu1 N2 C2 O2 160.7(4) . . . . ? C3 N2 C2 C1 166.1(4) . . . . ? Cu1 N2 C2 C1 -22.5(4) . . . . ? O1 C1 C2 O2 4.6(6) . . . . ? N1 C1 C2 O2 -179.2(4) . . . . ? O1 C1 C2 N2 -172.6(4) . . . . ? N1 C1 C2 N2 3.6(5) . . . . ? C2 N2 C3 C8 146.8(5) . . . . ? Cu1 N2 C3 C8 -23.1(6) . . . . ? C2 N2 C3 C4 -36.3(7) . . . . ? Cu1 N2 C3 C4 153.8(4) . . . . ? C8 C3 C4 C5 -3.4(8) . . . . ? N2 C3 C4 C5 179.7(5) . . . . ? C3 C4 C5 C6 0.9(9) . . . . ? C4 C5 C6 C7 1.9(9) . . . . ? C5 C6 C7 C8 -2.2(9) . . . . ? C4 C3 C8 C7 3.1(7) . . . . ? N2 C3 C8 C7 -179.9(5) . . . . ? C4 C3 C8 C9 -176.8(5) . . . . ? N2 C3 C8 C9 0.2(7) . . . . ? C6 C7 C8 C3 -0.3(8) . . . . ? C6 C7 C8 C9 179.6(5) . . . . ? C10 N3 C9 C8 -179.7(5) . . . . ? Cu1 N3 C9 C8 1.3(8) . . . . ? C3 C8 C9 N3 11.1(9) . . . . ? C7 C8 C9 N3 -168.8(6) . . . . ? C9 N3 C10 C11 -128.6(5) . . . . ? Cu1 N3 C10 C11 50.5(6) . . . . ? N3 C10 C11 C12 -77.8(6) . . . . ? C13 N4 C12 C11 150.5(4) . . . . ? Cu1 N4 C12 C11 -27.3(6) . . . . ? C10 C11 C12 N4 63.9(6) . . . . ? C12 N4 C13 C14 174.8(5) . . . . ? Cu1 N4 C13 C14 -7.3(7) . . . . ? N4 C13 C14 C15 173.0(5) . . . . ? N4 C13 C14 C19 -7.6(8) . . . . ? C19 C14 C15 C16 2.9(8) . . . . ? C13 C14 C15 C16 -177.6(5) . . . . ? C14 C15 C16 C17 -1.5(9) . . . . ? C15 C16 C17 C18 -0.7(9) . . . . ? C16 C17 C18 C19 1.4(8) . . . . ? C17 C18 C19 N1 174.4(5) . . . . ? C17 C18 C19 C14 0.0(7) . . . . ? C1 N1 C19 C18 18.8(6) . . . . ? Cu1 N1 C19 C18 -159.9(4) . . . . ? C1 N1 C19 C14 -166.9(4) . . . . ? Cu1 N1 C19 C14 14.4(6) . . . . ? C15 C14 C19 C18 -2.2(7) . . . . ? C13 C14 C19 C18 178.4(4) . . . . ? C15 C14 C19 N1 -176.8(4) . . . . ? C13 C14 C19 N1 3.8(7) . . . . ? O5 S1 C20 C21 -43.7(5) . . . . ? O4 S1 C20 C21 -166.8(4) . . . . ? O3 S1 C20 C21 73.5(4) . . . . ? O5 S1 C20 C25 136.3(5) . . . . ? O4 S1 C20 C25 13.2(5) . . . . ? O3 S1 C20 C25 -106.5(4) . . . . ? C25 C20 C21 C22 -1.5(6) . . . . ? S1 C20 C21 C22 178.6(3) . . . . ? C20 C21 C22 C23 0.4(6) . . . . ? C20 C21 C22 C26 -179.3(4) . . . . ? Mn2 O8 C23 C22 -0.9(6) . . . . ? Mn1 O8 C23 C22 -176.0(3) 2_675 . . . ? Mn2 O8 C23 C24 177.7(3) . . . . ? Mn1 O8 C23 C24 2.6(6) 2_675 . . . ? C21 C22 C23 O8 179.5(4) . . . . ? C26 C22 C23 O8 -0.9(7) . . . . ? C21 C22 C23 C24 0.8(6) . . . . ? C26 C22 C23 C24 -179.5(4) . . . . ? O8 C23 C24 C25 -179.7(4) . . . . ? C22 C23 C24 C25 -0.9(7) . . . . ? C23 C24 C25 C20 -0.2(7) . . . . ? C21 C20 C25 C24 1.4(6) . . . . ? S1 C20 C25 C24 -178.7(3) . . . . ? Mn2 O7 C26 O6 -168.0(3) . . . . ? Mn1 O7 C26 O6 -6.2(6) 1_655 . . . ? Mn2 O7 C26 C22 13.4(6) . . . . ? Mn1 O7 C26 C22 175.2(3) 1_655 . . . ? C21 C22 C26 O6 -4.5(6) . . . . ? C23 C22 C26 O6 175.8(4) . . . . ? C21 C22 C26 O7 174.1(4) . . . . ? C23 C22 C26 O7 -5.6(7) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.02 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 1.853 _refine_diff_density_min -0.791 _refine_diff_density_rms 0.101 data_090313d _database_code_depnum_ccdc_archive 'CCDC 767161' #TrackingRef '- 080925a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C92 H78 Cu4 Gd2 N16 O28 S2' _chemical_formula_weight 2488.48 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' 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Gd Gd -0.1653 3.9035 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.6013(3) _cell_length_b 12.6027(3) _cell_length_c 16.6810(7) _cell_angle_alpha 98.0000(10) _cell_angle_beta 103.0790(10) _cell_angle_gamma 110.1200(0) _cell_volume 2353.73(13) _cell_formula_units_Z 1 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 9895 _cell_measurement_theta_min 2.42 _cell_measurement_theta_max 30.40 _exptl_crystal_description BLOCK _exptl_crystal_colour GREEN _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.32 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas NONE _exptl_crystal_density_diffrn 1.757 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1244 _exptl_absorpt_coefficient_mu 2.410 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.565848 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 '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 12141 _diffrn_reflns_av_R_equivalents 0.0102 _diffrn_reflns_av_sigmaI/netI 0.0193 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.77 _diffrn_reflns_theta_max 25.03 _reflns_number_total 8254 _reflns_number_gt 7768 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0335P)^2^+3.0743P] 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 8254 _refine_ls_number_parameters 650 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0256 _refine_ls_R_factor_gt 0.0237 _refine_ls_wR_factor_ref 0.0657 _refine_ls_wR_factor_gt 0.0644 _refine_ls_goodness_of_fit_ref 1.065 _refine_ls_restrained_S_all 1.067 _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 Gd1 Gd 0.692746(11) 0.679327(11) 0.659892(8) 0.02100(5) Uani 1 1 d . . . Cu1 Cu 0.76008(3) 0.97940(3) 0.97430(2) 0.03021(9) Uani 1 1 d . . . Cu2 Cu 1.06398(3) 0.74314(3) 0.50260(3) 0.03369(10) Uani 1 1 d . . . S1 S 0.61734(9) 0.08307(8) 0.78712(8) 0.0515(2) Uani 1 1 d . . . O1 O 0.81494(17) 0.86335(17) 0.76026(12) 0.0272(4) Uani 1 1 d . . . O2 O 0.60800(18) 0.72337(18) 0.76902(13) 0.0315(5) Uani 1 1 d . . . O3 O 0.80460(19) 0.78631(19) 0.57743(14) 0.0332(5) Uani 1 1 d . . . O4 O 0.87481(18) 0.6488(2) 0.65988(14) 0.0345(5) Uani 1 1 d . . . O5 O 0.6416(2) 0.48482(19) 0.69012(15) 0.0396(5) Uani 1 1 d . . . O6 O 0.7843(2) 0.62359(18) 0.79240(13) 0.0355(5) Uani 1 1 d . . . O7 O 0.9404(3) 0.5756(2) 0.8881(2) 0.0688(9) Uani 1 1 d . . . H7 H 0.9118 0.6166 0.8647 0.103 Uiso 1 1 calc R . . O8 O 0.6236(3) 0.0494(3) 0.8680(2) 0.0726(10) Uani 1 1 d . . . O9 O 0.5008(3) 0.0711(3) 0.7431(3) 0.0878(12) Uani 1 1 d . . . O10 O 0.6712(3) 0.0273(2) 0.73497(18) 0.0539(7) Uani 1 1 d . . . O11 O 0.65252(17) 0.55403(19) 0.52291(13) 0.0342(5) Uani 1 1 d . . . O12 O 0.51420(18) 0.41664(19) 0.41383(13) 0.0325(5) Uani 1 1 d . . . O13 O 0.6057(2) 0.8207(2) 0.61665(15) 0.0406(5) Uani 1 1 d . . . H13A H 0.6354 0.8869 0.6512 0.061 Uiso 1 1 d R . . H13B H 0.5318 0.7836 0.6070 0.061 Uiso 1 1 d R . . O14 O 0.3920(5) 0.8141(5) 0.6743(4) 0.0708(18) Uani 0.50 1 d PU . . N1 N 0.8434(2) 0.9837(2) 0.88896(15) 0.0260(5) Uani 1 1 d . . . N2 N 0.6545(2) 0.8231(2) 0.90812(15) 0.0283(5) Uani 1 1 d . . . N3 N 0.6592(3) 0.9874(3) 1.04560(17) 0.0383(6) Uani 1 1 d . . . N4 N 0.8995(2) 1.0965(2) 1.06138(16) 0.0351(6) Uani 1 1 d . . . N5 N 0.9245(2) 0.7772(2) 0.49218(17) 0.0344(6) Uani 1 1 d . . . N6 N 1.0158(2) 0.6602(2) 0.58811(16) 0.0299(5) Uani 1 1 d . . . N7 N 1.1751(3) 0.6747(3) 0.48758(19) 0.0390(6) Uani 1 1 d . . . N8 N 1.1399(3) 0.8766(3) 0.45759(19) 0.0406(7) Uani 1 1 d . . . C1 C 0.7858(2) 0.8912(2) 0.82469(17) 0.0236(6) Uani 1 1 d . . . C2 C 0.6714(2) 0.8037(2) 0.83289(18) 0.0256(6) Uani 1 1 d . . . C3 C 0.5640(3) 0.7437(3) 0.9312(2) 0.0358(7) Uani 1 1 d . . . C4 C 0.5115(4) 0.6251(3) 0.8908(3) 0.0584(11) Uani 1 1 d . . . H4 H 0.5342 0.5977 0.8455 0.070 Uiso 1 1 calc R . . C5 C 0.4264(5) 0.5485(4) 0.9175(3) 0.0856(18) Uani 1 1 d . . . H5 H 0.3926 0.4701 0.8899 0.103 Uiso 1 1 calc R . . C6 C 0.3908(5) 0.5858(5) 0.9841(4) 0.0880(18) Uani 1 1 d . . . H6 H 0.3326 0.5335 1.0010 0.106 Uiso 1 1 calc R . . C7 C 0.4418(4) 0.7002(4) 1.0250(3) 0.0663(13) Uani 1 1 d . . . H7A H 0.4177 0.7255 1.0702 0.080 Uiso 1 1 calc R . . C8 C 0.5297(3) 0.7812(3) 1.0009(2) 0.0427(8) Uani 1 1 d . . . C9 C 0.5731(3) 0.9010(3) 1.0493(2) 0.0468(9) Uani 1 1 d . . . H9 H 0.5330 0.9156 1.0872 0.056 Uiso 1 1 calc R . . C10 C 0.6815(4) 1.1045(4) 1.0934(3) 0.0559(10) Uani 1 1 d . . . H10A H 0.6213 1.0984 1.1220 0.067 Uiso 1 1 calc R . . H10B H 0.6742 1.1529 1.0539 0.067 Uiso 1 1 calc R . . C11 C 0.8024(4) 1.1635(4) 1.1587(2) 0.0577(11) Uani 1 1 d . . . H11A H 0.8350 1.2445 1.1565 0.069 Uiso 1 1 calc R . . H11B H 0.7923 1.1617 1.2145 0.069 Uiso 1 1 calc R . . C12 C 0.8916(4) 1.1112(3) 1.1487(2) 0.0478(9) Uani 1 1 d . . . H12A H 0.9686 1.1614 1.1875 0.057 Uiso 1 1 calc R . . H12B H 0.8687 1.0362 1.1630 0.057 