# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Jian-Ping Lang' _publ_contact_author_email JPLANG@SUDA.EDU.CN _publ_section_title ; Formation of Dimeric and Polymeric W/Cu/S Clusters via Degradation or Expansion of the Cluster Core in [Et4N]4[WS4Cu4I6] ; loop_ _publ_author_name 'Jian-Ping Lang.' 'Yang Chen.' 'Yu-Jian Huang.' 'Hong-Xi Li.' ; Ying-Lin Song ; 'Yong Zhang.' # Attachment 'Compound_2.cif' data_l _database_code_depnum_ccdc_archive 'CCDC 702177' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C28 H44 Cu6 I2 N8 S8 W2' _chemical_formula_sum 'C28 H44 Cu6 I2 N8 S8 W2' _chemical_formula_weight 1751.93 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'C m c a' _symmetry_space_group_name_Hall '-C 2bc 2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y, -z' 'x+1/2, y+1/2, z' '-x+1/2, -y+1, z+1/2' '-x+1/2, y+1, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x, y-1/2, -z-1/2' 'x, -y-1/2, z-1/2' '-x, y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, y, -z-1/2' 'x+1/2, -y, z-1/2' '-x+1/2, y+1/2, z' _cell_length_a 16.422(3) _cell_length_b 17.978(4) _cell_length_c 16.105(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 4754.8(16) _cell_formula_units_Z 4 _cell_measurement_temperature 291(2) _cell_measurement_reflns_used 6417 _cell_measurement_theta_min 3.0357 _cell_measurement_theta_max 25.3491 _exptl_crystal_description Block _exptl_crystal_colour red _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.14 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.447 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3296 _exptl_absorpt_coefficient_mu 9.128 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.250 _exptl_absorpt_correction_T_max 0.279 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication.' _exptl_special_details ; ? ; _diffrn_ambient_temperature 291(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 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 21939 _diffrn_reflns_av_R_equivalents 0.0843 _diffrn_reflns_av_sigmaI/netI 0.0422 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.04 _diffrn_reflns_theta_max 25.35 _reflns_number_total 2256 _reflns_number_gt 1970 _reflns_threshold_expression >2sigma(I) _computing_data_collection CrystalClear _computing_cell_refinement CrystalClear _computing_data_reduction CrystalStructure _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Shelxl-97 (Sheldrick, 1997)' _computing_publication_material 'Shelxl-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0161P)^2^+200.5513P] 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 2256 _refine_ls_number_parameters 131 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0809 _refine_ls_R_factor_gt 0.0674 _refine_ls_wR_factor_ref 0.1150 _refine_ls_wR_factor_gt 0.1100 _refine_ls_goodness_of_fit_ref 1.096 _refine_ls_restrained_S_all 1.096 _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 W1 W 1.0000 0.49641(4) 0.76310(4) 0.0439(2) Uani 1 2 d S . . Cu1 Cu 0.89357(10) 