Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'S. Brooker' _publ_contact_author_address ; Chemistry Department University of Otago PO Box 56 Dunedin 9001 NEW ZEALAND ; _publ_contact_author_email SBROOKER@ALKALI.OTAGO.AC.NZ _publ_section_title ; Tricopper(II) complexes of unsymmetrical macrocycles incorporating phenol and pyridine moieties: the development of two stepwise routes ; loop_ _publ_author_name 'S. Brooker' 'Paul D. Croucher' 'Marco H. Klingele' 'Andy Noble' data_paul _database_code_depnum_ccdc_archive 'CCDC 185491' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H35 Cu3 N9 O5 S2' _chemical_formula_weight 832.39 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 12.6504(7) _cell_length_b 25.8725(14) _cell_length_c 10.1766(5) _cell_angle_alpha 90.00 _cell_angle_beta 99.0210(10) _cell_angle_gamma 90.00 _cell_volume 3289.6(3) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.681 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1700 _exptl_absorpt_coefficient_mu 2.102 _exptl_absorpt_correction_type Semi-empirical(SADABS) _exptl_absorpt_correction_T_min 0.59 _exptl_absorpt_correction_T_max 0.83 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 'Bruker SMART area detector' _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6008 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0393 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 31 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 1.57 _diffrn_reflns_theta_max 25.37 _reflns_number_total 6008 _reflns_number_gt 4874 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0544P)^2^+5.2317P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6008 _refine_ls_number_parameters 427 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0551 _refine_ls_R_factor_gt 0.0401 _refine_ls_wR_factor_ref 0.1109 _refine_ls_wR_factor_gt 0.1011 _refine_ls_goodness_of_fit_ref 1.072 _refine_ls_restrained_S_all 1.072 _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 Cu1 Cu 0.28977(4) 0.536740(17) 0.98515(5) 0.02241(13) Uani 1 1 d . . . Cu2 Cu 0.20950(4) 0.546766(17) 0.65741(5) 0.02264(13) Uani 1 1 d . . . Cu3 Cu 0.19997(4) 0.641794(17) 0.82451(5) 0.02237(13) Uani 1 1 d . . . N1 N 0.4218(3) 0.56366(12) 0.9397(3) 0.0223(7) Uani 1 1 d . . . C2 C 0.4589(3) 0.60861(14) 0.9926(4) 0.0244(8) Uani 1 1 d . . . C3 C 0.5483(3) 0.63051(16) 0.9541(4) 0.0309(9) Uani 1 1 d . . . H3 H 0.5750 0.6626 0.9906 0.037 Uiso 1 1 calc R . . C4 C 0.5987(3) 0.60520(17) 0.8615(5) 0.0345(10) Uani 1 1 d . . . H4 H 0.6598 0.6201 0.8327 0.041 Uiso 1 1 calc R . . C5 C 