Uiso 1 1 calc R . . C13 C 0.9982(3) 1.1515(3) 1.0493(2) 0.0348(7) Uani 1 1 d . . . H13 H 1.0613 1.1957 1.0972 0.042 Uiso 1 1 calc R . . C14 C 1.0217(3) 1.1521(3) 0.9685(2) 0.0330(7) Uani 1 1 d . . . C15 C 1.1263(3) 1.2421(3) 0.9703(3) 0.0475(9) Uani 1 1 d . . . H15 H 1.1784 1.2893 1.0222 0.057 Uiso 1 1 calc R . . C16 C 1.1532(4) 1.2618(4) 0.8975(3) 0.0662(13) Uani 1 1 d . . . H16 H 1.2231 1.3215 0.8997 0.079 Uiso 1 1 calc R . . C17 C 1.0750(4) 1.1920(3) 0.8204(3) 0.0635(13) Uani 1 1 d . . . H17 H 1.0913 1.2070 0.7705 0.076 Uiso 1 1 calc R . . C18 C 0.9733(3) 1.1004(3) 0.8165(2) 0.0439(9) Uani 1 1 d . . . H18 H 0.9223 1.0542 0.7640 0.053 Uiso 1 1 calc R . . C19 C 0.9458(3) 1.0760(2) 0.8900(2) 0.0294(6) Uani 1 1 d . . . C20 C 0.8789(3) 0.7541(3) 0.55471(19) 0.0289(6) Uani 1 1 d . . . C21 C 0.9258(3) 0.6809(3) 0.60625(18) 0.0277(6) Uani 1 1 d . . . C22 C 1.0683(3) 0.5918(3) 0.6277(2) 0.0305(6) Uani 1 1 d . . . C23 C 1.0389(3) 0.5461(3) 0.6947(2) 0.0435(8) Uani 1 1 d . . . H23 H 0.9821 0.5619 0.7156 0.052 Uiso 1 1 calc R . . C24 C 1.0918(4) 0.4779(4) 0.7311(3) 0.0547(10) Uani 1 1 d . . . H24 H 1.0699 0.4486 0.7757 0.066 Uiso 1 1 calc R . . C25 C 1.1763(4) 0.4527(4) 0.7022(3) 0.0593(11) Uani 1 1 d . . . H25 H 1.2111 0.4060 0.7263 0.071 Uiso 1 1 calc R . . C26 C 1.2086(3) 0.4980(4) 0.6370(3) 0.0502(9) Uani 1 1 d . . . H26 H 1.2665 0.4821 0.6177 0.060 Uiso 1 1 calc R . . C27 C 1.1569(3) 0.5673(3) 0.5988(2) 0.0360(7) Uani 1 1 d . . . C28 C 1.2008(3) 0.6063(3) 0.5303(2) 0.0404(8) Uani 1 1 d . . . H28 H 1.2545 0.5776 0.5158 0.048 Uiso 1 1 calc R . . C29 C 1.2308(4) 0.7032(4) 0.4203(3) 0.0551(10) Uani 1 1 d . . . H29A H 1.1694 0.6838 0.3673 0.066 Uiso 1 1 calc R . . H29B H 1.2761 0.6558 0.4133 0.066 Uiso 1 1 calc R . . C30 C 1.3105(4) 0.8284(4) 0.4386(3) 0.0684(13) Uani 1 1 d . . . H30A H 1.3233 0.8458 0.3859 0.082 Uiso 1 1 calc R . . H30B H 1.3864 0.8391 0.4760 0.082 Uiso 1 1 calc R . . C31 C 1.2696(4) 0.9160(4) 0.4780(3) 0.0567(11) Uani 1 1 d . . . H31A H 1.3031 0.9347 0.5390 0.068 Uiso 1 1 calc R . . H31B H 1.2998 0.9869 0.4591 0.068 Uiso 1 1 calc R . . C32 C 1.0885(3) 0.9373(3) 0.4228(2) 0.0417(8) Uani 1 1 d . . . H32 H 1.1360 1.0023 0.4086 0.050 Uiso 1 1 calc R . . C33 C 0.9634(3) 0.9146(3) 0.4032(2) 0.0395(8) Uani 1 1 d . . . C34 C 0.9207(4) 0.9766(4) 0.3494(2) 0.0510(10) Uani 1 1 d . . . H34 H 0.9736 1.0317 0.3304 0.061 Uiso 1 1 calc R . . C35 C 0.8039(4) 0.9582(4) 0.3243(3) 0.0622(12) Uani 1 1 d . . . H35 H 0.7778 1.0009 0.2891 0.075 Uiso 1 1 calc R . . C36 C 0.7245(4) 0.8756(4) 0.3513(3) 0.0611(11) Uani 1 1 d . . . H36 H 0.6442 0.8602 0.3321 0.073 Uiso 1 1 calc R . . C37 C 0.7635(3) 0.8156(4) 0.4069(2) 0.0491(9) Uani 1 1 d . . . H37 H 0.7095 0.7614 0.4258 0.059 Uiso 1 1 calc R . . C38 C 0.8828(3) 0.8360(3) 0.4346(2) 0.0373(7) Uani 1 1 d . . . C39 C 0.7230(3) 0.5157(3) 0.75764(19) 0.0309(7) Uani 1 1 d . . . C40 C 0.7540(3) 0.4289(3) 0.79928(19) 0.0323(7) Uani 1 1 d . . . C41 C 0.6783(3) 0.3115(3) 0.7745(2) 0.0337(7) Uani 1 1 d . . . H41 H 0.6080 0.2868 0.7309 0.040 Uiso 1 1 calc R . . C42 C 0.7071(3) 0.2320(3) 0.8143(2) 0.0400(8) Uani 1 1 d . . . C43 C 0.8126(4) 0.2700(4) 0.8786(3) 0.0558(11) Uani 1 1 d . . . H43 H 0.8313 0.2167 0.9062 0.067 Uiso 1 1 calc R . . C44 C 0.8897(4) 0.3832(4) 0.9024(3) 0.0636(12) Uani 1 1 d . . . H44 H 0.9608 0.4062 0.9449 0.076 Uiso 1 1 calc R . . C45 C 0.8617(3) 0.4644(3) 0.8631(2) 0.0462(9) Uani 1 1 d . . . C46 C 0.5482(2) 0.4914(2) 0.48176(17) 0.0243(6) Uani 1 1 d . . . 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 Gd1 0.02121(8) 0.01946(8) 0.02020(8) 0.00134(5) 0.00572(5) 0.00689(6) Cu1 0.0338(2) 0.02758(19) 0.02425(18) -0.00091(15) 0.01012(15) 0.00767(16) Cu2 0.0368(2) 0.0381(2) 0.0391(2) 0.01539(17) 0.02273(17) 0.02023(17) S1 0.0517(5) 0.0376(5) 0.0845(7) 0.0304(5) 0.0315(5) 0.0270(4) O1 0.0263(10) 0.0237(10) 0.0279(11) 0.0002(8) 0.0103(8) 0.0059(8) O2 0.0267(11) 0.0290(11) 0.0281(11) -0.0043(9) 0.0088(9) 0.0019(9) O3 0.0351(12) 0.0341(12) 0.0425(13) 0.0158(10) 0.0208(10) 0.0191(10) O4 0.0303(11) 0.0474(13) 0.0366(12) 0.0191(10) 0.0176(10) 0.0193(10) O5 0.0419(13) 0.0299(12) 0.0387(13) 0.0110(10) 0.0010(11) 0.0098(10) O6 0.0456(13) 0.0272(12) 0.0308(11) 0.0052(9) 0.0094(10) 0.0127(10) O7 0.0678(19) 0.0406(16) 0.070(2) -0.0067(14) -0.0203(16) 0.0210(14) O8 0.097(2) 0.076(2) 0.105(3) 0.067(2) 0.074(2) 0.0608(19) O9 0.0527(18) 0.0480(18) 0.154(4) 0.036(2) 0.009(2) 0.0185(15) O10 0.0663(18) 0.0352(14) 0.0625(17) 0.0079(12) 0.0194(14) 0.0235(13) O11 0.0215(11) 0.0422(13) 0.0294(11) -0.0091(9) 0.0064(9) 0.0087(9) O12 0.0253(11) 0.0369(12) 0.0290(11) -0.0084(9) 0.0069(9) 0.0116(9) O13 0.0408(13) 0.0374(13) 0.0437(13) 0.0061(10) 0.0089(11) 0.0189(11) O14 0.035(3) 0.055(3) 0.079(4) -0.021(3) 0.001(3) -0.010(2) N1 0.0267(12) 0.0236(12) 0.0246(12) 0.0021(10) 0.0069(10) 0.0078(10) N2 0.0323(13) 0.0245(13) 0.0250(12) 0.0041(10) 0.0105(10) 0.0066(10) N3 0.0438(16) 0.0414(16) 0.0313(14) 0.0025(12) 0.0139(12) 0.0191(14) N4 0.0410(16) 0.0323(14) 0.0247(13) -0.0005(11) 0.0027(11) 0.0129(12) N5 0.0377(15) 0.0416(16) 0.0354(14) 0.0158(12) 0.0188(12) 0.0214(12) N6 0.0300(13) 0.0313(14) 0.0345(14) 0.0104(11) 0.0151(11) 0.0146(11) N7 0.0425(16) 0.0407(16) 0.0458(16) 0.0121(13) 0.0267(13) 0.0211(13) N8 0.0482(17) 0.0382(16) 0.0472(17) 0.0149(13) 0.0295(14) 0.0194(14) C1 0.0241(14) 0.0217(14) 0.0234(14) 0.0034(11) 0.0046(11) 0.0092(11) C2 0.0248(14) 0.0250(15) 0.0271(15) 0.0042(12) 0.0080(12) 0.0103(12) C3 0.0377(17) 0.0347(18) 0.0339(17) 0.0103(14) 0.0146(14) 0.0094(14) C4 0.070(3) 0.040(2) 0.055(2) 0.0052(18) 0.035(2) 0.0005(19) C5 0.102(4) 0.045(3) 0.085(4) 0.004(2) 0.056(3) -0.013(3) C6 0.094(4) 0.067(3) 0.092(4) 0.020(3) 0.063(3) -0.005(3) C7 0.071(3) 0.066(3) 0.066(3) 0.016(2) 0.047(2) 0.014(2) C8 0.0417(19) 0.046(2) 0.0423(19) 0.0104(16) 0.0215(16) 0.0133(16) C9 0.050(2) 0.058(2) 0.0399(19) 0.0090(17) 0.0272(17) 0.0230(19) C10 0.068(3) 0.051(2) 0.054(2) -0.0015(19) 0.022(2) 0.033(2) C11 0.079(3) 0.050(2) 0.039(2) -0.0072(18) 0.017(2) 0.025(2) C12 0.059(2) 0.051(2) 0.0238(16) 0.0009(15) 0.0052(16) 0.0167(18) C13 0.0359(17) 0.0260(16) 0.0311(16) -0.0028(13) -0.0053(13) 0.0118(14) C14 0.0282(16) 0.0253(15) 0.0395(18) 0.0009(13) 0.0037(13) 0.0098(13) C15 0.0348(18) 0.0325(18) 0.056(2) -0.0059(16) 0.0082(17) 0.0004(15) C16 0.053(2) 0.040(2) 0.081(3) -0.006(2) 0.035(2) -0.0128(18) C17 0.073(3) 0.037(2) 0.063(3) -0.0028(19) 0.041(2) -0.0069(19) C18 0.051(2) 0.0296(17) 0.0409(19) -0.0019(14) 0.0218(16) 0.0026(15) C19 0.0271(15) 0.0213(14) 0.0359(16) 0.0003(12) 0.0096(13) 0.0070(12) C20 0.0277(15) 0.0269(15) 0.0327(16) 0.0074(12) 0.0118(13) 0.0092(12) C21 0.0259(15) 0.0271(15) 0.0273(15) 0.0024(12) 0.0075(12) 0.0088(12) C22 0.0287(15) 0.0281(16) 0.0339(16) 0.0059(13) 0.0083(13) 0.0112(13) C23 0.045(2) 0.056(2) 0.047(2) 0.0212(17) 0.0234(17) 0.0307(18) C24 0.066(3) 0.066(3) 0.057(2) 0.035(2) 0.030(2) 0.040(2) C25 0.069(3) 0.067(3) 0.072(3) 0.036(2) 0.029(2) 0.048(2) C26 0.050(2) 0.057(2) 0.064(2) 0.021(2) 0.0271(19) 0.0360(19) C27 0.0331(17) 0.0341(17) 0.0433(19) 0.0067(14) 0.0135(14) 0.0156(14) C28 0.0380(18) 0.0409(19) 0.052(2) 0.0094(16) 0.0238(16) 0.0214(15) C29 0.067(3) 0.060(3) 0.065(3) 0.024(2) 0.047(2) 0.035(2) C30 0.069(3) 0.066(3) 0.098(4) 0.035(3) 0.059(3) 0.032(2) C31 0.048(2) 0.051(2) 0.080(3) 0.019(2) 0.035(2) 0.0182(19) C32 0.061(2) 0.0365(18) 0.0392(19) 0.0138(15) 0.0308(17) 0.0211(17) C33 0.060(2) 0.0381(18) 0.0290(17) 0.0085(14) 0.0211(16) 0.0243(17) C34 0.083(3) 0.052(2) 0.0362(19) 0.0209(17) 0.0280(19) 0.038(2) C35 0.091(3) 0.080(3) 0.043(2) 0.032(2) 0.025(2) 0.058(3) C36 0.067(3) 0.086(3) 0.047(2) 0.023(2) 0.015(2) 0.049(3) C37 0.052(2) 0.063(3) 0.046(2) 0.0228(19) 0.0188(18) 0.032(2) C38 0.050(2) 0.0421(19) 0.0306(16) 0.0121(14) 0.0173(15) 0.0257(16) C39 0.0379(17) 0.0312(17) 0.0297(16) 0.0107(13) 0.0153(14) 0.0158(14) C40 0.0437(18) 0.0328(17) 0.0283(15) 0.0093(13) 0.0136(14) 0.0215(14) C41 0.0400(18) 0.0343(17) 0.0365(17) 