0.40630(9) 0.68682(10) 0.0523(4) Uani 1 1 d . . . Cu2 Cu 1.0000 0.54667(17) 0.60761(16) 0.0686(8) Uani 1 2 d S . . I1 I 1.0000 0.61793(7) 0.47683(7) 0.0502(3) Uani 1 2 d S . . S1 S 1.0000 0.3711(3) 0.7680(3) 0.0526(12) Uani 1 2 d S . . S2 S 0.8894(2) 0.53227(18) 0.6910(2) 0.0474(8) Uani 1 1 d . . . S3 S 1.0000 0.5409(4) 0.8861(4) 0.0798(18) Uani 1 2 d S . . N1 N 0.8075(6) 0.3388(6) 0.6511(6) 0.047(3) Uani 1 1 d . . . N2 N 0.7370(7) 0.3596(6) 0.6141(6) 0.050(3) Uani 1 1 d . . . C1 C 0.8069(9) 0.2642(7) 0.6534(8) 0.056(4) Uani 1 1 d . . . C2 C 0.7353(9) 0.2396(9) 0.6187(8) 0.064(4) Uani 1 1 d . . . H2A H 0.7194 0.1901 0.6140 0.077 Uiso 1 1 calc R . . C3 C 0.6907(9) 0.3005(9) 0.5919(8) 0.058(4) Uani 1 1 d . . . C4 C 0.8753(10) 0.2218(7) 0.6898(9) 0.068(4) Uani 1 1 d . . . H4A H 0.9245 0.2329 0.6601 0.103 Uiso 1 1 calc R . . H4B H 0.8640 0.1695 0.6860 0.103 Uiso 1 1 calc R . . H4C H 0.8817 0.2354 0.7471 0.103 Uiso 1 1 calc R . . C5 C 0.6115(9) 0.3064(10) 0.5504(10) 0.083(5) Uani 1 1 d . . . H5A H 0.5751 0.3353 0.5841 0.124 Uiso 1 1 calc R . . H5B H 0.5892 0.2576 0.5423 0.124 Uiso 1 1 calc R . . H5C H 0.6183 0.3303 0.4975 0.124 Uiso 1 1 calc R . . C6 C 0.7205(8) 0.4371(7) 0.5939(8) 0.052(3) Uani 1 1 d . . . H6A H 0.7502 0.4687 0.6323 0.063 Uiso 1 1 calc R . . H6B H 0.6629 0.4468 0.6016 0.063 Uiso 1 1 calc R . . C7 C 0.7439(10) 0.4578(7) 0.5064(9) 0.065(4) Uani 1 1 d . . . H7A H 0.7059 0.4351 0.4679 0.078 Uiso 1 1 calc R . . H7B H 0.7977 0.4383 0.4943 0.078 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 W1 0.0485(4) 0.0463(4) 0.0368(4) -0.0050(3) 0.000 0.000 Cu1 0.0559(10) 0.0440(9) 0.0569(10) -0.0007(7) -0.0053(8) -0.0060(8) Cu2 0.0572(16) 0.092(2) 0.0564(15) 0.0253(14) 0.000 0.000 I1 0.0666(8) 0.0406(6) 0.0433(7) 0.0004(5) 0.000 0.000 S1 0.061(3) 0.054(3) 0.043(3) 0.012(2) 0.000 0.000 S2 0.0445(18) 0.0430(18) 0.0547(19) -0.0037(15) -0.0003(15) 0.0013(15) S3 0.079(4) 0.097(5) 0.063(4) -0.021(3) 0.000 0.000 N1 0.048(6) 0.045(6) 0.049(6) 0.001(5) 0.010(5) -0.010(5) N2 0.052(7) 0.047(6) 0.051(6) -0.007(5) 0.007(5) -0.001(6) C1 0.065(9) 0.043(8) 0.060(9) -0.005(7) 0.024(7) -0.007(7) C2 0.075(11) 0.063(10) 0.056(9) -0.010(7) 0.017(8) -0.027(9) C3 0.051(8) 0.074(10) 0.050(8) -0.019(7) 0.012(7) -0.018(8) C4 0.102(13) 0.033(7) 0.070(10) 0.004(7) 0.007(9) 0.006(8) C5 0.060(10) 0.119(14) 0.069(10) -0.040(10) 0.004(8) -0.024(10) C6 0.038(7) 0.055(8) 0.064(9) -0.018(7) 0.006(6) -0.002(6) C7 0.071(9) 0.058(8) 0.067(9) -0.002(8) 0.009(8) -0.005(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag W1 S3 2.136(6) . ? W1 S2 2.250(3) . ? W1 S2 2.250(3) 12_755 ? W1 S1 2.254(5) . ? W1 Cu2 2.662(3) . ? W1 Cu1 2.6811(17) . ? W1 Cu1 2.6811(17) 12_755 ? Cu1 N1 1.950(10) . ? Cu1 S2 2.267(4) . ? Cu1 S1 2.272(3) . ? Cu2 S2 2.274(4) 12_755 ? Cu2 S2 2.274(4) . ? Cu2 I1 2.465(3) . ? S1 Cu1 2.272(3) 12_755 ? N1 C1 1.343(15) . ? N1 N2 1.354(14) . ? N2 C3 1.355(16) . ? N2 C6 1.456(16) . ? C1 C2 1.375(19) . ? C1 C4 1.479(19) . ? C2 C3 1.39(2) . ? C2 H2A 0.9300 . ? C3 C5 1.47(2) . ? C4 H4A 0.9600 . ? C4 H4B 0.9600 . ? C4 H4C 0.9600 . ? C5 H5A 0.9600 . ? C5 H5B 0.9600 . ? C5 H5C 0.9600 . ? C6 C7 1.508(18) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C7 1.53(3) 4_566 ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? 