0.5594(3) 0.55766(17) 0.8106(4) 0.0333(10) Uani 1 1 d . . . H5 H 0.5944 0.5394 0.7489 0.040 Uiso 1 1 calc R . . C6 C 0.4694(3) 0.53782(15) 0.8510(4) 0.0263(9) Uani 1 1 d . . . C7 C 0.4138(3) 0.48732(15) 0.8086(4) 0.0280(9) Uani 1 1 d . . . O1 O 0.4549(2) 0.45825(11) 0.7325(3) 0.0368(7) Uani 1 1 d . . . N2 N 0.3248(3) 0.48111(12) 0.8607(3) 0.0256(7) Uani 1 1 d . . . C8 C 0.2637(4) 0.43348(14) 0.8319(4) 0.0296(9) Uani 1 1 d . . . H8A H 0.2565 0.4161 0.9167 0.036 Uiso 1 1 calc R . . H8B H 0.3036 0.4100 0.7805 0.036 Uiso 1 1 calc R . . C9 C 0.1524(3) 0.44300(15) 0.7532(4) 0.0287(9) Uani 1 1 d . . . H9A H 0.1179 0.4093 0.7283 0.034 Uiso 1 1 calc R . . H9B H 0.1083 0.4613 0.8107 0.034 Uiso 1 1 calc R . . N3 N 0.1548(3) 0.47390(12) 0.6309(3) 0.0255(7) Uani 1 1 d . . . H3A H 0.0815 0.4769 0.5888 0.031 Uiso 1 1 d . . . C10 C 0.2170(4) 0.44853(15) 0.5355(4) 0.0311(9) Uani 1 1 d . . . H10A H 0.1756 0.4194 0.4899 0.037 Uiso 1 1 calc R . . H10B H 0.2854 0.4348 0.5836 0.037 Uiso 1 1 calc R . . C11 C 0.2387(4) 0.48871(16) 0.4349(4) 0.0336(10) Uani 1 1 d . . . H11A H 0.2901 0.4751 0.3795 0.040 Uiso 1 1 calc R . . H11B H 0.1714 0.4978 0.3757 0.040 Uiso 1 1 calc R . . N4 N 0.2833(3) 0.53442(12) 0.5090(3) 0.0268(7) Uani 1 1 d . . . C12 C 0.3574(3) 0.56119(15) 0.4699(4) 0.0270(9) Uani 1 1 d . . . H12 H 0.3879 0.5482 0.3970 0.032 Uiso 1 1 calc R . . O2 O 0.2808(2) 0.61440(9) 0.6894(3) 0.0230(6) Uani 1 1 d . . . C13 C 0.3557(3) 0.63608(14) 0.6311(4) 0.0222(8) Uani 1 1 d . . . C14 C 0.3994(3) 0.61027(15) 0.5283(4) 0.0252(8) Uani 1 1 d . . . C15 C 0.4810(3) 0.63308(16) 0.4717(4) 0.0287(9) Uani 1 1 d . . . H15 H 0.5090 0.6152 0.4033 0.034 Uiso 1 1 calc R . . C16 C 0.5230(3) 0.68119(16) 0.5119(4) 0.0317(9) Uani 1 1 d . . . C17 C 0.4782(3) 0.70705(15) 0.6091(4) 0.0309(9) Uani 1 1 d . . . H17 H 0.5051 0.7403 0.6365 0.037 Uiso 1 1 calc R . . C18 C 0.3950(3) 0.68618(14) 0.6687(4) 0.0232(8) Uani 1 1 d . . . C19 C 0.6129(4) 0.70360(19) 0.4482(5) 0.0475(13) Uani 1 1 d . . . H19A H 0.6140 0.7413 0.4586 0.057 Uiso 1 1 calc R . . H19B H 0.6019 0.6948 0.3533 0.057 Uiso 1 1 calc R . . H19C H 0.6813 0.6892 0.4913 0.057 Uiso 1 1 calc R . . C20 C 0.3480(3) 0.71941(14) 0.7591(4) 0.0256(9) Uani 1 1 d . . . H20 H 0.3784 0.7528 0.7754 0.031 Uiso 1 1 calc R . . N5 N 0.2697(3) 0.70782(12) 0.8187(3) 0.0247(7) Uani 1 1 d . . . C21 C 0.2196(3) 0.74659(14) 0.8947(4) 0.0286(9) Uani 1 1 d . . . H21A H 0.1552 0.7612 0.8395 0.034 Uiso 1 1 calc R . . H21B H 0.2704 0.7751 0.9225 0.034 Uiso 1 1 calc R . . C22 C 0.1893(4) 0.71978(15) 1.0157(4) 0.0291(9) Uani 1 1 d . . . H22A H 0.2546 0.7115 1.0794 0.035 Uiso 1 1 calc R . . H22B H 0.1438 0.7428 1.0607 0.035 Uiso 1 1 calc R . . N6 N 0.1300(3) 0.67131(12) 0.9725(3) 0.0255(7) Uani 1 1 d . . . H6A H 0.0590 0.6831 0.9413 0.031 Uiso 1 1 d . . . C23 C 0.1181(3) 0.63697(16) 1.0866(4) 0.0281(9) Uani 1 1 d . . . H23A H 0.0794 0.6053 1.0520 0.034 Uiso 1 1 calc R . . H23B H 0.0736 0.6549 1.1444 0.034 Uiso 1 1 calc R . . C24 C 0.2239(3) 0.62121(16) 1.1710(4) 0.0280(9) Uani 1 1 d . . . H24A H 0.2544 0.6512 1.2242 0.034 Uiso 1 1 calc R . . H24B H 0.2105 0.5935 1.2334 0.034 Uiso 1 1 calc R . . N7 N 0.3014(3) 0.60281(12) 1.0882(3) 0.0238(7) Uani 1 1 d . . . C25 C 0.3908(3) 0.63017(14) 1.0889(4) 0.0247(8) Uani 1 1 d . . . O3 O 0.4210(2) 0.67033(10) 1.1531(3) 0.0315(7) Uani 1 1 d . . . O4 O 0.1553(2) 0.57049(9) 0.8149(3) 0.0223(6) Uani 1 1 d . . . H4A H 0.0874 0.5629 0.8350 0.027 Uiso 1 1 d . . . N30 N 0.1877(3) 0.49912(14) 1.0729(4) 0.0324(8) Uani 1 1 d . . . C30 C 0.1500(3) 0.46277(16) 1.1139(4) 0.0264(9) Uani 1 1 d . . . S30 S 0.10070(9) 0.41178(4) 1.17713(11) 0.0340(3) Uani 1 1 d . . . N40 N 0.0520(3) 0.57758(16) 0.4895(4) 0.0426(10) Uani 1 1 d . . . C40 C 0.0371(4) 0.61676(18) 0.5355(5) 0.0375(11) Uani 1 1 d . . . S40 S 0.01743(11) 0.67172(4) 0.61211(13) 0.0416(3) Uani 1 1 d . . . O50 O -0.0477(4) 0.75907(18) 0.3758(5) 0.0804(15) Uani 1 1 d . . . H50 H -0.0387 0.7332 0.4261 0.096 Uiso 1 1 calc R . . C51 C -0.1547(5) 0.7595(2) 0.3073(6) 0.0621(16) Uani 1 1 d . . . H51A H -0.1670 0.7916 0.2543 0.074 Uiso 1 1 calc R . . H51B H -0.2047 0.7594 0.3730 0.074 Uiso 1 1 calc R . . C52 C -0.1778(6) 0.7135(3) 0.2164(8) 0.084(2) Uani 1 1 d . . . H52A H -0.1300 0.7141 0.1494 0.101 Uiso 1 1 calc R . . H52B H -0.2523 0.7149 0.1720 0.101 Uiso 1 1 calc R . . H52C H -0.1662 0.6816 0.2686 0.101 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.0277(3) 0.0163(2) 0.0233(3) -0.00031(18) 0.00431(19) 0.00100(18) Cu2 0.0298(3) 0.0165(2) 0.0220(3) -0.00227(18) 0.00538(19) -0.00156(18) Cu3 0.0276(3) 0.0160(2) 0.0237(3) -0.00186(18) 0.00464(19) 0.00140(18) N1 0.0233(17) 0.0190(16) 0.0241(17) 0.0023(13) 0.0022(13) 0.0033(13) C2 0.028(2) 0.0183(18) 0.024(2) 0.0012(15) -0.0033(16) 0.0054(15) C3 0.027(2) 0.025(2) 0.039(2) 0.0044(18) -0.0025(18) -0.0008(17) C4 0.022(2) 0.038(2) 0.044(3) 0.009(2) 0.0058(19) 0.0020(18) C5 0.028(2) 0.040(2) 0.033(2) 0.0017(19) 0.0054(18) 0.0080(19) C6 0.029(2) 0.026(2) 0.024(2) 0.0056(16) 0.0021(17) 0.0083(16) C7 0.035(2) 0.024(2) 0.024(2) 0.0021(16) 0.0004(18) 0.0089(17) O1 0.0396(18) 0.0335(17) 0.0382(17) -0.0085(14) 0.0094(14) 