0.0136(14) 0.0166(14) 0.0205(14) C42 0.055(2) 0.0359(18) 0.048(2) 0.0182(16) 0.0282(17) 0.0284(17) C43 0.081(3) 0.057(3) 0.047(2) 0.0179(19) 0.011(2) 0.050(2) C44 0.080(3) 0.055(3) 0.048(2) 0.0004(19) -0.012(2) 0.042(2) C45 0.058(2) 0.043(2) 0.0375(19) 0.0011(16) 0.0026(17) 0.0302(18) C46 0.0249(14) 0.0250(14) 0.0225(14) 0.0026(11) 0.0072(12) 0.0104(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 Gd1 O12 2.396(2) 2_666 ? Gd1 O2 2.402(2) . ? Gd1 O3 2.405(2) . ? Gd1 O1 2.4183(19) . ? Gd1 O11 2.428(2) . ? Gd1 O4 2.454(2) . ? Gd1 O5 2.466(2) . ? Gd1 O13 2.498(2) . ? Gd1 O6 2.558(2) . ? Gd1 C39 2.873(3) . ? Cu1 N3 1.945(3) . ? Cu1 N1 1.947(2) . ? Cu1 N2 1.948(2) . ? Cu1 N4 1.960(3) . ? Cu2 N7 1.923(3) . ? Cu2 N5 1.924(3) . ? Cu2 N6 1.966(3) . ? Cu2 N8 1.969(3) . ? S1 O9 1.431(3) . ? S1 O10 1.461(3) . ? S1 O8 1.463(3) . ? S1 C42 1.754(4) . ? O1 C1 1.255(3) . ? O2 C2 1.248(3) . ? O3 C20 1.250(4) . ? O4 C21 1.249(4) . ? O5 C39 1.246(4) . ? O6 C39 1.280(4) . ? O7 C45 1.347(5) . ? O7 H7 0.8200 . ? O11 C46 1.245(3) . ? O12 C46 1.250(3) . ? O12 Gd1 2.396(2) 2_666 ? O13 H13A 0.8500 . ? O13 H13B 0.8497 . ? N1 C1 1.324(4) . ? N1 C19 1.403(4) . ? N2 C2 1.323(4) . ? N2 C3 1.404(4) . ? N3 C9 1.266(5) . ? N3 C10 1.476(4) . ? N4 C13 1.276(4) . ? N4 C12 1.473(4) . ? N5 C20 1.321(4) . ? N5 C38 1.409(4) . ? N6 C21 1.335(4) . ? N6 C22 1.403(4) . ? N7 C28 1.270(5) . ? N7 C29 1.476(4) . ? N8 C32 1.279(5) . ? N8 C31 1.475(5) . ? C1 C2 1.533(4) . ? C3 C4 1.401(5) . ? C3 C8 1.406(5) . ? C4 C5 1.380(6) . ? C4 H4 0.9300 . ? C5 C6 1.371(7) . ? C5 H5 0.9300 . ? C6 C7 1.360(7) . ? C6 H6 0.9300 . ? C7 C8 1.404(5) . ? C7 H7A 0.9300 . ? C8 C9 1.457(5) . ? C9 H9 0.9300 . ? C10 C11 1.519(6) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 C12 1.512(6) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 C14 1.443(5) . ? C13 H13 0.9300 . ? C14 C15 1.403(5) . ? C14 C19 1.415(4) . ? C15 C16 1.365(6) . ? C15 H15 0.9300 . ? C16 C17 1.383(6) . ? C16 H16 0.9300 . ? C17 C18 1.379(5) . ? C17 H17 0.9300 . ? C18 C19 1.393(5) . ? C18 H18 0.9300 . ? C20 C21 1.519(4) . ? C22 C23 1.392(5) . ? C22 C27 1.419(4) . ? C23 C24 1.382(5) . ? C23 H23 0.9300 . ? C24 C25 1.375(6) . ? C24 H24 0.9300 . ? C25 C26 1.373(6) . ? C25 H25 0.9300 . ? C26 C27 1.397(5) . ? C26 H26 0.9300 . ? C27 C28 1.453(5) . ? C28 H28 0.9300 . ? C29 C30 1.492(6) . ? C29 H29A 0.9700 . ? C29 H29B 0.9700 . ? C30 C31 1.504(6) . ? C30 H30A 0.9700 . ? C30 H30B 0.9700 . ? C31 H31A 0.9700 . ? C31 H31B 0.9700 . ? C32 C33 1.451(5) . ? C32 H32 0.9300 . ? C33 C34 1.404(5) . ? C33 C38 1.407(5) . ? C34 C35 1.362(6) . ? C34 H34 0.9300 . ? C35 C36 1.381(7) . ? C35 H35 0.9300 . ? C36 C37 1.385(5) . ? C36 H36 0.9300 . ? C37 C38 1.388(5) . ? C37 H37 0.9300 . ? C39 C40 1.488(4) . ? C40 C41 1.396(5) . ? C40 C45 1.404(5) . ? C41 C42 1.380(5) . ? C41 H41 0.9300 . ? C42 C43 1.387(6) . ? C43 C44 1.360(6) . ? C43 H43 0.9300 . ? C44 C45 1.391(5) . ? C44 H44 0.9300 . ? C46 C46 1.539(5) 2_666 ? 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 O12 Gd1 O2 78.91(7) 2_666 . ? O12 Gd1 O3 112.87(8) 2_666 . ? O2 Gd1 O3 136.40(7) . . ? O12 Gd1 O1 134.52(7) 2_666 . ? O2 Gd1 O1 66.65(7) . . ? O3 Gd1 O1 77.78(7) . . ? O12 Gd1 O11 67.03(7) 2_666 . ? O2 Gd1 O11 144.47(7) . . ? O3 Gd1 O11 69.99(8) . . ? O1 Gd1 O11 147.19(7) . . ? O12 Gd1 O4 137.52(7) 2_666 . ? O2 Gd1 O4 133.97(7) . . ? O3 Gd1 O4 65.17(7) . . ? O1 Gd1 O4 87.74(7) . . ? O11 Gd1 O4 73.53(7) . . ? O12 Gd1 O5 76.88(8) 2_666 . ? O2 Gd1 O5 85.77(8) . . ? O3 Gd1 O5 137.10(8) . . ? O1 Gd1 O5 126.45(7) . . ? O11 Gd1 O5 77.22(8) . . ? O4 Gd1 O5 79.72(8) . . ? O12 Gd1 O13 68.55(8) 2_666 . ? O2 Gd1 O13 74.60(8) . . ? O3 Gd1 O13 71.99(7) . . ? O1 Gd1 O13 74.15(7) . . ? O11 Gd1 O13 100.80(8) . . ? O4 Gd1 O13 136.12(8) . . ? O5 Gd1 O13 142.75(8) . . ? O12 Gd1 O6 120.92(8) 2_666 . ? O2 Gd1 O6 71.10(7) . . ? O3 Gd1 O6 124.13(7) . . ? O1 Gd1 O6 75.56(7) . . ? O11 Gd1 O6 117.94(7) . . ? O4 Gd1 O6 65.60(7) . . ? O5 Gd1 O6 51.77(7) . . ? O13 Gd1 O6 140.96(7) . . ? O12 Gd1 C39 100.10(9) 2_666 . ? O2 Gd1 C39 79.82(8) . . ? O3 Gd1 C39 133.61(8) . . ? O1 Gd1 C39 101.93(8) . . ? O11 Gd1 C39 96.00(8) . . ? O4 Gd1 C39 68.47(8) . . ? O5 Gd1 C39 25.56(8) . . ? O13 Gd1 C39 153.52(8) . . ? O6 Gd1 C39 26.45(8) . . ? N3 Cu1 N1 169.03(11) . . ? N3 Cu1 N2 93.83(11) . . ? N1 Cu1 N2 86.14(10) . . ? N3 Cu1 N4 91.40(12) . . ? N1 Cu1 N4 93.09(11) . . ? N2 Cu1 N4 155.77(11) . . ? N7 Cu2 N5 164.51(13) . . ? N7 Cu2 N6 95.07(11) . . ? N5 Cu2 N6 86.05(11) . . ? N7 Cu2 N8 92.86(12) . . ? N5 Cu2 N8 91.94(12) . . ? N6 Cu2 N8 157.21(12) . . ? O9 S1 O10 113.6(2) . . ? O9 S1 O8 112.6(2) . . ? O10 S1 O8 112.45(17) . . ? O9 S1 C42 106.92(18) . . ? O10 S1 C42 105.49(16) . . ? O8 S1 C42 104.9(2) . . ? C1 O1 Gd1 119.40(17) . . ? C2 O2 Gd1 119.10(18) . . ? C20 O3 Gd1 119.07(19) . . ? C21 O4 Gd1 119.35(19) . . ? C39 O5 Gd1 95.77(19) . . ? C39 O6 Gd1 90.62(18) . . ? C45 O7 H7 109.5 . . ? C46 O11 Gd1 119.07(17) . . ? C46 O12 Gd1 119.76(18) . 2_666 ? Gd1 O13 H13A 114.8 . . ? Gd1 O13 H13B 103.6 . . ? H13A O13 H13B 115.7 . . ? C1 N1 C19 123.0(2) . . ? C1 N1 Cu1 111.18(19) . . ? C19 N1 Cu1 125.61(19) . . ? C2 N2 C3 122.9(3) . . ? C2 N2 Cu1 110.65(19) . . ? C3 N2 Cu1 126.2(2) . . ? C9 N3 C10 119.0(3) . . ? C9 N3 Cu1 124.5(2) . . ? C10 N3 Cu1 116.4(2) . . ? C13 N4 C12 118.5(3) . . ? C13 N4 Cu1 125.1(2) . . ? C12 N4 Cu1 116.1(2) . . ? C20 N5 C38 121.3(3) . . ? C20 N5 Cu2 111.6(2) . . ? C38 N5 Cu2 126.4(2) . . ? C21 N6 C22 123.5(3) . . ? C21 N6 Cu2 109.9(2) . . ? C22 N6 Cu2 126.6(2) . . ? C28 N7 C29 119.2(3) . . ? C28 N7 Cu2 124.4(2) . . ? C29 N7 Cu2 116.4(2) . . ? C32 N8 C31 119.4(3) . . ? C32 N8 Cu2 125.4(3) . . ? C31 N8 Cu2 114.6(2) . . ? O1 C1 N1 128.7(3) . . ? O1 C1 C2 116.1(2) . . ? N1 C1 C2 115.2(2) . . ? O2 C2 N2 128.7(3) . . ? O2 C2 C1 116.4(2) . . ? N2 C2 C1 114.9(2) . . ? C4 C3 N2 122.1(3) . . ? C4 C3 C8 118.0(3) . . ? N2 C3 C8 119.7(3) . . ? C5 C4 C3 120.6(4) . . ? C5 C4 H4 119.7 . . ? C3 C4 H4 119.7 . . ? C6 C5 C4 121.3(4) . . ? C6 C5 H5 119.4 . . ? C4 C5 H5 119.4 . . ? C7 C6 C5 119.1(4) . . ? C7 C6 H6 120.4 . . ? C5 C6 H6 120.4 . . ? C6 C7 C8 121.7(4) . . ? C6 C7 H7A 119.1 . . ? C8 C7 H7A 119.1 . . ? C7 C8 C3 119.2(3) . . ? C7 C8 C9 115.2(3) . . ? C3 C8 C9 125.5(3) . . ? N3 C9 C8 127.4(3) . . ? N3 C9 H9 116.3 . . ? C8 C9 H9 116.3 . . ? N3 C10 C11 113.6(3) . . ? N3 C10 H10A 108.8 . . ? C11 C10 H10A 108.8 . . ? N3 C10 H10B 108.8 . . ? C11 C10 H10B 108.8 . . ? H10A C10 H10B 107.7 . . ? C12 C11 C10 115.7(3) . . ? C12 C11 H11A 108.4 . . ? C10 C11 H11A 108.4 . . ? C12 C11 H11B 108.4 . . ? C10 C11 H11B 108.4 . . ? H11A C11 H11B 107.4 . . ? N4 C12 C11 111.3(3) . . ? N4 C12 H12A 109.4 . . ? C11 C12 H12A 109.4 . . ? N4 C12 H12B 109.4 . . ? C11 C12 H12B 109.4 . . ? H12A C12 H12B 108.0 . . ? N4 C13 C14 126.5(3) . . ? N4 C13 H13 116.8 . . ? C14 C13 H13 116.8 . . ? C15 C14 C19 119.3(3) . . ? C15 C14 C13 114.8(3) . . ? C19 C14 C13 125.7(3) . . ? C16 C15 C14 121.4(3) . . ? C16 C15 H15 119.3 . . ? C14 C15 H15 119.3 . . ? C15 C16 C17 119.1(4) . . ? C15 C16 H16 120.4 . . ? C17 C16 H16 120.4 . . ? C18 C17 C16 120.9(4) . . ? C18 C17 H17 119.5 . . ? C16 C17 H17 119.5 . . ? C17 C18 C19 121.0(3) . . ? C17 C18 H18 119.5 . . ? C19 C18 H18 119.5 . . ? C18 C19 N1 123.0(3) . . ? C18 C19 C14 117.9(3) . . ? N1 C19 C14 119.0(3) . . ? O3 C20 N5 128.5(3) . . ? O3 C20 C21 116.6(3) . . ? N5 C20 C21 114.8(3) . . ? O4 C21 N6 129.2(3) . . ? O4 C21 C20 115.2(3) . . ? N6 C21 C20 115.6(3) . . ? C23 C22 N6 123.8(3) . . ? C23 C22 C27 117.3(3) . . ? N6 C22 C27 118.9(3) . . ? C24 C23 C22 121.9(3) . . ? C24 C23 H23 119.1 . . ? C22 C23 H23 119.1 . . ? C25 C24 C23 120.8(4) . . ? C25 C24 H24 119.6 . . ? C23 C24 H24 119.6 . . ? C26 C25 C24 118.8(4) . . ? C26 C25 H25 120.6 . . ? C24 C25 H25 120.6 . . ? C25 C26 C27 121.9(3) . . ? C25 C26 H26 119.1 . . ? C27 C26 H26 119.1 . . ? C26 C27 C22 119.4(3) . . ? C26 C27 C28 114.3(3) . . ? C22 C27 C28 126.3(3) . . ? N7 C28 C27 128.1(3) . . ? N7 C28 H28 115.9 . . ? C27 C28 H28 