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 S3 W1 S2 111.80(13) . . ? S3 W1 S2 111.80(13) . 12_755 ? S2 W1 S2 107.64(17) . 12_755 ? S3 W1 S1 110.0(2) . . ? S2 W1 S1 107.72(10) . . ? S2 W1 S1 107.72(10) 12_755 . ? S3 W1 Cu2 138.2(2) . . ? S2 W1 Cu2 54.36(9) . . ? S2 W1 Cu2 54.36(9) 12_755 . ? S1 W1 Cu2 111.84(14) . . ? S3 W1 Cu1 130.62(11) . . ? S2 W1 Cu1 53.88(9) . . ? S2 W1 Cu1 117.57(9) 12_755 . ? S1 W1 Cu1 53.99(8) . . ? Cu2 W1 Cu1 76.94(6) . . ? S3 W1 Cu1 130.62(11) . 12_755 ? S2 W1 Cu1 117.57(9) . 12_755 ? S2 W1 Cu1 53.88(9) 12_755 12_755 ? S1 W1 Cu1 53.99(8) . 12_755 ? Cu2 W1 Cu1 76.94(6) . 12_755 ? Cu1 W1 Cu1 81.37(8) . 12_755 ? N1 Cu1 S2 127.5(3) . . ? N1 Cu1 S1 123.7(3) . . ? S2 Cu1 S1 106.51(16) . . ? N1 Cu1 W1 169.7(3) . . ? S2 Cu1 W1 53.30(9) . . ? S1 Cu1 W1 53.36(13) . . ? S2 Cu2 S2 106.03(19) 12_755 . ? S2 Cu2 I1 124.33(10) 12_755 . ? S2 Cu2 I1 124.33(10) . . ? S2 Cu2 W1 53.53(10) 12_755 . ? S2 Cu2 W1 53.53(10) . . ? I1 Cu2 W1 168.53(14) . . ? W1 S1 Cu1 72.64(13) . . ? W1 S1 Cu1 72.64(13) . 12_755 ? Cu1 S1 Cu1 100.55(19) . 12_755 ? W1 S2 Cu1 72.83(11) . . ? W1 S2 Cu2 72.11(11) . . ? Cu1 S2 Cu2 94.14(15) . . ? C1 N1 N2 106.4(11) . . ? C1 N1 Cu1 128.2(10) . . ? N2 N1 Cu1 125.3(8) . . ? N1 N2 C3 112.3(11) . . ? N1 N2 C6 121.4(10) . . ? C3 N2 C6 126.0(12) . . ? N1 C1 C2 108.4(13) . . ? N1 C1 C4 121.4(13) . . ? C2 C1 C4 130.1(13) . . ? C1 C2 C3 108.9(13) . . ? C1 C2 H2A 125.5 . . ? C3 C2 H2A 125.5 . . ? N2 C3 C2 104.0(12) . . ? N2 C3 C5 124.1(15) . . ? C2 C3 C5 131.9(14) . . ? C1 C4 H4A 109.5 . . ? C1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? N2 C6 C7 113.4(10) . . ? N2 C6 H6A 108.9 . . ? C7 C6 H6A 108.9 . . ? N2 C6 H6B 108.9 . . ? C7 C6 H6B 108.9 . . ? H6A C6 H6B 107.7 . . ? C6 C7 C7 111.6(14) . 4_566 ? C6 C7 H7A 109.3 . . ? C7 C7 H7A 109.3 4_566 . ? C6 C7 H7B 109.3 . . ? C7 C7 H7B 109.3 4_566 . ? H7A C7 H7B 108.0 . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 1.475 _refine_diff_density_min -1.212 _refine_diff_density_rms 0.179 # Attachment 'Compound_3.cif' data_t _database_code_depnum_ccdc_archive 'CCDC 702178' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C54 H72 Cu6 I2 N12 S8 W2, C3 N O, C3 N O' _chemical_formula_sum 'C60 H72 Cu6 I2 N14 O2 S8 W2' _chemical_formula_weight 2280.54 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' 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' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 12.6498(15) _cell_length_b 12.943(3) _cell_length_c 15.041(3) _cell_angle_alpha 111.395(10) _cell_angle_beta 95.08(2) _cell_angle_gamma 105.55(3) _cell_volume 2160.8(9) _cell_formula_units_Z 1 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 