0.0083(13) N2 0.0303(19) 0.0179(16) 0.0275(18) -0.0024(13) 0.0009(15) 0.0028(13) C8 0.045(3) 0.0131(18) 0.029(2) -0.0011(16) 0.0027(19) 0.0042(17) C9 0.035(2) 0.0191(19) 0.032(2) 0.0002(16) 0.0044(18) -0.0066(16) N3 0.0293(19) 0.0204(16) 0.0260(18) -0.0001(13) 0.0020(14) -0.0018(13) C10 0.038(3) 0.023(2) 0.032(2) -0.0086(17) 0.0057(19) -0.0015(17) C11 0.046(3) 0.026(2) 0.031(2) -0.0106(18) 0.011(2) -0.0082(19) N4 0.034(2) 0.0223(17) 0.0240(17) -0.0029(14) 0.0046(15) -0.0027(14) C12 0.033(2) 0.024(2) 0.024(2) -0.0015(16) 0.0062(17) 0.0005(17) O2 0.0303(15) 0.0156(12) 0.0241(14) -0.0030(10) 0.0072(12) -0.0031(11) C13 0.024(2) 0.0211(19) 0.0206(19) 0.0043(15) -0.0012(16) 0.0015(15) C14 0.031(2) 0.0213(19) 0.024(2) 0.0008(16) 0.0047(17) 0.0021(16) C15 0.030(2) 0.028(2) 0.029(2) 0.0016(17) 0.0068(18) 0.0035(17) C16 0.034(2) 0.029(2) 0.035(2) 0.0012(18) 0.0117(19) -0.0024(18) C17 0.036(2) 0.0196(19) 0.036(2) 0.0026(17) 0.0024(19) -0.0045(17) C18 0.027(2) 0.0169(18) 0.024(2) 0.0016(15) 0.0011(16) 0.0027(15) C19 0.051(3) 0.037(3) 0.060(3) -0.008(2) 0.026(3) -0.012(2) C20 0.033(2) 0.0142(18) 0.026(2) 0.0021(15) -0.0047(17) -0.0004(15) N5 0.033(2) 0.0154(15) 0.0243(17) 0.0007(13) 0.0012(15) 0.0045(13) C21 0.036(2) 0.0170(19) 0.031(2) -0.0025(16) 0.0019(18) 0.0073(16) C22 0.040(3) 0.0202(19) 0.025(2) -0.0056(16) 0.0009(18) 0.0076(17) N6 0.0275(18) 0.0249(17) 0.0238(17) -0.0032(13) 0.0030(14) 0.0061(14) C23 0.032(2) 0.030(2) 0.024(2) -0.0011(16) 0.0085(17) 0.0035(17) C24 0.038(2) 0.025(2) 0.021(2) -0.0031(16) 0.0057(18) 0.0043(17) N7 0.0282(18) 0.0196(16) 0.0231(17) 0.0009(13) 0.0022(14) 0.0045(13) C25 0.029(2) 0.0172(18) 0.026(2) 0.0029(16) -0.0024(17) 0.0059(16) O3 0.0373(17) 0.0193(14) 0.0368(17) -0.0055(12) 0.0024(13) 0.0009(12) O4 0.0285(15) 0.0167(13) 0.0225(13) -0.0009(10) 0.0068(11) -0.0016(11) N30 0.036(2) 0.0295(19) 0.033(2) 0.0028(16) 0.0085(16) -0.0036(16) C30 0.026(2) 0.030(2) 0.023(2) -0.0026(17) 0.0037(16) 0.0017(17) S30 0.0341(6) 0.0286(5) 0.0392(6) 0.0040(5) 0.0050(5) -0.0076(4) N40 0.035(2) 0.044(2) 0.045(2) -0.0166(19) -0.0056(18) 0.0044(18) C40 0.027(2) 0.036(3) 0.045(3) 0.009(2) -0.006(2) -0.0040(19) S40 0.0504(7) 0.0248(6) 0.0489(7) 0.0051(5) 0.0060(6) -0.0026(5) O50 0.064(3) 0.066(3) 0.100(4) 0.039(3) -0.021(2) -0.027(2) C51 0.048(3) 0.059(4) 0.076(4) 0.015(3) 0.000(3) -0.016(3) C52 0.082(5) 0.069(5) 0.096(5) 0.000(4) -0.002(4) -0.007(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 N1 1.931(3) . y Cu1 N30 1.943(4) . y Cu1 N7 1.999(3) . y Cu1 N2 2.012(3) . y Cu1 O4 2.395(3) . y Cu2 N4 1.922(3) . y