115.9 . . ? N7 C29 C30 113.0(3) . . ? N7 C29 H29A 109.0 . . ? C30 C29 H29A 109.0 . . ? N7 C29 H29B 109.0 . . ? C30 C29 H29B 109.0 . . ? H29A C29 H29B 107.8 . . ? C29 C30 C31 117.0(3) . . ? C29 C30 H30A 108.0 . . ? C31 C30 H30A 108.0 . . ? C29 C30 H30B 108.0 . . ? C31 C30 H30B 108.0 . . ? H30A C30 H30B 107.3 . . ? N8 C31 C30 114.0(4) . . ? N8 C31 H31A 108.7 . . ? C30 C31 H31A 108.7 . . ? N8 C31 H31B 108.7 . . ? C30 C31 H31B 108.7 . . ? H31A C31 H31B 107.6 . . ? N8 C32 C33 126.3(3) . . ? N8 C32 H32 116.8 . . ? C33 C32 H32 116.8 . . ? C34 C33 C38 118.2(4) . . ? C34 C33 C32 117.1(3) . . ? C38 C33 C32 124.7(3) . . ? C35 C34 C33 121.7(4) . . ? C35 C34 H34 119.2 . . ? C33 C34 H34 119.2 . . ? C34 C35 C36 119.6(4) . . ? C34 C35 H35 120.2 . . ? C36 C35 H35 120.2 . . ? C35 C36 C37 120.5(4) . . ? C35 C36 H36 119.7 . . ? C37 C36 H36 119.7 . . ? C36 C37 C38 120.3(4) . . ? C36 C37 H37 119.9 . . ? C38 C37 H37 119.9 . . ? C37 C38 C33 119.6(3) . . ? C37 C38 N5 121.2(3) . . ? C33 C38 N5 119.3(3) . . ? O5 C39 O6 120.7(3) . . ? O5 C39 C40 121.3(3) . . ? O6 C39 C40 117.9(3) . . ? O5 C39 Gd1 58.67(16) . . ? O6 C39 Gd1 62.93(16) . . ? C40 C39 Gd1 169.4(2) . . ? C41 C40 C45 119.3(3) . . ? C41 C40 C39 120.8(3) . . ? C45 C40 C39 119.9(3) . . ? C42 C41 C40 120.4(3) . . ? C42 C41 H41 119.8 . . ? C40 C41 H41 119.8 . . ? C41 C42 C43 119.1(3) . . ? C41 C42 S1 123.4(3) . . ? C43 C42 S1 117.5(3) . . ? C44 C43 C42 121.8(3) . . ? C44 C43 H43 119.1 . . ? C42 C43 H43 119.1 . . ? C43 C44 C45 119.7(4) . . ? C43 C44 H44 120.2 . . ? C45 C44 H44 120.2 . . ? O7 C45 C44 117.9(4) . . ? O7 C45 C40 122.3(3) . . ? C44 C45 C40 119.7(4) . . ? O11 C46 O12 126.4(3) . . ? O11 C46 C46 116.6(3) . 2_666 ? O12 C46 C46 117.0(3) . 2_666 ? 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 O12 Gd1 O1 C1 50.7(2) 2_666 . . . ? O2 Gd1 O1 C1 6.6(2) . . . . ? O3 Gd1 O1 C1 160.9(2) . . . . ? O11 Gd1 O1 C1 171.73(19) . . . . ? O4 Gd1 O1 C1 -134.1(2) . . . . ? O5 Gd1 O1 C1 -58.6(2) . . . . ? O13 Gd1 O1 C1 86.4(2) . . . . ? O6 Gd1 O1 C1 -68.7(2) . . . . ? C39 Gd1 O1 C1 -66.6(2) . . . . ? O12 Gd1 O2 C2 -163.2(2) 2_666 . . . ? O3 Gd1 O2 C2 -51.6(3) . . . . ? O1 Gd1 O2 C2 -13.5(2) . . . . ? O11 Gd1 O2 C2 -179.6(2) . . . . ? O4 Gd1 O2 C2 48.0(3) . . . . ? O5 Gd1 O2 C2 119.4(2) . . . . ? O13 Gd1 O2 C2 -92.6(2) . . . . ? O6 Gd1 O2 C2 68.5(2) . . . . ? C39 Gd1 O2 C2 94.3(2) . . . . ? O12 Gd1 O3 C20 -114.2(2) 2_666 . . . ? O2 Gd1 O3 C20 147.7(2) . . . . ? O1 Gd1 O3 C20 112.4(2) . . . . ? O11 Gd1 O3 C20 -61.4(2) . . . . ? O4 Gd1 O3 C20 19.2(2) . . . . ? O5 Gd1 O3 C20 -18.9(3) . . . . ? O13 Gd1 O3 C20 -170.5(2) . . . . ? O6 Gd1 O3 C20 49.4(2) . . . . ? C39 Gd1 O3 C20 17.5(3) . . . . ? O12 Gd1 O4 C21 82.9(2) 2_666 . . . ? O2 Gd1 O4 C21 -145.9(2) . . . . ? O3 Gd1 O4 C21 -14.4(2) . . . . ? O1 Gd1 O4 C21 -92.0(2) . . . . ? O11 Gd1 O4 C21 60.7(2) . . . . ? O5 Gd1 O4 C21 140.3(2) . . . . ? O13 Gd1 O4 C21 -27.8(3) . . . . ? O6 Gd1 O4 C21 -167.2(2) . . . . ? C39 Gd1 O4 C21 164.2(2) . . . . ? O12 Gd1 O5 C39 -154.7(2) 2_666 . . . ? O2 Gd1 O5 C39 -75.16(19) . . . . ? O3 Gd1 O5 C39 95.7(2) . . . . ? O1 Gd1 O5 C39 -18.4(2) . . . . ? O11 Gd1 O5 C39 136.2(2) . . . . ? O4 Gd1 O5 C39 60.97(19) . . . . ? O13 Gd1 O5 C39 -132.67(19) . . . . ? O6 Gd1 O5 C39 -5.97(17) . . . . ? O12 Gd1 O6 C39 41.84(19) 2_666 . . . ? O2 Gd1 O6 C39 105.60(18) . . . . ? O3 Gd1 O6 C39 -120.56(18) . . . . ? O1 Gd1 O6 C39 175.45(18) . . . . ? O11 Gd1 O6 C39 -36.79(19) . . . . ? O4 Gd1 O6 C39 -90.41(18) . . . . ? O5 Gd1 O6 C39 5.78(17) . . . . ? O13 Gd1 O6 C39 135.39(18) . . . . ? O12 Gd1 O11 C46 -6.3(2) 2_666 . . . ? O2 Gd1 O11 C46 11.2(3) . . . . ? O3 Gd1 O11 C46 -133.5(2) . . . . ? O1 Gd1 O11 C46 -144.8(2) . . . . ? O4 Gd1 O11 C46 157.5(2) . . . . ? O5 Gd1 O11 C46 74.7(2) . . . . ? O13 Gd1 O11 C46 -67.3(2) . . . . ? O6 Gd1 O11 C46 107.7(2) . . . . ? C39 Gd1 O11 C46 92.1(2) . . . . ? N3 Cu1 N1 C1 -83.0(6) . . . . ? N2 Cu1 N1 C1 7.2(2) . . . . ? N4 Cu1 N1 C1 163.0(2) . . . . ? N3 Cu1 N1 C19 91.8(6) . . . . ? N2 Cu1 N1 C19 -177.9(3) . . . . ? N4 Cu1 N1 C19 -22.2(3) . . . . ? N3 Cu1 N2 C2 156.4(2) . . . . ? N1 Cu1 N2 C2 -12.6(2) . . . . ? N4 Cu1 N2 C2 -101.5(3) . . . . ? N3 Cu1 N2 C3 -17.7(3) . . . . ? N1 Cu1 N2 C3 173.3(3) . . . . ? N4 Cu1 N2 C3 84.4(4) . . . . ? N1 Cu1 N3 C9 102.4(6) . . . . ? N2 Cu1 N3 C9 12.9(3) . . . . ? N4 Cu1 N3 C9 -143.4(3) . . . . ? N1 Cu1 N3 C10 -73.2(7) . . . . ? N2 Cu1 N3 C10 -162.7(3) . . . . ? N4 Cu1 N3 C10 41.0(3) . . . . ? N3 Cu1 N4 C13 -165.2(3) . . . . ? N1 Cu1 N4 C13 4.8(3) . . . . ? N2 Cu1 N4 C13 92.3(4) . . . . ? N3 Cu1 N4 C12 21.8(3) . . . . ? N1 Cu1 N4 C12 -168.3(2) . . . . ? N2 Cu1 N4 C12 -80.8(4) . . . . ? N7 Cu2 N5 C20 107.8(4) . . . . ? N6 Cu2 N5 C20 13.0(2) . . . . ? N8 Cu2 N5 C20 -144.2(2) . . . . ? N7 Cu2 N5 C38 -81.7(5) . . . . ? N6 Cu2 N5 C38 -176.4(3) . . . . ? N8 Cu2 N5 C38 26.3(3) . . . . ? N7 Cu2 N6 C21 -173.4(2) . . . . ? N5 Cu2 N6 C21 -8.9(2) . . . . ? N8 Cu2 N6 C21 76.7(4) . . . . ? N7 Cu2 N6 C22 8.5(3) . . . . ? N5 Cu2 N6 C22 173.0(3) . . . . ? N8 Cu2 N6 C22 -101.4(4) . . . . ? N5 Cu2 N7 C28 -97.5(5) . . . . ? N6 Cu2 N7 C28 -4.0(3) . . . . ? N8 Cu2 N7 C28 154.6(3) . . . . ? N5 Cu2 N7 C29 81.2(5) . . . . ? N6 Cu2 N7 C29 174.7(3) . . . . ? N8 Cu2 N7 C29 -26.7(3) . . . . ? N7 Cu2 N8 C32 154.4(3) . . . . ? N5 Cu2 N8 C32 -10.9(3) . . . . ? N6 Cu2 N8 C32 -95.3(4) . . . . ? N7 Cu2 N8 C31 -34.5(3) . . . . ? N5 Cu2 N8 C31 160.2(3) . . . . ? N6 Cu2 N8 C31 75.8(4) . . . . ? Gd1 O1 C1 N1 175.7(2) . . . . ? Gd1 O1 C1 C2 -0.7(3) . . . . ? C19 N1 C1 O1 7.5(5) . . . . ? Cu1 N1 C1 O1 -177.5(2) . . . . ? C19 N1 C1 C2 -176.0(3) . . . . ? Cu1 N1 C1 C2 -1.0(3) . . . . ? Gd1 O2 C2 N2 -160.5(2) . . . . ? Gd1 O2 C2 C1 18.2(3) . . . . ? C3 N2 C2 O2 8.0(5) . . . . ? Cu1 N2 C2 O2 -166.4(3) . . . . ? C3 N2 C2 C1 -170.8(3) . . . . ? Cu1 N2 C2 C1 14.9(3) . . . . ? O1 C1 C2 O2 -11.6(4) . . . . ? N1 C1 C2 O2 171.5(3) . . . . ? O1 C1 C2 N2 167.3(3) . . . . ? N1 C1 C2 N2 -9.7(4) . . . . ? C2 N2 C3 C4 22.3(5) . . . . ? Cu1 N2 C3 C4 -164.3(3) . . . . ? C2 N2 C3 C8 -162.3(3) . . . . ? Cu1 N2 C3 C8 11.1(5) . . . . ? N2 C3 C4 C5 177.1(5) . . . . ? C8 C3 C4 C5 1.7(7) . . . . ? C3 C4 C5 C6 0.0(9) . . . . ? C4 C5 C6 C7 -0.9(10) . . . . ? C5 C6 C7 C8 0.1(10) . . . . ? C6 C7 C8 C3 1.6(8) . . . . ? C6 C7 C8 C9 178.3(5) . . . . ? C4 C3 C8 C7 -2.4(6) . . . . ? N2 C3 C8 C7 -178.0(4) . . . . ? C4 C3 C8 C9 -178.7(4) . . . . ? N2 C3 C8 C9 5.7(6) . . . . ? C10 N3 C9 C8 173.6(4) . . . . ? Cu1 N3 C9 C8 -1.9(6) . . . . ? C7 C8 C9 N3 172.6(4) . . . . ? C3 C8 C9 N3 -11.0(7) . . . . ? C9 N3 C10 C11 119.9(4) . . . . ? Cu1 N3 C10 C11 -64.2(4) . . . . ? N3 C10 C11 C12 16.3(5) . . . . ? C13 N4 C12 C11 118.3(4) . . . . ? Cu1 N4 C12 C11 -68.1(4) . . . . ? C10 C11 C12 N4 50.4(5) . . . . ? C12 N4 C13 C14 -177.2(3) . . . . ? Cu1 N4 C13 C14 9.9(5) . . . . ? N4 C13 C14 C15 163.6(3) . . . . ? N4 C13 C14 C19 -12.0(5) . . . . ? C19 C14 C15 C16 3.6(6) . . . . ? C13 C14 C15 C16 -172.3(4) . . . . ? C14 C15 C16 C17 0.5(7) . . . . ? C15 C16 C17 C18 -2.6(8) . . . . ? C16 C17 C18 C19 0.5(7) . . . . ? C17 C18 C19 N1 -179.9(4) . . . . ? C17 C18 C19 C14 3.6(6) . . . . ? C1 N1 C19 C18 23.0(5) . . . . ? Cu1 N1 C19 C18 -151.3(3) . . . . ? C1 N1 C19 C14 -160.5(3) . . . . ? Cu1 N1 C19 C14 25.2(4) . . . . ? C15 C14 C19 C18 -5.5(5) . . . . ? C13 C14 C19 C18 169.9(3) . . . . ? C15 C14 C19 N1 177.8(3) . . . . ? C13 C14 C19 N1 -6.8(5) . . . . ? Gd1 O3 C20 N5 159.4(3) . . . . ? Gd1 O3 C20 C21 -22.2(3) . . . . ? C38 N5 C20 O3 -6.7(5) . . . . ? Cu2 N5 C20 O3 164.4(3) . . . . ? C38 N5 C20 C21 174.8(3) . . . . ? Cu2 N5 C20 C21 -14.1(3) . . . . ? Gd1 O4 C21 N6 -170.8(2) . . . . ? Gd1 O4 C21 C20 9.5(3) . . . . ? C22 N6 C21 O4 2.0(5) . . . . ? Cu2 N6 C21 O4 -176.2(3) . . . . ? C22 N6 C21 C20 -178.3(3) . . . . ? Cu2 N6 C21 C20 3.6(3) . . . . ? O3 C20 C21 O4 8.2(4) . . . . ? N5 C20 C21 O4 -173.1(3) . . . . ? O3 C20 C21 N6 -171.6(3) . . . . ? N5 C20 C21 N6 7.1(4) . . . . ? C21 N6 C22 C23 -5.4(5) . . . . ? Cu2 N6 C22 C23 