7469 _cell_measurement_theta_min 3.10 _cell_measurement_theta_max 25.25 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.753 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1102 _exptl_absorpt_coefficient_mu 5.048 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.315 _exptl_absorpt_correction_T_max 0.635 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private Communication.' _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 21266 _diffrn_reflns_av_R_equivalents 0.0501 _diffrn_reflns_av_sigmaI/netI 0.0655 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.11 _diffrn_reflns_theta_max 25.35 _reflns_number_total 7855 _reflns_number_gt 6030 _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^)+(0.0920P)^2^+13.7823P] 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 7855 _refine_ls_number_parameters 396 _refine_ls_number_restraints 13 _refine_ls_R_factor_all 0.0942 _refine_ls_R_factor_gt 0.0701 _refine_ls_wR_factor_ref 0.1973 _refine_ls_wR_factor_gt 0.1815 _refine_ls_goodness_of_fit_ref 1.099 _refine_ls_restrained_S_all 1.102 _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 W1 W 0.87831(4) 0.14601(4) 0.27394(3) 0.03920(18) Uani 1 1 d . . . Cu1 Cu 0.66799(11) 0.14305(13) 0.23846(10) 0.0438(4) Uani 1 1 d . . . Cu2 Cu 0.80006(13) -0.07381(13) 0.14543(11) 0.0479(4) Uani 1 1 d . . . Cu3 Cu 0.94553(15) 0.36955(15) 0.40910(13) 0.0625(5) Uani 1 1 d . . . I1 I 0.92051(10) 0.56582(9) 0.41729(8) 0.0807(4) Uani 1 1 d . . . S1 S 0.9188(3) -0.0029(3) 0.2887(3) 0.0615(9) Uani 1 1 d . . . S2 S 1.0318(3) 0.2835(3) 0.2889(3) 0.0598(9) Uani 1 1 d . . . S3 S 0.7836(3) 0.2183(3) 0.3872(2) 0.0478(7) Uani 1 1 d . . . S4 S 0.7662(2) 0.0798(3) 0.1242(2) 0.0422(7) Uani 1 1 d . . . O1 O 0.839(2) 0.190(2) 0.8201(18) 0.104(5) Uiso 0.50 1 d PD . . O2 O 0.6778(15) 0.4613(16) 0.0693(13) 0.059(3) Uiso 0.50 1 d PD . . N1 N 0.5273(8) 0.1746(8) 0.2271(7) 0.041(2) Uani 1 1 d . . . N2 N 0.4225(7) 0.0944(8) 0.1946(7) 0.036(2) Uani 1 1 d . . . N3 N 0.7804(8) -0.2187(8) 0.0364(7) 0.039(2) Uani 1 1 d . . . N4 N 0.6845(7) -0.3107(7) -0.0040(6) 0.0323(19) Uani 1 1 d . . . N5 N 0.4764(13) -0.2481(12) 0.4022(9) 0.069(4) Uani 1 1 d . . . N6 N 0.5878(14) -0.1886(12) 0.4318(8) 0.070(4) Uani 1 1 d . . . N7 N 0.8605(18) 0.1796(19) 0.6547(18) 0.104(5) Uiso 0.50 1 d PD . . N8 N 0.8568(15) 0.4637(16) 0.1031(11) 0.059(3) Uiso 0.50 1 d PD . . C1 C 0.6115(12) 0.3888(12) 0.2987(12) 0.072(4) Uani 1 1 d . . . H1A H 0.6725 0.3761 0.3313 0.107 Uiso 1 1 calc R . . H1B H 0.5919 0.4514 0.3443 0.107 Uiso 1 1 calc R . . H1C H 0.6338 0.4092 0.2463 0.107 Uiso 1 1 calc R . . C2 C 0.5143(10) 0.2812(10) 0.2593(8) 0.045(3) Uani 1 1 d . . . C3 C 0.4011(10) 0.2677(11) 0.2452(9) 0.048(3) Uani 1 1 d . . . H3 H 0.3699 0.3279 0.2612 0.058 Uiso 1 1 calc R . . C4 C 0.3435(10) 0.1511(12) 0.2041(9) 0.047(3) Uani 1 1 d . . . C5 C 0.2204(10) 0.0848(14) 0.1717(12) 0.070(4) Uani 1 1 d . . . H5A H 0.1789 0.1390 0.1875 0.105 Uiso 1 1 calc R . . H5B H 0.2007 