Cu2 O4 1.939(3) . y Cu2 O2 1.972(3) . y Cu2 N3 2.012(3) . y Cu2 N40 2.541(4) . y Cu3 O4 1.928(2) . y Cu3 N5 1.928(3) . y Cu3 O2 1.969(3) . y Cu3 N6 2.013(3) . y Cu3 S40 3.0064(14) . y N1 C2 1.336(5) . ? N1 C6 1.340(5) . ? C2 C3 1.376(6) . ? C2 C25 1.510(6) . ? C3 C4 1.383(6) . ? C4 C5 1.396(6) . ? C5 C6 1.369(6) . ? C6 C7 1.514(6) . ? C7 O1 1.250(5) . ? C7 N2 1.327(5) . ? N2 C8 1.460(5) . ? C8 C9 1.527(6) . ? C9 N3 1.484(5) . ? N3 C10 1.494(5) . ? C10 C11 1.514(6) . ? C11 N4 1.467(5) . ? N4 C12 1.279(5) . ? C12 C14 1.466(5) . ? O2 C13 1.319(5) . ? C13 C18 1.419(5) . ? C13 C14 1.424(5) . ? C14 C15 1.390(6) . ? C15 C16 1.390(6) . ? C16 C17 1.386(6) . ? C16 C19 1.511(6) . ? C17 C18 1.403(6) . ? C18 C20 1.453(5) . ? C20 N5 1.275(5) . ? N5 C21 1.470(5) . ? C21 C22 1.513(6) . ? C22 N6 1.492(5) . ? N6 C23 1.489(5) . ? C23 C24 1.528(6) . ? C24 N7 1.468(5) . ? N7 C25 1.333(5) . ? C25 O3 1.254(5) . ? N30 C30 1.161(5) . ? C30 S30 1.633(4) . ? N40 C40 1.144(6) . ? C40 S40 1.659(5) . ? O50 C51 1.421(7) . ? C51 C52 1.508(9) . ? 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 N1 Cu1 N30 162.32(14) . . y N1 Cu1 N7 79.75(13) . . y N30 Cu1 N7 100.76(14) . . y N1 Cu1 N2 79.82(13) . . y N30 Cu1 N2 99.14(14) . . y N7 Cu1 N2 159.51(14) . . y N1 Cu1 O4 103.77(11) . . y N30 Cu1 O4 93.87(13) . . y N7 Cu1 O4 93.05(11) . . y N2 Cu1 O4 90.40(11) . . y N4 Cu2 O4 168.53(13) . . y N4 Cu2 O2 90.65(12) . . y O4 Cu2 O2 78.15(10) . . y N4 Cu2 N3 86.44(14) . . y O4 Cu2 N3 104.40(12) . . y O2 Cu2 N3 172.93(13) . . y N4 Cu2 N40 87.13(14) . . y O4 Cu2 N40 96.58(12) . . y O2 Cu2 N40 97.05(12) . . y N3 Cu2 N40 89.24(13) . . y O4 Cu3 N5 168.12(13) . . y O4 Cu3 O2 78.49(10) . . y N5 Cu3 O2 90.41(12) . . y O4 Cu3 N6 103.96(12) . . y N5 Cu3 N6 86.77(14) . . y O2 Cu3 N6 174.88(13) . . y O4 Cu3 S40 91.36(8) . . y N5 Cu3 S40 93.07(10) . . y O2 Cu3 S40 90.88(8) . . y N6 Cu3 S40 93.55(10) . . y C2 N1 C6 122.6(4) . . ? C2 N1 Cu1 118.7(3) . . ? C6 N1 Cu1 118.6(3) . . ? N1 C2 C3 119.8(4) . . ? N1 C2 C25 112.5(3) . . ? C3 C2 C25 127.7(4) . . ? C2 C3 C4 119.1(4) . . ? C3 C4 C5 119.6(4) . . ? C6 C5 C4 118.9(4) . . ? N1 C6 C5 119.9(4) . . ? N1 C6 C7 112.6(4) . . ? C5 C6 C7 127.5(4) . . ? O1 C7 N2 129.5(4) . . ? O1 C7 C6 118.4(4) . . ? N2 C7 C6 112.1(3) . . ? C7 N2 C8 118.5(3) . . ? C7 N2 Cu1 116.7(3) . . ? C8 N2 Cu1 124.7(3) . . ? N2 C8 C9 112.6(3) . . ? N3 C9 C8 112.9(3) . . ? C9 N3 C10 113.0(3) . . ? C9 N3 Cu2 116.4(2) . . ? C10 N3 Cu2 107.1(2) . . ? N3 C10 C11 107.9(3) . . ? N4 C11 C10 107.5(3) . . ? C12 N4 C11 121.2(3) . . ? C12 N4 Cu2 128.7(3) . . ? C11 