172.4(3) . . . . ? C21 N6 C22 C27 174.8(3) . . . . ? Cu2 N6 C22 C27 -7.4(4) . . . . ? N6 C22 C23 C24 179.1(4) . . . . ? C27 C22 C23 C24 -1.1(6) . . . . ? C22 C23 C24 C25 0.1(7) . . . . ? C23 C24 C25 C26 0.8(7) . . . . ? C24 C25 C26 C27 -0.8(7) . . . . ? C25 C26 C27 C22 -0.1(6) . . . . ? C25 C26 C27 C28 -179.3(4) . . . . ? C23 C22 C27 C26 1.1(5) . . . . ? N6 C22 C27 C26 -179.1(3) . . . . ? C23 C22 C27 C28 -179.9(3) . . . . ? N6 C22 C27 C28 -0.1(5) . . . . ? C29 N7 C28 C27 179.8(4) . . . . ? Cu2 N7 C28 C27 -1.6(6) . . . . ? C26 C27 C28 N7 -175.8(4) . . . . ? C22 C27 C28 N7 5.1(6) . . . . ? C28 N7 C29 C30 -114.7(4) . . . . ? Cu2 N7 C29 C30 66.6(4) . . . . ? N7 C29 C30 C31 -39.9(6) . . . . ? C32 N8 C31 C30 -123.4(4) . . . . ? Cu2 N8 C31 C30 64.9(4) . . . . ? C29 C30 C31 N8 -27.3(6) . . . . ? C31 N8 C32 C33 -176.2(3) . . . . ? Cu2 N8 C32 C33 -5.5(5) . . . . ? N8 C32 C33 C34 -166.9(3) . . . . ? N8 C32 C33 C38 13.5(6) . . . . ? C38 C33 C34 C35 -3.2(5) . . . . ? C32 C33 C34 C35 177.2(4) . . . . ? C33 C34 C35 C36 -0.7(6) . . . . ? C34 C35 C36 C37 3.1(7) . . . . ? C35 C36 C37 C38 -1.4(6) . . . . ? C36 C37 C38 C33 -2.6(6) . . . . ? C36 C37 C38 N5 179.0(4) . . . . ? C34 C33 C38 C37 4.8(5) . . . . ? C32 C33 C38 C37 -175.6(3) . . . . ? C34 C33 C38 N5 -176.8(3) . . . . ? C32 C33 C38 N5 2.8(5) . . . . ? C20 N5 C38 C37 -37.5(5) . . . . ? Cu2 N5 C38 C37 152.8(3) . . . . ? C20 N5 C38 C33 144.1(3) . . . . ? Cu2 N5 C38 C33 -25.6(4) . . . . ? Gd1 O5 C39 O6 11.0(3) . . . . ? Gd1 O5 C39 C40 -167.6(3) . . . . ? Gd1 O6 C39 O5 -10.5(3) . . . . ? Gd1 O6 C39 C40 168.1(2) . . . . ? O12 Gd1 C39 O5 25.0(2) 2_666 . . . ? O2 Gd1 C39 O5 101.64(19) . . . . ? O3 Gd1 C39 O5 -110.7(2) . . . . ? O1 Gd1 C39 O5 164.93(18) . . . . ? O11 Gd1 C39 O5 -42.71(19) . . . . ? O4 Gd1 C39 O5 -112.3(2) . . . . ? O13 Gd1 C39 O5 86.6(3) . . . . ? O6 Gd1 C39 O5 169.4(3) . . . . ? O12 Gd1 C39 O6 -144.46(17) 2_666 . . . ? O2 Gd1 C39 O6 -67.79(17) . . . . ? O3 Gd1 C39 O6 79.9(2) . . . . ? O1 Gd1 C39 O6 -4.50(18) . . . . ? O11 Gd1 C39 O6 147.86(17) . . . . ? O4 Gd1 C39 O6 78.23(18) . . . . ? O5 Gd1 C39 O6 -169.4(3) . . . . ? O13 Gd1 C39 O6 -82.8(3) . . . . ? O12 Gd1 C39 C40 118.2(12) 2_666 . . . ? O2 Gd1 C39 C40 -165.1(12) . . . . ? O3 Gd1 C39 C40 -17.4(13) . . . . ? O1 Gd1 C39 C40 -101.8(12) . . . . ? O11 Gd1 C39 C40 50.5(12) . . . . ? O4 Gd1 C39 C40 -19.1(12) . . . . ? O5 Gd1 C39 C40 93.2(12) . . . . ? O13 Gd1 C39 C40 179.8(11) . . . . ? O6 Gd1 C39 C40 -97.3(13) . . . . ? O5 C39 C40 C41 -13.6(5) . . . . ? O6 C39 C40 C41 167.8(3) . . . . ? Gd1 C39 C40 C41 -100.4(12) . . . . ? O5 C39 C40 C45 165.0(3) . . . . ? O6 C39 C40 C45 -13.6(4) . . . . ? Gd1 C39 C40 C45 78.2(13) . . . . ? C45 C40 C41 C42 2.2(5) . . . . ? C39 C40 C41 C42 -179.2(3) . . . . ? C40 C41 C42 C43 -0.5(5) . . . . ? C40 C41 C42 S1 -179.9(2) . . . . ? O9 S1 C42 C41 -20.2(4) . . . . ? O10 S1 C42 C41 101.1(3) . . . . ? O8 S1 C42 C41 -140.0(3) . . . . ? O9 S1 C42 C43 160.4(3) . . . . ? O10 S1 C42 C43 -78.3(3) . . . . ? O8 S1 C42 C43 40.6(3) . . . . ? C41 C42 C43 C44 -1.4(6) . . . . ? S1 C42 C43 C44 178.1(4) . . . . ? C42 C43 C44 C45 1.5(7) . . . . ? C43 C44 C45 O7 -179.7(4) . . . . ? C43 C44 C45 C40 0.2(7) . . . . ? C41 C40 C45 O7 177.8(3) . . . . ? C39 C40 C45 O7 -0.8(5) . . . . ? C41 C40 C45 C44 -2.0(5) . . . . ? C39 C40 C45 C44 179.3(4) . . . . ? Gd1 O11 C46 O12 -174.3(2) . . . . ? Gd1 O11 C46 C46 6.0(4) . . . 2_666 ? Gd1 O12 C46 O11 -174.0(2) 2_666 . . . ? Gd1 O12 C46 C46 5.7(4) 2_666 . . 2_666 ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.490 _refine_diff_density_min -1.147 _refine_diff_density_rms 0.074 data_090405c _database_code_depnum_ccdc_archive 'CCDC 767162' #TrackingRef '- 080925a.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C90 H76 Cu6 N16 O22 S2' _chemical_formula_weight 2179.03 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' 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.3201 1.2651 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.7031(14) _cell_length_b 12.7099(14) _cell_length_c 14.5477(16) _cell_angle_alpha 88.314(2) _cell_angle_beta 67.466(2) _cell_angle_gamma 83.157(2) _cell_volume 2153.7(4) _cell_formula_units_Z 1 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 3275 _cell_measurement_theta_min 2.51 _cell_measurement_theta_max 26.67 _exptl_crystal_description BLOCK _exptl_crystal_colour BLUE _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas NONE _exptl_crystal_density_diffrn 1.702 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1126 _exptl_absorpt_coefficient_mu 1.592 _exptl_absorpt_correction_type MULTI-SCAN _exptl_absorpt_correction_T_min 0.608828 _exptl_absorpt_correction_T_max 1.000000 _exptl_absorpt_process_details SADABS _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 '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 11003 _diffrn_reflns_av_R_equivalents 0.0242 _diffrn_reflns_av_sigmaI/netI 0.0526 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 25.03 _reflns_number_total 7562 _reflns_number_gt 5280 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0684P)^2^+4.5938P] 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 7562 _refine_ls_number_parameters 618 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0803 _refine_ls_R_factor_gt 0.0495 _refine_ls_wR_factor_ref 0.1475 _refine_ls_wR_factor_gt 0.1274 _refine_ls_goodness_of_fit_ref 1.022 _refine_ls_restrained_S_all 1.022 _refine_ls_shift/su_max 0.000 _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 Cu1 Cu 0.36005(5) 0.35594(5) 0.15713(5) 0.03514(18) Uani 1 1 d . . . Cu2 Cu 0.28316(6) 0.02974(5) -0.00896(5) 0.03724(19) Uani 1 1 d . . . Cu3 Cu 0.24966(5) 0.49752(5) 0.52901(5) 0.03617(19) Uani 1 1 d . . . S1 S 0.83322(14) 0.75042(12) 0.12640(14) 0.0558(4) Uani 1 1 d . . . O1 O 0.2441(3) 0.2571(3) 0.1869(3) 0.0442(10) Uani 1 1 d . . . O2 O 0.4374(3) 0.2629(3) 0.0409(3) 0.0398(9) Uani 1 1 d . . . O3 O 0.2497(3) 0.4504(3) 0.2617(3) 0.0362(8) Uani 1 1 d . . . O4 O 0.4090(3) 0.3139(3) 0.2897(3) 0.0440(9) Uani 1 1 d . . . O5 O 0.4876(3) 0.4378(3) 0.1018(3) 0.0391(9) Uani 1 1 d . . . O6 O 0.4565(3) 0.5570(3) 0.2227(3) 0.0476(10) Uani 1 1 d . . . O7 O 0.7811(6) 0.8478(4) 0.1098(5) 0.110(2) Uani 1 1 d . . . O8 O 0.7998(8) 0.7301(5) 0.2297(5) 0.133(3) Uani 1 1 d . . . O9 O 0.9522(5) 0.7360(7) 0.0838(8) 0.186(5) Uani 1 1 d . . . O10 O 0.6847(3) 0.4027(3) -0.0378(3) 0.0469(10) Uani 1 1 d . . . H10 H 0.6157 0.3988 -0.0097 0.070 Uiso 1 1 calc R . . N1 N 0.2099(4) 0.1066(3) 0.1198(3) 0.0352(10) Uani 1 1 d . . . N2 N 0.4092(4) 0.1162(3) -0.0352(3) 0.0335(10) Uani 1 1 d . . . N3 N 0.3825(5) -0.0835(4) -0.1008(4) 0.0507(13) Uani 1 1 d . . . N4 N 0.1516(5) -0.0454(4) 0.0142(4) 0.0530(13) Uani 1 1 d . . . N5 N 0.2058(3) 0.5255(3) 0.4164(3) 0.0338(10) Uani 1 1 d . . . N6 N 0.3686(4) 0.3922(3) 0.4441(3) 0.0364(10) Uani 1 1 d . . . N7 N 0.3212(4) 0.5048(4) 0.6248(3) 0.0420(11) Uani 1 1 d . . . N8 N 0.1007(4) 0.5572(4) 0.6242(3) 0.0412(11) Uani 1 1 d . . . C1 C 0.2681(4) 0.1846(4) 0.1215(4) 0.0351(12) Uani 1 1 d . . . C2 C 0.3811(4) 0.1894(4) 0.0346(4) 0.0341(12) Uani 1 1 d . . . C3 C 0.5123(4) 0.1096(4) -0.1205(4) 0.0344(12) Uani 1 1 d . . . C4 C 0.5827(6) 0.1886(5) -0.1489(5) 0.0576(17) Uani 1 1 d . . . H4 H 0.5617 0.2512 -0.1114 0.069 Uiso 1 1 calc R . . C5 C 0.6840(6) 0.1772(6) -0.2317(5) 0.069(2) Uani 1 1 d . . . H5 H 0.7302 0.2319 -0.2484 0.083 Uiso 1 1 calc R . . C6 C 0.7173(6) 0.0875(6) -0.2894(5) 0.0627(19) Uani 1 1 d . . . H6 H 0.7866 0.0797 -0.3441 0.075 Uiso 1 1 calc R . . C7 C 0.6480(6) 0.0107(5) -0.2654(5) 0.0589(17) Uani 1 1 d . . . H7 H 0.6701 -0.0500 -0.3055 0.071 Uiso 1 1 calc R . . C8 C 0.5442(5) 0.0177(4) -0.1830(4) 0.0434(14) Uani 1 1 d . . . C9 C 0.4836(6) -0.0745(5) -0.1649(5) 0.0545(16) Uani 1 1 d . . . H9 H 0.5222 -0.1342 -0.2042 0.065 Uiso 1 1 calc R . . C10 C 0.3413(6) -0.1905(5) -0.0861(6) 0.0648(19) Uani 1 1 d . . . H10A H 0.4023 -0.2419 -0.1281 0.078 Uiso 1 1 calc R . . H10B H 0.3236 -0.2107 -0.0174 