0.0333 0.2045 0.105 Uiso 1 1 calc R . . H5C H 0.2027 0.0395 0.1025 0.105 Uiso 1 1 calc R . . C6 C 0.9675(10) -0.1533(11) 0.0009(11) 0.060(4) Uani 1 1 d . . . H6A H 0.9678 -0.0769 0.0432 0.090 Uiso 1 1 calc R . . H6B H 0.9888 -0.1509 -0.0582 0.090 Uiso 1 1 calc R . . H6C H 1.0198 -0.1767 0.0331 0.090 Uiso 1 1 calc R . . C7 C 0.8520(9) -0.2398(10) -0.0230(8) 0.041(3) Uani 1 1 d . . . C8 C 0.7993(10) -0.3467(11) -0.1035(9) 0.048(3) Uani 1 1 d . . . H8 H 0.8297 -0.3809 -0.1563 0.058 Uiso 1 1 calc R . . C9 C 0.6947(9) -0.3906(10) -0.0892(8) 0.040(3) Uani 1 1 d . . . C10 C 0.6013(11) -0.5010(11) -0.1498(9) 0.058(3) Uani 1 1 d . . . H10A H 0.5912 -0.5531 -0.1170 0.087 Uiso 1 1 calc R . . H10B H 0.6192 -0.5379 -0.2119 0.087 Uiso 1 1 calc R . . H10C H 0.5334 -0.4831 -0.1595 0.087 Uiso 1 1 calc R . . C11 C 0.3427(19) -0.4196(18) 0.4207(13) 0.103(3) Uani 1 1 d . . . H11A H 0.3496 -0.4905 0.4235 0.155 Uiso 1 1 calc R . . H11B H 0.3037 -0.4366 0.3568 0.155 Uiso 1 1 calc R . . H11C H 0.3015 -0.3874 0.4683 0.155 Uiso 1 1 calc R . . C12 C 0.463(2) -0.3280(19) 0.4433(13) 0.103(3) Uani 1 1 d . . . C13 C 0.560(2) -0.3157(19) 0.4927(13) 0.103(3) Uani 1 1 d . . . H13 H 0.5700 -0.3619 0.5258 0.124 Uiso 1 1 calc R . . C14 C 0.641(2) -0.231(2) 0.4897(13) 0.103(3) Uani 1 1 d . . . C15 C 0.7673(19) -0.1742(18) 0.5314(13) 0.103(3) Uani 1 1 d . . . H15A H 0.7939 -0.2222 0.5577 0.155 Uiso 1 1 calc R . . H15B H 0.7817 -0.0979 0.5823 0.155 Uiso 1 1 calc R . . H15C H 0.8055 -0.1669 0.4806 0.155 Uiso 1 1 calc R . . C16 C 0.4006(9) -0.0309(10) 0.1474(9) 0.042(3) Uani 1 1 d . . . H16A H 0.3915 -0.0523 0.0777 0.050 Uiso 1 1 calc R . . H16B H 0.3294 -0.0696 0.1589 0.050 Uiso 1 1 calc R . . C17 C 0.4992(10) -0.1720(11) -0.0020(8) 0.047(3) Uani 1 1 d . . . H17A H 0.5521 -0.2024 -0.0363 0.070 Uiso 1 1 calc R . . H17B H 0.5043 -0.0975 -0.0038 0.070 Uiso 1 1 calc R . . H17C H 0.4247 -0.2257 -0.0326 0.070 Uiso 1 1 calc R . . C18 C 0.5929(9) -0.3298(9) 0.0463(8) 0.037(2) Uani 1 1 d . . . H18A H 0.5998 -0.3855 0.0737 0.044 Uiso 1 1 calc R . . H18B H 0.5229 -0.3657 -0.0016 0.044 Uiso 1 1 calc R . . C19 C 0.6910(11) -0.2683(12) 0.2499(9) 0.053(3) Uani 1 1 d . . . H19A H 0.6460 -0.3244 0.2705 0.079 Uiso 1 1 calc R . . H19B H 0.7537 -0.2146 0.3019 0.079 Uiso 1 1 calc R . . H19C H 0.7178 -0.3084 0.1938 0.079 Uiso 1 1 calc R . . C20 C 0.6331(13) -0.0935(12) 0.4021(9) 0.059(4) Uani 1 1 d . . . H20A H 0.7141 -0.0736 0.4138 0.071 Uiso 1 1 calc R . . H20B H 0.6159 -0.0252 0.4436 0.071 Uiso 1 1 calc R . . C21 C 0.4682(10) 0.0080(11) 0.3551(8) 0.047(3) Uani 1 1 d . . . H21A H 0.4621 -0.0239 0.4036 0.070 Uiso 1 1 calc R . . H21B H 0.3954 0.0053 0.3281 0.070 Uiso 1 1 calc R . . H21C H 0.5171 0.0879 0.3845 0.070 Uiso 1 1 calc R . . C22 C 0.4864(9) -0.0805(10) 0.1770(8) 0.039(3) Uani 1 1 d . . . C23 C 0.5257(8) -0.1568(9) 0.1044(7) 0.034(2) Uani 1 1 d . . . C24 C 0.5855(8) -0.2226(9) 0.1266(8) 0.033(2) Uani 1 1 d . . . C25 C 0.6210(9) -0.2011(10) 0.2238(8) 0.038(2) Uani 1 