N4 Cu2 110.1(3) . . ? N4 C12 C14 125.4(4) . . ? C13 O2 Cu3 130.5(2) . . ? C13 O2 Cu2 130.2(2) . . ? Cu3 O2 Cu2 99.23(11) . . ? O2 C13 C18 120.9(3) . . ? O2 C13 C14 121.3(3) . . ? C18 C13 C14 117.8(3) . . ? C15 C14 C13 120.3(4) . . ? C15 C14 C12 116.4(4) . . ? C13 C14 C12 123.1(4) . . ? C16 C15 C14 122.2(4) . . ? C17 C16 C15 117.5(4) . . ? C17 C16 C19 122.7(4) . . ? C15 C16 C19 119.8(4) . . ? C16 C17 C18 122.7(4) . . ? C17 C18 C13 119.4(4) . . ? C17 C18 C20 117.1(3) . . ? C13 C18 C20 123.3(4) . . ? N5 C20 C18 126.0(4) . . ? C20 N5 C21 121.4(3) . . ? C20 N5 Cu3 128.0(3) . . ? C21 N5 Cu3 110.6(3) . . ? N5 C21 C22 107.5(3) . . ? N6 C22 C21 109.0(3) . . ? C23 N6 C22 112.3(3) . . ? C23 N6 Cu3 117.9(2) . . ? C22 N6 Cu3 106.2(2) . . ? N6 C23 C24 114.2(3) . . ? N7 C24 C23 111.6(3) . . ? C25 N7 C24 117.8(3) . . ? C25 N7 Cu1 116.7(3) . . ? C24 N7 Cu1 125.3(3) . . ? O3 C25 N7 129.1(4) . . ? O3 C25 C2 119.1(4) . . ? N7 C25 C2 111.7(3) . . ? Cu3 O4 Cu2 101.88(12) . . y Cu3 O4 Cu1 98.20(11) . . y Cu2 O4 Cu1 100.32(11) . . y C30 N30 Cu1 155.7(3) . . ? N30 C30 S30 177.6(4) . . ? C40 N40 Cu2 99.5(3) . . ? N40 C40 S40 176.1(5) . . ? C40 S40 Cu3 87.85(16) . . ? O50 C51 C52 111.9(6) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N30 Cu1 N1 C2 -92.3(5) . . . . ? N7 Cu1 N1 C2 1.0(3) . . . . ? N2 Cu1 N1 C2 179.6(3) . . . . ? O4 Cu1 N1 C2 91.7(3) . . . . ? N30 Cu1 N1 C6 91.2(5) . . . . ? N7 Cu1 N1 C6 -175.6(3) . . . . ? N2 Cu1 N1 C6 3.0(3) . . . . ? O4 Cu1 N1 C6 -84.9(3) . . . . ? C6 N1 C2 C3 1.3(6) . . . . ? Cu1 N1 C2 C3 -175.1(3) . . . . ? C6 N1 C2 C25 179.6(3) . . . . ? Cu1 N1 C2 C25 3.1(4) . . . . ? N1 C2 C3 C4 -0.5(6) . . . . ? C25 C2 C3 C4 -178.4(4) . . . . ? C2 C3 C4 C5 -1.1(6) . . . . ? C3 C4 C5 C6 1.8(6) . . . . ? C2 N1 C6 C5 -0.5(6) . . . . ? Cu1 N1 C6 C5 175.9(3) . . . . ? C2 N1 C6 C7 178.5(3) . . . . ? Cu1 N1 C6 C7 -5.0(4) . . . . ? C4 C5 C6 N1 -1.1(6) . . . . ? C4 C5 C6 C7 -180.0(4) . . . . ? N1 C6 C7 O1 -175.5(3) . . . . ? C5 C6 C7 O1 3.4(6) . . . . ? N1 C6 C7 N2 4.7(5) . . . . ? C5 C6 C7 N2 -176.3(4) . . . . ? O1 C7 N2 C8 2.0(6) . . . . ? C6 C7 N2 C8 -178.3(3) . . . . ? O1 C7 N2 Cu1 177.8(3) . . . . ? C6 C7 N2 Cu1 -2.5(4) . . . . ? N1 Cu1 N2 C7 0.0(3) . . . . ? N30 Cu1 N2 C7 -162.1(3) . . . . ? N7 Cu1 N2 C7 4.1(6) . . . . ? O4 Cu1 N2 C7 103.9(3) . . . . ? N1 Cu1 N2 C8 175.5(3) . . . . ? N30 Cu1 N2 C8 13.4(3) . . . . ? N7 Cu1 N2 C8 179.6(3) . . . . ? O4 Cu1 N2 C8 -80.5(3) . . . . ? C7 N2 C8 C9 -116.2(4) . . . . ? Cu1 N2 C8 C9 68.3(4) . . . . ? N2 C8 C9 N3 52.7(5) . . . . ? C8 C9 N3 C10 60.5(4) . . . . ? C8 C9 N3 Cu2 -64.0(4) . . . . ? N4 Cu2 N3 C9 138.8(3) . . . . ? O4 Cu2 N3 C9 -37.4(3) . . . . ? O2 Cu2 N3 C9 73.0(11) . . . . ? N40 Cu2 N3 C9 -134.0(3) . . . . ? N4 Cu2 N3 C10 11.4(3) . . . . ? O4 Cu2 N3 C10 -164.8(2) . . . . ? O2 Cu2 N3 C10 -54.5(11) . . . . ? N40 Cu2 N3 C10 98.6(3) . . . . ? C9 N3 C10 C11 -165.2(3) . . . . ? Cu2 N3 C10 C11 -35.8(4) . . . . ? N3 C10 C11 N4 50.1(5) . . . . ? C10 C11 N4 C12 142.3(4) . . . . ? C10 C11 N4 Cu2 -40.4(4) . . . . ? O4 Cu2 N4 C12 -5.3(9) . . . . ? O2 Cu2 N4 C12 6.9(4) . . . . ? N3 Cu2 N4 C12 -166.6(4) . . . . ? N40 Cu2 N4 C12 103.9(4) . . . . ? O4 Cu2 N4 C11 177.7(6) . . . . ? O2 Cu2 N4 C11 -170.1(3) . . . . ? N3 Cu2 N4 C11 16.4(3) . . . . ? N40 Cu2 N4 C11 -73.0(3) . . . . ? C11 N4 C12 C14 173.2(4) . . . . ? Cu2 N4 C12 C14 -3.5(6) . . . . ? O4 Cu3 O2 C13 -172.6(3) . . . . ? N5 Cu3 O2 C13 3.1(3) . . . . ? N6 Cu3 O2 C13 -53.6(15) . . . . ? S40 Cu3 O2 C13 96.2(3) . . . . ? O4 Cu3 O2 Cu2 11.28(11) . . . . ? N5 Cu3 O2 Cu2 -173.00(13) . . . . ? N6 Cu3 O2 Cu2 130.3(13) . . . . ? S40 Cu3 O2 Cu2 -79.93(9) . . . . ? N4 Cu2 O2 C13 -4.9(3) . . . . ? O4 Cu2 O2 C13 172.7(3) . . . . ? N3 Cu2 O2 C13 60.7(11) . . . . ? N40 Cu2 O2 C13 -92.1(3) . . . . ? N4 Cu2 O2 Cu3 171.25(13) . . . . ? O4 Cu2 O2 Cu3 -11.23(11) . . . . ? N3 Cu2 O2 Cu3 -123.1(10) . . . . ? N40 Cu2 O2 Cu3 84.05(13) . . . . ? Cu3 O2 C13 C18 4.0(5) . . . . ? Cu2 O2 C13 C18 178.9(3) . . . . ? Cu3 O2 C13 C14 -175.8(3) . . . . ? Cu2 O2 C13 C14 -0.8(5) . . . . ? O2 C13 C14 C15 -177.6(4) . . . . ? C18 C13 C14 C15 2.6(6) . . . . ? O2 C13 C14 C12 6.9(6) . . . . ? C18 C13 C14 C12 -172.8(4) . . . . ? N4 C12 C14 C15 179.4(4) . . . . ? N4 C12 C14 C13 -4.9(7) . . . . ? C13 C14 C15 C16 0.0(6) . . . . ? C12 C14 C15 C16 175.7(4) . . . . ? C14 C15 C16 C17 -1.9(6) . . . . ? C14 C15 C16 C19 179.0(4) . . . . ? C15 C16 C17 C18 1.2(7) . . . . ? C19 C16 C17 C18 -179.7(4) . . . . ? C16 C17 C18 C13 1.4(6) . . . . ? C16 C17 C18 C20 -173.8(4) . . . . ? O2 C13 C18 C17 177.0(4) . . . . ? C14 C13 C18 C17 -3.3(5) . . . . ? O2 C13 C18 C20 -8.1(6) . . . . ? C14 C13 C18 C20 171.7(3) . . . . ? C17 C18 C20 N5 177.5(4) . . . . ? C13 C18 C20 N5 2.4(6) . . . . ? C18 C20 N5 C21 -172.1(4) . . . . ? C18 C20 N5 Cu3 7.4(6) . . . . ? O4 Cu3 N5 C20 12.2(8) . . . . ? O2 Cu3 N5 C20 -8.7(4) . . . . ? N6 Cu3 N5 C20 167.0(4) . . . . ? S40 Cu3 N5 C20 -99.6(3) . . . . ? O4 Cu3 N5 C21 -168.3(5) . . . . ? O2 Cu3 N5 C21 170.9(3) . . . . ? N6 Cu3 N5 C21 -13.4(3) . . . . ? S40 Cu3 N5 C21 80.0(2) . . . . ? C20 N5 C21 C22 -143.3(4) . . . . ? Cu3 N5 C21 C22 37.1(4) . . . . ? N5 C21 C22 N6 -49.3(4) . . . . ? C21 C22 N6 C23 167.5(3) . . . . ? C21 C22 N6 Cu3 37.3(4) . . . . ? O4 Cu3 N6 C23 34.3(3) . . . . ? N5 Cu3 N6 C23 -140.6(3) . . . . ? O2 Cu3 N6 C23 -83.8(14) . . . . ? S40 Cu3 N6 C23 126.5(3) . . . . ? O4 Cu3 N6 C22 161.2(2) . . . . ? N5 Cu3 N6 C22 -13.6(2) . . . . ? O2 Cu3 N6 C22 43.2(15) . . . . ? S40 Cu3 N6 C22 -106.5(2) . . . . ? C22 N6 C23 C24 -57.5(4) . . . . ? Cu3 N6 C23 C24 66.5(4) . . . . ? N6 C23 C24 N7 -48.3(5) . . . . ? C23 C24 N7 C25 115.7(4) . . . . ? C23 C24 N7 Cu1 -69.5(4) . . . . ? N1 Cu1 N7 C25 -5.7(3) . . . . ? N30 Cu1 N7 C25 156.3(3) . . . . ? N2 Cu1 N7 C25 -9.8(5) . . . . ? O4 Cu1 N7 C25 -109.1(3) . . . . ? N1 Cu1 N7 C24 179.5(3) . . . . ? N30 Cu1 N7 C24 -18.4(3) . . . . ? N2 Cu1 N7 C24 175.4(3) . . . . ? O4 Cu1 N7 C24 76.1(3) . . . . ? C24 N7 C25 O3 1.1(6) . . . . ? Cu1 N7 C25 O3 -174.1(3) . . . . ? C24 N7 C25 C2 -176.2(3) . . . . ? Cu1 N7 C25 C2 8.6(4) . . . . ? N1 C2 C25 O3 174.9(3) . . . . ? C3 C2 C25 O3 -7.1(6) . . . . ? N1 C2 C25 N7 -7.5(5) . . . . ? C3 C2 C25 N7 170.5(4) . . . . ? N5 Cu3 O4 Cu2 -32.9(7) . . . . ? O2 Cu3 O4 Cu2 -11.58(11) . . . . ? N6 Cu3 O4 Cu2 173.04(12) . . . . ? S40 Cu3 O4 Cu2 79.04(10) . . . . ? N5 Cu3 O4 Cu1 69.6(6) . . . . ? O2 Cu3 O4 Cu1 90.85(11) . . . . ? N6 Cu3 O4 Cu1 -84.53(12) . . . . ? S40 Cu3 O4 Cu1 -178.53(7) . . . . ? N4 Cu2 O4 Cu3 24.1(7) . . . . ? O2 Cu2 O4 Cu3 11.57(11) . . . . ? N3 Cu2 O4 Cu3 -175.19(12) . . . . ? N40 Cu2 O4 Cu3 -84.28(14) . . . . ? N4 Cu2 O4 Cu1 -76.6(7) . . . . ? O2 Cu2 O4 Cu1 -89.17(11) . . . . ? N3 Cu2 O4 Cu1 84.06(13) . . . . ? N40 Cu2 O4 Cu1 174.97(12) . . . . ? N1 Cu1 O4 Cu3 -49.46(14) . . . . ? N30 Cu1 O4 Cu3 131.74(13) . . . . ? N7 Cu1 O4 Cu3 30.73(13) . . . . ? N2 Cu1 O4 Cu3 -129.07(13) . . . . ? N1 Cu1 O4 Cu2 54.29(13) . . . . ? N30 Cu1 O4 Cu2 -124.51(14) . . . . ? N7 Cu1 O4 Cu2 134.48(12) . . . . ? N2 Cu1 O4 Cu2 -25.32(13) . . . . ? N1 Cu1 N30 C30 -55.7(11) . . . . ? N7 Cu1 N30 C30 -145.7(8) . . . . ? N2 Cu1 N30 C30 29.4(9) . . . . ? O4 Cu1 N30 C30 120.4(8) . . . . ? Cu1 N30 C30 S30 82(9) . . . . ? N4 Cu2 N40 C40 -128.1(4) . . . . ? O4 Cu2 N40 C40 41.0(4) . . . . ? O2 Cu2 N40 C40 -37.8(4) . . . . ? N3 Cu2 N40 C40 145.4(4) . . . . ? Cu2 N40 C40 S40 -37(7) . . . . ? N40 C40 S40 Cu3 36(6) . . . . ? O4 Cu3 S40 C40 -38.78(18) . . . . ? N5 Cu3 S40 C40 130.19(19) . . . . ? O2 Cu3 S40 C40 39.73(18) . . . . ? N6 Cu3 S40 C40 -142.86(19) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.37 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.831 _refine_diff_density_min -0.518 _refine_diff_density_rms 0.102