0.078 Uiso 1 1 calc R . . C11 C 0.2376(6) -0.1934(5) -0.1100(6) 0.067(2) Uani 1 1 d . . . H11A H 0.2015 -0.2557 -0.0801 0.081 Uiso 1 1 calc R . . H11B H 0.2620 -0.2011 -0.1815 0.081 Uiso 1 1 calc R . . C12 C 0.1491(6) -0.0975(5) -0.0754(5) 0.0614(18) Uani 1 1 d . . . H12A H 0.1632 -0.0469 -0.1289 0.074 Uiso 1 1 calc R . . H12B H 0.0734 -0.1189 -0.0599 0.074 Uiso 1 1 calc R . . C13 C 0.0661(6) -0.0495(5) 0.0971(5) 0.0593(18) Uani 1 1 d . . . H13 H 0.0109 -0.0921 0.0982 0.071 Uiso 1 1 calc R . . C14 C 0.0465(5) 0.0053(4) 0.1893(4) 0.0416(13) Uani 1 1 d . . . C15 C -0.0507(5) -0.0192(5) 0.2702(5) 0.0545(16) Uani 1 1 d . . . H15 H -0.0932 -0.0702 0.2619 0.065 Uiso 1 1 calc R . . C16 C -0.0842(6) 0.0288(6) 0.3595(6) 0.075(2) Uani 1 1 d . . . H16 H -0.1502 0.0125 0.4115 0.090 Uiso 1 1 calc R . . C17 C -0.0207(7) 0.1017(6) 0.3735(6) 0.085(3) Uani 1 1 d . . . H17 H -0.0416 0.1327 0.4360 0.102 Uiso 1 1 calc R . . C18 C 0.0750(6) 0.1299(5) 0.2947(5) 0.069(2) Uani 1 1 d . . . H18 H 0.1168 0.1803 0.3052 0.083 Uiso 1 1 calc R . . C19 C 0.1096(5) 0.0842(4) 0.2001(4) 0.0404(13) Uani 1 1 d . . . C20 C 0.2652(4) 0.4593(4) 0.3413(4) 0.0317(11) Uani 1 1 d . . . C21 C 0.3572(4) 0.3806(4) 0.3568(4) 0.0319(11) Uani 1 1 d . . . C22 C 0.4522(5) 0.3307(5) 0.4696(4) 0.0450(14) Uani 1 1 d . . . C23 C 0.5157(6) 0.2386(6) 0.4171(5) 0.072(2) Uani 1 1 d . . . H23 H 0.4997 0.2142 0.3648 0.086 Uiso 1 1 calc R . . C24 C 0.6010(8) 0.1836(7) 0.4411(6) 0.100(3) Uani 1 1 d . . . H24 H 0.6420 0.1230 0.4045 0.120 Uiso 1 1 calc R . . C25 C 0.6270(7) 0.2167(8) 0.5189(6) 0.098(3) Uani 1 1 d . . . H25 H 0.6871 0.1808 0.5330 0.117 Uiso 1 1 calc R . . C26 C 0.5619(6) 0.3041(6) 0.5749(5) 0.0662(19) Uani 1 1 d . . . H26 H 0.5773 0.3259 0.6285 0.079 Uiso 1 1 calc R . . C27 C 0.4734(5) 0.3606(5) 0.5530(4) 0.0449(14) Uani 1 1 d . . . C28 C 0.4114(5) 0.4471(5) 0.6214(4) 0.0440(14) Uani 1 1 d . . . H28 H 0.4408 0.4625 0.6683 0.053 Uiso 1 1 calc R . . C29 C 0.2753(6) 0.5909(5) 0.6989(5) 0.0657(19) Uani 1 1 d . . . H29A H 0.2814 0.6579 0.6646 0.079 Uiso 1 1 calc R . . H29B H 0.3225 0.5888 0.7380 0.079 Uiso 1 1 calc R . . C30 C 0.1548(6) 0.5878(7) 0.7672(5) 0.071(2) Uani 1 1 d . . . H30A H 0.1200 0.6602 0.7859 0.085 Uiso 1 1 calc R . . H30B H 0.1547 0.5525 0.8273 0.085 Uiso 1 1 calc R . . C31 C 0.0791(6) 0.5335(6) 0.7290(4) 0.0592(17) Uani 1 1 d . . . H31A H 0.0927 0.4575 0.7359 0.071 Uiso 1 1 calc R . . H31B H -0.0007 0.5563 0.7694 0.071 Uiso 1 1 calc R . . C32 C 0.0194(5) 0.6041(4) 0.6016(4) 0.0453(15) Uani 1 1 d . . . H32 H -0.0502 0.6223 0.6543 0.054 Uiso 1 1 calc R . . C33 C 0.0233(5) 0.6316(4) 0.5042(4) 0.0375(12) Uani 1 1 d . . . C34 C -0.0728(5) 0.6967(4) 0.5017(5) 0.0504(15) Uani 1 1 d . . . H34 H -0.1335 0.7176 0.5611 0.060 Uiso 1 1 calc R . . C35 C -0.0789(6) 0.7304(5) 0.4124(6) 0.0615(19) Uani 1 1 d . . . H35 H -0.1435 0.7728 0.4116 0.074 Uiso 1 1 calc R . . C36 C 0.0123(6) 0.7003(5) 0.3240(5) 0.0553(16) Uani 1 1 d . . . H36 H 0.0098 0.7247 0.2638 0.066 Uiso 1 1 calc R . . C37 C 0.1062(5) 0.6350(4) 0.3243(4) 0.0436(14) Uani 1 1 d . . . H37 H 0.1663 0.6150 0.2643 0.052 Uiso 1 1 calc R . . C38 C 0.1130(4) 0.5981(4) 0.4135(4) 0.0342(12) Uani 1 1 d . . . C39 C 0.5171(5) 0.5130(4) 0.1428(4) 0.0356(12) Uani 1 1 d . . . C40 C 0.6367(4) 0.5409(4) 0.0864(4) 0.0321(11) Uani 1 1 d . . . C41 C 0.6738(4) 0.6240(4) 0.1210(4) 0.0357(12) Uani 1 1 d . . . H41 H 0.6226 0.6640 0.1758 0.043 Uiso 1 1 calc R . . C42 C 0.7851(5) 0.6488(4) 0.0758(4) 0.0415(13) Uani 1 1 d . . . C43 C 0.8599(5) 0.5886(5) -0.0042(5) 0.0568(17) Uani 1 1 d . . . H43 H 0.9353 0.6037 -0.0342 0.068 Uiso 1 1 calc R . . C44 C 0.8260(5) 0.5065(5) -0.0412(5) 0.0572(17) Uani 1 1 d . . . H44 H 0.8783 0.4664 -0.0955 0.069 Uiso 1 1 calc R . . C45 C 0.7134(5) 0.4832(4) 0.0027(4) 0.0392(13) Uani 1 1 d . . . O11 O 0.6663(16) 0.9657(12) 0.3023(11) 0.131(4) Uani 0.457(9) 1 d P A 1 O11' O 0.6503(13) 0.9080(10) 0.3712(9) 0.131(4) Uani 0.543(9) 1 d P 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 Cu1 0.0380(4) 0.0364(4) 0.0306(4) -0.0079(3) -0.0093(3) -0.0139(3) Cu2 0.0386(4) 0.0328(3) 0.0431(4) -0.0100(3) -0.0167(3) -0.0086(3) Cu3 0.0392(4) 0.0408(4) 0.0286(4) -0.0054(3) -0.0127(3) -0.0046(3) S1 0.0568(10) 0.0445(9) 0.0801(13) 0.0001(8) -0.0368(9) -0.0223(7) O1 0.044(2) 0.046(2) 0.037(2) -0.0126(18) -0.0046(18) -0.0196(18) O2 0.042(2) 0.039(2) 0.036(2) -0.0100(16) -0.0076(17) -0.0172(17) O3 0.0336(19) 0.045(2) 0.032(2) -0.0073(16) -0.0140(17) -0.0075(16) O4 0.051(2) 0.041(2) 0.038(2) -0.0122(18) -0.0163(19) 0.0035(18) O5 0.040(2) 0.041(2) 0.036(2) -0.0075(16) -0.0101(17) -0.0181(17) O6 0.044(2) 0.053(2) 0.042(2) -0.0172(19) -0.0081(19) -0.0162(19) O7 0.206(7) 0.040(3) 0.159(6) 0.012(3) -0.150(6) -0.021(3) O8 0.259(9) 0.088(4) 0.124(6) 0.023(4) -0.139(6) -0.073(5) O9 0.063(4) 0.158(7) 0.316(12) -0.132(8) -0.031(6) -0.039(4) O10 0.051(2) 0.042(2) 0.045(2) -0.0121(18) -0.012(2) -0.0137(19) N1 0.036(2) 0.032(2) 0.040(3) -0.0035(19) -0.014(2) -0.0113(19) N2 0.034(2) 0.034(2) 0.032(2) -0.0076(19) -0.010(2) -0.0067(18) N3 0.056(3) 0.040(3) 0.061(3) -0.013(2) -0.028(3) -0.006(2) N4 0.055(3) 0.048(3) 0.062(4) -0.009(3) -0.025(3) -0.020(3) N5 0.033(2) 0.036(2) 0.028(2) -0.0057(19) -0.0062(19) -0.0064(19) N6 0.039(2) 0.040(2) 0.033(3) -0.0018(19) -0.018(2) -0.004(2) N7 0.049(3) 0.042(3) 0.038(3) -0.005(2) -0.020(2) -0.006(2) N8 0.046(3) 0.042(3) 0.030(3) -0.007(2) -0.006(2) -0.011(2) C1 0.038(3) 0.037(3) 0.033(3) -0.003(2) -0.013(2) -0.010(2) C2 0.037(3) 0.032(3) 0.037(3) -0.002(2) -0.018(3) -0.008(2) C3 0.037(3) 0.036(3) 0.032(3) -0.001(2) -0.015(2) -0.002(2) C4 0.063(4) 0.050(4) 0.051(4) -0.009(3) -0.008(3) -0.021(3) C5 0.060(4) 0.069(5) 0.061(5) -0.004(4) 0.003(4) -0.027(4) C6 0.057(4) 0.069(5) 0.039(4) 0.003(3) 0.003(3) 0.002(4) C7 0.061(4) 0.059(4) 0.045(4) -0.012(3) -0.010(3) 0.006(3) C8 0.043(3) 0.047(3) 0.037(3) -0.008(3) -0.013(3) -0.001(3) C9 0.061(4) 0.048(4) 0.056(4) -0.014(3) -0.023(4) -0.005(3) C10 0.073(5) 0.034(3) 0.096(6) -0.010(3) -0.040(4) -0.010(3) C11 0.073(5) 0.047(4) 0.093(6) -0.028(4) -0.043(4) -0.007(3) C12 0.064(4) 0.062(4) 0.073(5) -0.008(4) -0.040(4) -0.015(3) C13 0.063(4) 0.052(4) 0.071(5) -0.001(3) -0.029(4) -0.028(3) C14 0.040(3) 0.039(3) 0.047(3) 0.004(3) -0.015(3) -0.013(2) C15 0.045(4) 0.047(4) 0.070(5) 0.005(3) -0.017(3) -0.019(3) C16 0.054(4) 0.067(5) 0.078(5) -0.009(4) 0.011(4) -0.029(4) C17 0.078(5) 0.077(5) 0.069(5) -0.021(4) 0.014(4) -0.032(4) C18 0.065(4) 0.062(4) 0.058(4) -0.017(3) 0.011(4) -0.034(4) C19 0.034(3) 0.038(3) 0.046(3) -0.002(3) -0.011(3) -0.007(2) C20 0.031(3) 0.033(3) 0.028(3) 0.001(2) -0.006(2) -0.011(2) C21 0.032(3) 0.034(3) 0.029(3) -0.002(2) -0.009(2) -0.011(2) C22 0.042(3) 0.052(3) 0.035(3) -0.006(3) -0.010(3) 0.004(3) C23 0.076(5) 0.081(5) 0.060(5) -0.024(4) -0.035(4) 0.026(4) C24 0.115(7) 0.106(7) 0.077(6) -0.034(5) -0.054(6) 0.062(6) C25 0.087(6) 0.134(8) 0.068(5) -0.027(5) -0.044(5) 0.057(6) C26 0.063(4) 0.089(5) 0.054(4) -0.005(4) -0.034(4) 0.006(4) C27 0.045(3) 0.054(4) 0.037(3) 0.002(3) -0.018(3) -0.005(3) C28 0.052(4) 0.051(3) 0.035(3) 0.001(3) -0.021(3) -0.013(3) C29 0.079(5) 0.057(4) 0.073(5) -0.026(4) -0.042(4) -0.002(4) C30 0.075(5) 0.096(6) 0.037(4) -0.027(4) -0.014(4) -0.011(4) C31 0.063(4) 0.078(5) 0.031(3) -0.002(3) -0.009(3) -0.022(4) C32 0.034(3) 0.040(3) 0.048(4) -0.014(3) 0.001(3) -0.009(3) C33 0.037(3) 0.030(3) 0.043(3) -0.004(2) -0.012(3) -0.009(2) C34 0.044(3) 0.040(3) 0.064(4) -0.006(3) -0.017(3) -0.001(3) C35 0.050(4) 0.042(3) 0.097(6) 0.000(4) -0.036(4) 0.001(3) C36 0.065(4) 0.044(3) 0.068(5) 0.006(3) -0.039(4) -0.005(3) C37 0.051(3) 0.037(3) 0.046(4) -0.001(3) -0.020(3) -0.011(3) C38 0.034(3) 0.030(3) 0.042(3) -0.001(2) -0.016(3) -0.008(2) C39 0.042(3) 0.032(3) 0.039(3) 0.001(2) -0.019(3) -0.014(2) C40 0.037(3) 0.030(3) 0.034(3) 0.004(2) -0.015(2) -0.010(2) C41 0.036(3) 0.031(3) 0.041(3) 0.001(2) -0.016(3) -0.005(2) C42 0.045(3) 0.033(3) 0.052(4) 0.005(3) -0.022(3) -0.014(2) C43 0.045(4) 