1 d . . . C26 C 0.5916(9) -0.1177(9) 0.2987(7) 0.037(2) Uani 1 1 d . . . C27 C 0.5163(10) -0.0641(10) 0.2739(8) 0.040(3) Uani 1 1 d . . . C28 C 0.920(3) 0.130(3) 0.577(2) 0.104(5) Uiso 0.50 1 d PD . . C29 C 0.790(3) 0.246(3) 0.643(3) 0.104(5) Uiso 0.50 1 d PD . . C30 C 0.873(3) 0.156(3) 0.740(2) 0.104(5) Uiso 0.50 1 d PD . . C31 C 0.894(2) 0.5936(19) 0.1294(19) 0.059(3) Uiso 0.50 1 d PD . . C32 C 0.944(2) 0.415(2) 0.1162(18) 0.059(3) Uiso 0.50 1 d PD . . C33 C 0.7461(16) 0.409(2) 0.0708(18) 0.059(3) Uiso 0.50 1 d PD . . 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 W1 0.0352(3) 0.0356(3) 0.0364(3) 0.0060(2) 0.0042(2) 0.0084(2) Cu1 0.0375(7) 0.0466(9) 0.0444(8) 0.0144(7) 0.0075(6) 0.0152(7) Cu2 0.0494(9) 0.0344(8) 0.0466(9) 0.0038(7) 0.0062(7) 0.0117(7) Cu3 0.0603(10) 0.0460(10) 0.0585(10) 0.0029(8) 0.0118(8) 0.0081(8) I1 0.0850(8) 0.0529(6) 0.0757(7) 0.0100(5) -0.0132(6) 0.0105(5) S1 0.060(2) 0.053(2) 0.062(2) 0.0163(18) -0.0079(17) 0.0214(17) S2 0.0477(18) 0.050(2) 0.060(2) 0.0071(17) 0.0163(16) 0.0033(15) S3 0.0441(16) 0.0512(18) 0.0347(15) 0.0069(14) 0.0084(13) 0.0094(14) S4 0.0473(16) 0.0397(16) 0.0309(14) 0.0066(12) 0.0058(12) 0.0119(13) N1 0.048(6) 0.042(6) 0.037(5) 0.012(4) 0.011(4) 0.023(5) N2 0.033(5) 0.039(5) 0.041(5) 0.014(4) 0.012(4) 0.019(4) N3 0.042(5) 0.039(5) 0.037(5) 0.017(4) 0.014(4) 0.013(4) N4 0.041(5) 0.021(4) 0.034(5) 0.008(4) 0.012(4) 0.011(4) N5 0.116(11) 0.070(9) 0.058(8) 0.044(7) 0.039(8) 0.053(9) N6 0.131(12) 0.080(9) 0.036(6) 0.032(6) 0.026(7) 0.072(9) C1 0.065(9) 0.048(9) 0.091(12) 0.019(8) 0.011(8) 0.017(7) C2 0.053(7) 0.043(7) 0.037(6) 0.012(6) 0.000(5) 0.020(6) C3 0.049(7) 0.051(8) 0.052(7) 0.019(6) 0.016(6) 0.028(6) C4 0.041(6) 0.061(8) 0.050(7) 0.030(7) 0.012(6) 0.024(6) C5 0.040(7) 0.087(11) 0.088(11) 0.032(9) 0.007(7) 0.035(8) C6 0.032(6) 0.049(8) 0.090(11) 0.019(7) 0.024(7) 0.007(6) C7 0.043(6) 0.036(6) 0.046(7) 0.016(6) 0.013(5) 0.015(5) C8 0.046(7) 0.046(7) 0.047(7) 0.010(6) 0.022(6) 0.015(6) C9 0.038(6) 0.038(6) 0.045(7) 0.020(6) 0.013(5) 0.008(5) C10 0.064(8) 0.047(8) 0.043(7) -0.002(6) 0.018(6) 0.014(7) C11 0.165(10) 0.102(7) 0.062(5) 0.029(5) 0.033(6) 0.075(7) C12 0.165(10) 0.102(7) 0.062(5) 0.029(5) 0.033(6) 0.075(7) C13 0.165(10) 0.102(7) 0.062(5) 0.029(5) 0.033(6) 0.075(7) C14 0.165(10) 0.102(7) 0.062(5) 0.029(5) 0.033(6) 0.075(7) C15 0.165(10) 0.102(7) 0.062(5) 0.029(5) 0.033(6) 0.075(7) C16 0.034(6) 0.037(6) 0.044(7) 0.009(5) 0.000(5) 0.009(5) C17 0.056(7) 0.053(7) 0.033(6) 0.019(6) 0.009(6) 0.019(6) C18 0.036(6) 0.030(6) 0.046(6) 0.013(5) 0.020(5) 0.013(5) C19 0.051(7) 0.059(8) 0.054(8) 0.023(7) 0.012(6) 0.027(7) C20 0.088(10) 0.055(8) 0.037(7) 0.012(6) 0.017(7) 0.034(8) C21 0.058(7) 0.054(8) 0.031(6) 0.013(6) 0.021(6) 0.026(6) C22 0.032(6) 0.047(7) 0.040(6) 0.019(5) 0.009(5) 0.015(5) C23 0.030(5) 0.033(6) 0.034(6) 0.011(5) 0.015(5) 0.005(5) C24 0.033(5) 0.029(5) 0.041(6) 0.015(5) 0.014(5) 0.015(5) C25 0.042(6) 0.036(6) 0.037(6) 0.018(5) 0.007(5) 0.010(5) C26 