0.061(4) 0.057(4) 0.004(3) -0.006(3) -0.025(3) C44 0.052(4) 0.063(4) 0.041(4) -0.009(3) 0.004(3) -0.020(3) C45 0.045(3) 0.036(3) 0.034(3) 0.000(2) -0.011(3) -0.010(2) O11 0.178(9) 0.088(8) 0.086(8) -0.022(5) 0.008(8) -0.053(7) O11' 0.178(9) 0.088(8) 0.086(8) -0.022(5) 0.008(8) -0.053(7) _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 Cu1 O5 1.926(3) . ? Cu1 O3 1.947(3) . ? Cu1 O2 1.947(3) . ? Cu1 O1 1.963(3) . ? Cu1 O4 2.273(4) . ? Cu2 N4 1.937(5) . ? Cu2 N3 1.958(5) . ? Cu2 N2 1.960(4) . ? Cu2 N1 1.972(4) . ? Cu2 O7 2.393(5) 2_665 ? Cu3 N5 1.934(4) . ? Cu3 N7 1.942(5) . ? Cu3 N6 1.945(4) . ? Cu3 N8 1.946(5) . ? S1 O9 1.388(6) . ? S1 O7 1.392(5) . ? S1 O8 1.421(7) . ? S1 C42 1.781(5) . ? O1 C1 1.268(6) . ? O2 C2 1.267(6) . ? O3 C20 1.258(6) . ? O4 C21 1.236(6) . ? O5 C39 1.304(6) . ? O6 C39 1.226(6) . ? O7 Cu2 2.393(5) 2_665 ? O10 C45 1.347(6) . ? O10 H10 0.8200 . ? N1 C1 1.311(6) . ? N1 C19 1.413(7) . ? N2 C2 1.313(6) . ? N2 C3 1.413(6) . ? N3 C9 1.281(8) . ? N3 C10 1.495(7) . ? N4 C13 1.281(8) . ? N4 C12 1.492(8) . ? N5 C20 1.319(6) . ? N5 C38 1.421(6) . ? N6 C21 1.347(6) . ? N6 C22 1.402(7) . ? N7 C28 1.270(7) . ? N7 C29 1.462(7) . ? N8 C32 1.278(7) . ? N8 C31 1.470(7) . ? C1 C2 1.512(7) . ? C3 C4 1.372(8) . ? C3 C8 1.423(7) . ? C4 C5 1.380(9) . ? C4 H4 0.9300 . ? C5 C6 1.360(9) . ? C5 H5 0.9300 . ? C6 C7 1.342(9) . ? C6 H6 0.9300 . ? C7 C8 1.396(8) . ? C7 H7 0.9300 . ? C8 C9 1.441(8) . ? C9 H9 0.9300 . ? C10 C11 1.491(9) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 C12 1.510(9) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 C14 1.451(9) . ? C13 H13 0.9300 . ? C14 C15 1.401(8) . ? C14 C19 1.404(7) . ? C15 C16 1.342(10) . ? C15 H15 0.9300 . ? C16 C17 1.366(10) . ? C16 H16 0.9300 . ? C17 C18 1.390(9) . ? C17 H17 0.9300 . ? C18 C19 1.394(8) . ? C18 H18 0.9300 . ? C20 C21 1.526(7) . ? C22 C23 1.399(8) . ? C22 C27 1.411(8) . ? C23 C24 1.371(10) . ? C23 H23 0.9300 . ? C24 C25 1.383(11) . ? C24 H24 0.9300 . ? C25 C26 1.378(10) . ? C25 H25 0.9300 . ? C26 C27 1.396(8) . ? C26 H26 0.9300 . ? C27 C28 1.441(8) . ? C28 H28 0.9300 . ? C29 C30 1.476(10) . ? C29 H29A 0.9700 . ? C29 H29B 0.9700 . ? C30 C31 1.517(9) . ? C30 H30A 0.9700 . ? C30 H30B 0.9700 . ? C31 H31A 0.9700 . ? C31 H31B 0.9700 . ? C32 C33 1.433(8) . ? C32 H32 0.9300 . ? C33 C34 1.403(8) . ? C33 C38 1.409(7) . ? C34 C35 1.384(9) . ? C34 H34 0.9300 . ? C35 C36 1.387(9) . ? C35 H35 0.9300 . ? C36 C37 1.372(8) . ? C36 H36 0.9300 . ? C37 C38 1.396(8) . ? C37 H37 0.9300 . ? C39 C40 1.505(7) . ? C40 C41 1.387(7) . ? C40 C45 1.393(7) . ? C41 C42 1.383(7) . ? C41 H41 0.9300 . ? C42 C43 1.369(8) . ? C43 C44 1.372(8) . ? C43 H43 0.9300 . ? C44 C45 1.389(8) . ? C44 H44 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 O5 Cu1 O3 102.20(14) . . ? O5 Cu1 O2 86.35(14) . . ? O3 Cu1 O2 165.01(15) . . ? O5 Cu1 O1 168.20(15) . . ? O3 Cu1 O1 88.78(14) . . ? O2 Cu1 O1 82.01(14) . . ? O5 Cu1 O4 90.66(15) . . ? O3 Cu1 O4 77.37(14) . . ? O2 Cu1 O4 115.22(15) . . ? O1 Cu1 O4 96.04(15) . . ? N4 Cu2 N3 90.0(2) . . ? N4 Cu2 N2 175.2(2) . . ? N3 Cu2 N2 92.85(19) . . ? N4 Cu2 N1 93.0(2) . . ? N3 Cu2 N1 155.4(2) . . ? N2 Cu2 N1 86.00(17) . . ? N4 Cu2 O7 89.3(2) . 2_665 ? N3 Cu2 O7 105.2(2) . 2_665 ? N2 Cu2 O7 86.2(2) . 2_665 ? N1 Cu2 O7 99.2(2) . 2_665 ? N5 Cu3 N7 162.48(19) . . ? N5 Cu3 N6 86.57(17) . . ? N7 Cu3 N6 94.28(18) . . ? N5 Cu3 N8 93.13(19) . . ? N7 Cu3 N8 92.3(2) . . ? N6 Cu3 N8 158.86(18) . . ? O9 S1 O7 115.9(6) . . ? O9 S1 O8 107.6(6) . . ? O7 S1 O8 111.6(4) . . ? O9 S1 C42 106.6(3) . . ? O7 S1 C42 108.3(3) . . ? O8 S1 C42 106.3(3) . . ? C1 O1 Cu1 114.3(3) . . ? C2 O2 Cu1 114.6(3) . . ? C20 O3 Cu1 118.5(3) . . ? C21 O4 Cu1 108.8(3) . . ? C39 O5 Cu1 129.7(3) . . ? S1 O7 Cu2 152.8(4) . 2_665 ? C45 O10 H10 109.5 . . ? C1 N1 C19 123.4(4) . . ? C1 N1 Cu2 109.9(3) . . ? C19 N1 Cu2 126.7(3) . . ? C2 N2 C3 123.2(4) . . ? C2 N2 Cu2 110.3(3) . . ? C3 N2 Cu2 126.3(3) . . ? C9 N3 C10 118.4(5) . . ? C9 N3 Cu2 124.6(4) . . ? C10 N3 Cu2 116.6(4) . . ? C13 N4 C12 118.5(5) . . ? C13 N4 Cu2 126.0(4) . . ? C12 N4 Cu2 115.5(4) . . ? C20 N5 C38 121.0(4) . . ? C20 N5 Cu3 111.8(3) . . ? C38 N5 Cu3 126.8(3) . . ? C21 N6 C22 122.9(4) . . ? C21 N6 Cu3 110.9(3) . . ? C22 N6 Cu3 126.2(3) . . ? C28 N7 C29 117.7(5) . . ? C28 N7 Cu3 124.7(4) . . ? C29 N7 Cu3 117.2(4) . . ? C32 N8 C31 119.3(5) . . ? C32 N8 Cu3 125.1(4) . . ? C31 N8 Cu3 115.1(4) . . ? O1 C1 N1 129.2(5) . . ? O1 C1 C2 114.3(4) . . ? N1 C1 C2 116.5(4) . . ? O2 C2 N2 128.8(5) . . ? O2 C2 C1 114.8(4) . . ? N2 C2 C1 116.5(4) . . ? C4 C3 N2 123.8(5) . . ? C4 C3 C8 117.4(5) . . ? N2 C3 C8 118.7(5) . . ? C3 C4 C5 121.6(6) . . ? C3 C4 H4 119.2 . . ? C5 C4 H4 119.2 . . ? C6 C5 C4 121.2(6) . . ? C6 C5 H5 119.4 . . ? C4 C5 H5 119.4 . . ? C7 C6 C5 118.4(6) . . ? C7 C6 H6 120.8 . . ? C5 C6 H6 120.8 . . ? C6 C7 C8 123.1(6) . . ? C6 C7 H7 118.5 . . ? C8 C7 H7 118.5 . . ? C7 C8 C3 118.2(5) . . ? C7 C8 C9 115.8(5) . . ? C3 C8 C9 125.8(5) . . ? N3 C9 C8 127.3(6) . . ? N3 C9 H9 116.3 . . ? C8 C9 H9 116.3 . . ? C11 C10 N3 112.6(5) . . ? C11 C10 H10A 109.1 . . ? N3 C10 H10A 109.1 . . ? C11 C10 H10B 109.1 . . ? N3 C10 H10B 109.1 . . ? H10A C10 H10B 107.8 . . ? C10 C11 C12 115.2(5) . . ? C10 C11 H11A 108.5 . . ? C12 C11 H11A 108.5 . . ? C10 C11 H11B 108.5 . . ? C12 C11 H11B 108.5 . . ? H11A C11 H11B 107.5 . . ? N4 C12 C11 112.0(5) . . ? N4 C12 H12A 109.2 . . ? C11 C12 H12A 109.2 . . ? N4 C12 H12B 109.2 . . ? C11 C12 H12B 109.2 . . ? H12A C12 H12B 107.9 . . ? N4 C13 C14 126.8(5) . . ? N4 C13 H13 116.6 . . ? C14 C13 H13 116.6 . . ? C15 C14 C19 119.7(5) . . ? C15 C14 C13 114.5(5) . . ? C19 C14 C13 125.6(5) . . ? C16 C15 C14 121.8(6) . . ? C16 C15 H15 119.1 . . ? C14 C15 H15 119.1 . . ? C15 C16 C17 119.6(6) . . ? C15 C16 H16 120.2 . . ? C17 C16 H16 120.2 . . ? C16 C17 C18 120.4(7) . . ? C16 C17 H17 119.8 . . ? C18 C17 H17 119.8 . . ? C17 C18 C19 121.3(6) . . ? C17 C18 H18 119.3 . . ? C19 C18 H18 119.3 . . ? C18 C19 C14 117.0(5) . . ? C18 C19 N1 122.8(5) . . ? C14 C19 N1 119.9(5) . . ? O3 C20 N5 127.1(5) . . ? O3 C20 C21 117.0(4) . . ? N5 C20 C21 115.7(4) . . ? O4 C21 N6 128.8(5) . . ? O4 C21 C20 116.6(4) . . ? N6 C21 C20 114.6(4) . . ? C23 C22 N6 123.2(5) . . ? C23 C22 C27 117.4(6) . . ? N6 C22 C27 119.4(5) . . ? C24 C23 C22 121.5(7) . . ? C24 C23 H23 119.3 . . ? C22 C23 H23 119.3 . . ? C23 C24 C25 121.1(7) . . ? C23 C24 H24 119.4 . . ? C25 C24 H24 119.4 . . ? C26 C25 C24 118.5(7) . . ? C26 C25 H25 120.8 . . ? C24 C25 H25 120.8 . . ? C25 C26 C27 121.5(7) . . ? C25 C26 H26 119.2 . . ? C27 C26 H26 119.2 . . ? C26 C27 C22 119.7(6) . . ? C26 C27 C28 114.1(5) . . ? C22 C27 C28 126.2(5) . . ? N7 C28 C27 127.4(5) . . ? N7 C28 H28 116.3 . . ? C27 C28 H28 116.3 . . ? N7 C29 C30 114.6(6) . . ? N7 C29 H29A 108.6 . . ? C30 C29 H29A 108.6 . . ? N7 C29 H29B 108.6 . . ? C30 C29 H29B 108.6 . . ? H29A C29 H29B 107.6 . . ? C29 C30 C31 117.0(5) . . ? C29 C30 H30A 108.0 . . ? C31 C30 H30A 108.0 . . ? C29 C30 H30B 108.0 . . ? C31 C30 H30B 108.0 . . ? H30A C30 H30B 107.3 . . ? N8 C31 C30 112.4(5) . . ? N8 C31 H31A 109.1 . . ? C30 C31 H31A 109.1 . . ? N8 C31 H31B 109.1 . . ? C30 C31 H31B 109.1 . . ? H31A C31 H31B 107.9 . . ? N8 C32 C33 127.3(5) . . ? N8 C32 H32 116.4 . . ? C33 C32 H32 116.4 . . ? C34 C33 C38 118.8(5) . . ? C34 C33 C32 115.4(5) . . ? C38 C33 C32 125.9(5) . . ? C35 C34 C33 121.1(6) . . ? C35 C34 H34 119.4 . . ? C33 C34 H34 119.4 . . ? C34 C35 C36 119.3(6) . . ? C34 C35 H35 120.4 . . ? C36 C35 H35 120.4 . . ? C37 C36 C35 120.7(6) . . ? C37 C36 H36 119.7 . . ? C35 C36 H36 119.7 . . ? C36 C37 C38 121.0(6) . . ? C36 C37 H37 119.5 . . ? C38 C37 H37 119.5 . . ? C37 C38 C33 119.1(5) . . ? C37 C38 N5 122.5(5) . . ? C33 C38 N5 118.4(5) . . ? O6 C39 O5 124.7(5) . . ? O6 C39 C40 120.6(4) . . ? O5 C39 C40 114.7(5) . . ? C41 C40 C45 118.7(5) . . ? C41 C40 C39 119.0(5) . . ? C45 C40 C39 122.3(4) . . ? C42 C41 C40 121.5(5) . . ? C42 C41 H41 119.3 . . ? C40 C41 H41 119.3 . . ? C43 C42 C41 118.7(5) . . ? C43 C42 S1 120.5(4) . . ? C41 C42 S1 120.6(4) . . ? C42 C43 C44 121.5(6) . . ? C42 C43 H43 119.3 . . ? C44 C43 H43 119.3 . . ? C43 C44 C45 119.9(6) . . ? C43 C44 H44 120.1 . . ? C45 C44 H44 120.1 . . ? O10 C45 C44 117.2(5) . . ? O10 C45 C40 123.0(5) . . ? C44 C45 C40 119.8(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 O5 Cu1 O1 C1 8.0(11) . . . . ? O3 Cu1 O1 C1 166.6(4) . . . . ? O2 Cu1 O1 C1 -1.5(4) . . . . ? O4 Cu1 O1 C1 -116.2(4) . . . . ? O5 Cu1 O2 C2 -175.3(4) . . . . ? O3 Cu1 O2 C2 -49.8(8) . . . . ? O1 Cu1 O2 C2 2.8(4) . . . . ? O4 Cu1 O2 C2 95.7(4) . . . . ? O5 Cu1 O3 C20 -76.5(4) . . . . ? O2 Cu1 O3 C20 159.8(5) . . . . ? O1 Cu1 O3 C20 107.9(4) . . . . ? O4 Cu1 O3 C20 11.4(3) . . . . ? O5 Cu1 O4 C21 91.5(3) . . . . ? O3 Cu1 O4 C21 -10.8(3) . . . . ? O2 Cu1 O4 C21 177.8(3) . . . . ? O1 Cu1 O4 C21 -98.2(3) . . . . ? O3 Cu1 O5 C39 25.2(5) . . . . ? O2 Cu1 O5 C39 -167.2(5) . . . . ? O1 Cu1 O5 C39 -176.7(7) . . . . ? O4 Cu1 O5 C39 -52.0(4) . . . . ? O9 S1 O7 Cu2 77.3(10) . . . 