0.041(6) 0.031(6) 0.027(5) 0.005(5) 0.002(5) 0.006(5) C27 0.048(7) 0.037(6) 0.038(6) 0.011(5) 0.013(5) 0.024(5) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag W1 S2 2.183(3) . ? W1 S1 2.202(4) . ? W1 S3 2.239(3) . ? W1 S4 2.278(3) . ? W1 Cu2 2.6361(17) . ? W1 Cu1 2.6540(15) . ? W1 Cu3 2.7038(19) . ? Cu1 N1 1.936(9) . ? Cu1 S4 2.250(3) . ? Cu1 S3 2.271(3) . ? Cu2 N3 1.924(9) . ? Cu2 S1 2.233(4) . ? Cu2 S4 2.266(3) . ? Cu3 S2 2.288(4) . ? Cu3 S3 2.323(4) . ? Cu3 I1 2.603(2) . ? Cu3 I1 2.693(2) 2_766 ? I1 Cu3 2.693(2) 2_766 ? O1 C30 1.279(18) . ? O2 C33 1.233(17) . ? N1 C2 1.347(14) . ? N1 N2 1.361(13) . ? N2 C4 1.379(14) . ? N2 C16 1.447(14) . ? N3 C7 1.339(14) . ? N3 N4 1.351(12) . ? N4 C9 1.364(14) . ? N4 C18 1.454(12) . ? N5 N6 1.355(18) . ? N5 C12 1.37(2) . ? N6 C14 1.40(2) . ? N6 C20 1.453(18) . ? N7 C30 1.423(19) . ? N7 C29 1.435(19) . ? N7 C28 1.482(19) . ? N8 C33 1.340(17) . ? N8 C32 1.435(17) . ? N8 C31 1.504(18) . ? C1 C2 1.467(18) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 C3 1.382(16) . ? C3 C4 1.356(18) . ? C3 H3 0.9300 . ? C4 C5 1.497(17) . ? C5 H5A 0.9600 . ? C5 H5B 0.9600 . ? C5 H5C 0.9600 . ? C6 C7 1.502(16) . ? C6 H6A 0.9600 . ? C6 H6B 0.9600 . ? C6 H6C 0.9600 . ? C7 C8 1.401(16) . ? C8 C9 1.363(15) . ? C8 H8 0.9300 . ? C9 C10 1.491(17) . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 C12 1.58(3) . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 C13 1.32(3) . ? C13 C14 1.30(3) . ? C13 H13 0.9300 . ? C14 C15 1.53(3) . ? C15 H15A 0.9600 . ? C15 H15B 0.9600 . ? C15 H15C 0.9600 . ? C16 C22 1.511(15) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 C23 1.534(15) . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? C18 C24 1.503(14) . ? C18 H18A 0.9700 . ? C18 H18B 0.9700 . ? C19 C25 1.515(15) . ? C19 H19A 0.9600 . ? C19 H19B 0.9600 . ? C19 H19C 0.9600 . ? C20 C26 1.485(16) . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C21 C27 1.528(14) . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9600 . ? C22 C27 1.395(15) . ? C22 C23 1.410(14) . ? C23 C24 1.384(14) . ? C24 C25 1.392(15) . ? C25 C26 1.406(15) . ? C26 C27 1.417(15) . ? 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 S2 W1 S1 110.21(14) . . ? S2 W1 S3 109.68(12) . . ? S1 W1 S3 110.38(14) . . ? S2 W1 S4 110.17(13) . . ? S1 W1 S4 108.29(12) . . ? S3 W1 S4 108.07(11) . . ? S2 W1 Cu2 129.05(10) . . ? S1 W1 Cu2 54.08(10) . . ? S3 W1 Cu2 121.25(9) . . ? S4 W1 Cu2 54.32(8) . . ? S2 W1 Cu1 128.06(11) . . ? S1 W1 Cu1 121.71(11) . . ? S3 W1 Cu1 54.52(9) . . ? S4 W1 Cu1 53.63(8) . . ? Cu2 W1 Cu1 84.66(6) . . ? S2 W1 Cu3 54.58(10) . . ? S1 W1 Cu3 126.74(11) . . ? S3 W1 Cu3 55.11(9) . . ? S4 W1 Cu3 124.97(9) . . ? Cu2 W1 Cu3 176.30(5) . . ? Cu1 W1 Cu3 92.20(6) . . ? N1 Cu1 S4 130.4(3) . . ? N1 Cu1 S3 119.7(3) . . ? S4 Cu1 S3 107.92(12) . . ? N1 Cu1 W1 168.5(3) . . ? S4 Cu1 W1 54.62(8) . . ? S3 Cu1 W1 53.39(8) . . ? N3 Cu2 S1 126.0(3) . . ? N3 Cu2 S4 121.5(3) . . ? S1 Cu2 S4 107.65(13) . . ? N3 Cu2 W1 163.1(3) . . ? S1 Cu2 W1 52.99(10) . . ? S4 Cu2 W1 54.77(8) . . ? S2 Cu3 S3 103.26(13) . . ? S2 Cu3 I1 115.60(13) . . ? S3 Cu3 I1 116.83(11) . . ? S2 Cu3 I1 108.06(12) . 