2_665 ? O8 S1 O7 Cu2 -159.1(9) . . . 2_665 ? C42 S1 O7 Cu2 -42.4(11) . . . 2_665 ? N4 Cu2 N1 C1 -166.8(4) . . . . ? N3 Cu2 N1 C1 96.5(6) . . . . ? N2 Cu2 N1 C1 8.4(4) . . . . ? O7 Cu2 N1 C1 -77.1(4) 2_665 . . . ? N4 Cu2 N1 C19 12.9(5) . . . . ? N3 Cu2 N1 C19 -83.7(6) . . . . ? N2 Cu2 N1 C19 -171.8(4) . . . . ? O7 Cu2 N1 C19 102.7(4) 2_665 . . . ? N4 Cu2 N2 C2 70(2) . . . . ? N3 Cu2 N2 C2 -163.2(4) . . . . ? N1 Cu2 N2 C2 -7.8(4) . . . . ? O7 Cu2 N2 C2 91.8(4) 2_665 . . . ? N4 Cu2 N2 C3 -104(2) . . . . ? N3 Cu2 N2 C3 22.2(4) . . . . ? N1 Cu2 N2 C3 177.6(4) . . . . ? O7 Cu2 N2 C3 -82.8(4) 2_665 . . . ? N4 Cu2 N3 C9 162.5(6) . . . . ? N2 Cu2 N3 C9 -13.7(6) . . . . ? N1 Cu2 N3 C9 -100.3(7) . . . . ? O7 Cu2 N3 C9 73.2(6) 2_665 . . . ? N4 Cu2 N3 C10 -24.7(5) . . . . ? N2 Cu2 N3 C10 159.2(4) . . . . ? N1 Cu2 N3 C10 72.6(6) . . . . ? O7 Cu2 N3 C10 -113.9(5) 2_665 . . . ? N3 Cu2 N4 C13 143.8(6) . . . . ? N2 Cu2 N4 C13 -90(2) . . . . ? N1 Cu2 N4 C13 -11.9(6) . . . . ? O7 Cu2 N4 C13 -111.1(6) 2_665 . . . ? N3 Cu2 N4 C12 -39.8(5) . . . . ? N2 Cu2 N4 C12 87(2) . . . . ? N1 Cu2 N4 C12 164.6(4) . . . . ? O7 Cu2 N4 C12 65.4(5) 2_665 . . . ? N7 Cu3 N5 C20 98.4(7) . . . . ? N6 Cu3 N5 C20 5.0(3) . . . . ? N8 Cu3 N5 C20 -153.8(3) . . . . ? N7 Cu3 N5 C38 -88.8(7) . . . . ? N6 Cu3 N5 C38 177.8(4) . . . . ? N8 Cu3 N5 C38 19.0(4) . . . . ? N5 Cu3 N6 C21 -6.4(3) . . . . ? N7 Cu3 N6 C21 -168.9(3) . . . . ? N8 Cu3 N6 C21 83.4(6) . . . . ? N5 Cu3 N6 C22 176.9(5) . . . . ? N7 Cu3 N6 C22 14.5(5) . . . . ? N8 Cu3 N6 C22 -93.3(7) . . . . ? N5 Cu3 N7 C28 -96.0(7) . . . . ? N6 Cu3 N7 C28 -3.9(5) . . . . ? N8 Cu3 N7 C28 156.0(5) . . . . ? N5 Cu3 N7 C29 76.5(8) . . . . ? N6 Cu3 N7 C29 168.7(5) . . . . ? N8 Cu3 N7 C29 -31.4(5) . . . . ? N5 Cu3 N8 C32 -5.8(5) . . . . ? N7 Cu3 N8 C32 157.6(5) . . . . ? N6 Cu3 N8 C32 -94.4(7) . . . . ? N5 Cu3 N8 C31 166.6(4) . . . . ? N7 Cu3 N8 C31 -30.0(4) . . . . ? N6 Cu3 N8 C31 78.1(7) . . . . ? Cu1 O1 C1 N1 179.1(5) . . . . ? Cu1 O1 C1 C2 0.3(6) . . . . ? C19 N1 C1 O1 -6.1(9) . . . . ? Cu2 N1 C1 O1 173.6(5) . . . . ? C19 N1 C1 C2 172.8(5) . . . . ? Cu2 N1 C1 C2 -7.5(6) . . . . ? Cu1 O2 C2 N2 178.7(4) . . . . ? Cu1 O2 C2 C1 -3.3(6) . . . . ? C3 N2 C2 O2 -1.5(9) . . . . ? Cu2 N2 C2 O2 -176.3(5) . . . . ? C3 N2 C2 C1 -179.5(4) . . . . ? Cu2 N2 C2 C1 5.7(6) . . . . ? O1 C1 C2 O2 2.1(7) . . . . ? N1 C1 C2 O2 -177.0(5) . . . . ? O1 C1 C2 N2 -179.7(5) . . . . ? N1 C1 C2 N2 1.3(7) . . . . ? C2 N2 C3 C4 -12.7(8) . . . . ? Cu2 N2 C3 C4 161.3(5) . . . . ? C2 N2 C3 C8 169.4(5) . . . . ? Cu2 N2 C3 C8 -16.7(7) . . . . ? N2 C3 C4 C5 178.5(6) . . . . ? C8 C3 C4 C5 -3.6(10) . . . . ? C3 C4 C5 C6 0.8(12) . . . . ? C4 C5 C6 C7 1.6(12) . . . . ? C5 C6 C7 C8 -1.2(11) . . . . ? C6 C7 C8 C3 -1.6(10) . . . . ? C6 C7 C8 C9 -176.5(6) . . . . ? C4 C3 C8 C7 3.8(8) . . . . ? N2 C3 C8 C7 -178.1(5) . . . . ? C4 C3 C8 C9 178.3(6) . . . . ? N2 C3 C8 C9 -3.7(8) . . . . ? C10 N3 C9 C8 -172.9(6) . . . . ? Cu2 N3 C9 C8 -0.1(10) . . . . ? C7 C8 C9 N3 -172.5(7) . . . . ? C3 C8 C9 N3 13.0(11) . . . . ? C9 N3 C10 C11 -118.7(7) . . . . ? Cu2 N3 C10 C11 67.9(7) . . . . ? N3 C10 C11 C12 -40.6(9) . . . . ? C13 N4 C12 C11 -111.7(7) . . . . ? Cu2 N4 C12 C11 71.6(6) . . . . ? C10 C11 C12 N4 -27.9(9) . . . . ? C12 N4 C13 C14 -172.8(6) . . . . ? Cu2 N4 C13 C14 3.5(10) . . . . ? N4 C13 C14 C15 -176.0(6) . . . . ? N4 C13 C14 C19 9.5(11) . . . . ? C19 C14 C15 C16 -1.7(10) . . . . ? C13 C14 C15 C16 -176.5(7) . . . . ? C14 C15 C16 C17 -1.8(12) . . . . ? C15 C16 C17 C18 3.0(14) . . . . ? C16 C17 C18 C19 -0.8(13) . . . . ? C17 C18 C19 C14 -2.6(11) . . . . ? C17 C18 C19 N1 -176.4(7) . . . . ? C15 C14 C19 C18 3.8(9) . . . . ? C13 C14 C19 C18 178.0(6) . . . . ? C15 C14 C19 N1 177.8(5) . . . . ? C13 C14 C19 N1 -8.0(9) . . . . ? C1 N1 C19 C18 -12.1(9) . . . . ? Cu2 N1 C19 C18 168.2(5) . . . . ? C1 N1 C19 C14 174.3(5) . . . . ? Cu2 N1 C19 C14 -5.4(7) . . . . ? Cu1 O3 C20 N5 173.8(4) . . . . ? Cu1 O3 C20 C21 -10.7(5) . . . . ? C38 N5 C20 O3 -0.5(8) . . . . ? Cu3 N5 C20 O3 172.8(4) . . . . ? C38 N5 C20 C21 -176.0(4) . . . . ? Cu3 N5 C20 C21 -2.7(5) . . . . ? Cu1 O4 C21 N6 -173.1(4) . . . . ? Cu1 O4 C21 C20 8.7(5) . . . . ? C22 N6 C21 O4 5.1(8) . . . . ? Cu3 N6 C21 O4 -171.7(4) . . . . ? C22 N6 C21 C20 -176.8(5) . . . . ? Cu3 N6 C21 C20 6.5(5) . . . . ? O3 C20 C21 O4 -0.2(7) . . . . ? N5 C20 C21 O4 175.8(4) . . . . ? O3 C20 C21 N6 -178.6(4) . . . . ? N5 C20 C21 N6 -2.6(6) . . . . ? C21 N6 C22 C23 -13.3(9) . . . . ? Cu3 N6 C22 C23 162.9(5) . . . . ? C21 N6 C22 C27 167.8(5) . . . . ? Cu3 N6 C22 C27 -15.9(8) . . . . ? N6 C22 C23 C24 176.6(8) . . . . ? C27 C22 C23 C24 -4.6(11) . . . . ? C22 C23 C24 C25 0.5(15) . . . . ? C23 C24 C25 C26 2.8(16) . . . . ? C24 C25 C26 C27 -1.7(14) . . . . ? C25 C26 C27 C22 -2.4(11) . . . . ? C25 C26 C27 C28 177.7(7) . . . . ? C23 C22 C27 C26 5.5(9) . . . . ? N6 C22 C27 C26 -175.6(6) . . . . ? C23 C22 C27 C28 -174.7(6) . . . . ? N6 C22 C27 C28 4.2(9) . . . . ? C29 N7 C28 C27 -177.9(6) . . . . ? Cu3 N7 C28 C27 -5.4(9) . . . . ? C26 C27 C28 N7 -172.9(6) . . . . ? C22 C27 C28 N7 7.3(10) . . . . ? C28 N7 C29 C30 -123.8(7) . . . . ? Cu3 N7 C29 C30 63.1(7) . . . . ? N7 C29 C30 C31 -26.6(10) . . . . ? C32 N8 C31 C30 -119.1(6) . . . . ? Cu3 N8 C31 C30 68.0(7) . . . . ? C29 C30 C31 N8 -40.0(10) . . . . ? C31 N8 C32 C33 -178.7(5) . . . . ? Cu3 N8 C32 C33 -6.5(8) . . . . ? N8 C32 C33 C34 -170.8(5) . . . . ? N8 C32 C33 C38 10.1(9) . . . . ? C38 C33 C34 C35 -1.9(8) . . . . ? C32 C33 C34 C35 179.0(5) . . . . ? C33 C34 C35 C36 -0.8(9) . . . . ? C34 C35 C36 C37 2.2(9) . . . . ? C35 C36 C37 C38 -0.7(9) . . . . ? C36 C37 C38 C33 -2.1(8) . . . . ? C36 C37 C38 N5 176.3(5) . . . . ? C34 C33 C38 C37 3.4(7) . . . . ? C32 C33 C38 C37 -177.6(5) . . . . ? C34 C33 C38 N5 -175.1(5) . . . . ? C32 C33 C38 N5 3.9(7) . . . . ? C20 N5 C38 C37 -26.2(7) . . . . ? Cu3 N5 C38 C37 161.6(4) . . . . ? C20 N5 C38 C33 152.2(5) . . . . ? Cu3 N5 C38 C33 -20.0(6) . . . . ? Cu1 O5 C39 O6 -11.8(8) . . . . ? Cu1 O5 C39 C40 165.7(3) . . . . ? O6 C39 C40 C41 -6.1(8) . . . . ? O5 C39 C40 C41 176.3(5) . . . . ? O6 C39 C40 C45 171.2(5) . . . . ? O5 C39 C40 C45 -6.3(7) . . . . ? C45 C40 C41 C42 -1.6(8) . . . . ? C39 C40 C41 C42 175.9(5) . . . . ? C40 C41 C42 C43 -0.7(8) . . . . ? C40 C41 C42 S1 -175.9(4) . . . . ? O9 S1 C42 C43 -11.9(8) . . . . ? O7 S1 C42 C43 113.5(6) . . . . ? O8 S1 C42 C43 -126.5(6) . . . . ? O9 S1 C42 C41 163.3(7) . . . . ? O7 S1 C42 C41 -71.4(6) . . . . ? O8 S1 C42 C41 48.7(6) . . . . ? C41 C42 C43 C44 1.4(10) . . . . ? S1 C42 C43 C44 176.6(5) . . . . ? C42 C43 C44 C45 0.2(10) . . . . ? C43 C44 C45 O10 179.0(6) . . . . ? C43 C44 C45 C40 -2.5(10) . . . . ? C41 C40 C45 O10 -178.5(5) . . . . ? C39 C40 C45 O10 4.2(8) . . . . ? C41 C40 C45 C44 3.1(8) . . . . ? C39 C40 C45 C44 -174.2(5) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.03 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.839 _refine_diff_density_min -0.546 _refine_diff_density_rms 0.091