2_766 ? S3 Cu3 I1 109.92(11) . 2_766 ? I1 Cu3 I1 102.99(7) . 2_766 ? S2 Cu3 W1 51.04(9) . . ? S3 Cu3 W1 52.23(8) . . ? I1 Cu3 W1 135.62(8) . . ? I1 Cu3 W1 121.34(8) 2_766 . ? Cu3 I1 Cu3 77.01(7) . 2_766 ? W1 S1 Cu2 72.93(11) . . ? W1 S2 Cu3 74.39(11) . . ? W1 S3 Cu1 72.09(9) . . ? W1 S3 Cu3 72.66(10) . . ? Cu1 S3 Cu3 114.32(15) . . ? Cu1 S4 Cu2 104.15(13) . . ? Cu1 S4 W1 71.75(9) . . ? Cu2 S4 W1 70.92(10) . . ? C2 N1 N2 106.7(9) . . ? C2 N1 Cu1 126.2(8) . . ? N2 N1 Cu1 126.9(7) . . ? N1 N2 C4 109.8(9) . . ? N1 N2 C16 123.6(8) . . ? C4 N2 C16 126.3(10) . . ? C7 N3 N4 106.9(9) . . ? C7 N3 Cu2 126.4(8) . . ? N4 N3 Cu2 125.9(7) . . ? N3 N4 C9 110.4(8) . . ? N3 N4 C18 123.4(8) . . ? C9 N4 C18 125.3(9) . . ? N6 N5 C12 102.6(15) . . ? N5 N6 C14 111.5(16) . . ? N5 N6 C20 118.3(11) . . ? C14 N6 C20 130.2(18) . . ? C30 N7 C29 120.9(19) . . ? C30 N7 C28 117.8(17) . . ? C29 N7 C28 121(3) . . ? C33 N8 C32 129(2) . . ? C33 N8 C31 114.6(19) . . ? C32 N8 C31 117(2) . . ? C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 C3 109.2(11) . . ? N1 C2 C1 121.2(11) . . ? C3 C2 C1 129.7(11) . . ? C4 C3 C2 107.9(10) . . ? C4 C3 H3 126.0 . . ? C2 C3 H3 126.0 . . ? C3 C4 N2 106.5(10) . . ? C3 C4 C5 131.9(11) . . ? N2 C4 C5 121.7(12) . . ? C4 C5 H5A 109.5 . . ? C4 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C4 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? C7 C6 H6A 109.5 . . ? C7 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C7 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? N3 C7 C8 109.2(10) . . ? N3 C7 C6 120.4(11) . . ? C8 C7 C6 130.4(11) . . ? C9 C8 C7 106.5(10) . . ? C9 C8 H8 126.7 . . ? C7 C8 H8 126.7 . . ? C8 C9 N4 107.0(10) . . ? C8 C9 C10 130.9(11) . . ? N4 C9 C10 122.1(10) . . ? C9 C10 H10A 109.5 . . ? C9 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C9 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C12 C11 H11A 109.5 . . ? C12 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C12 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C13 C12 N5 110(2) . . ? C13 C12 C11 132(2) . . ? N5 C12 C11 117.9(19) . . ? C14 C13 C12 112(2) . . ? C14 C13 H13 124.1 . . ? C12 C13 H13 124.1 . . ? C13 C14 N6 104(2) . . ? C13 C14 C15 137(2) . . ? N6 C14 C15 120(2) . . ? C14 C15 H15A 109.5 . . ? C14 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? C14 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? N2 C16 C22 118.0(9) . . ? N2 C16 H16A 107.8 . . ? C22 C16 H16A 107.8 . . ? N2 C16 H16B 107.8 . . ? C22 C16 H16B 107.8 . . ? H16A C16 H16B 107.2 . . ? C23 C17 H17A 109.5 . . ? C23 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C23 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? N4 C18 C24 116.1(9) . . ? N4 C18 H18A 108.3 . . ? C24 C18 H18A 108.3 . . ? N4 C18 H18B 108.3 . . ? C24 C18 H18B 108.3 . . ? H18A C18 H18B 107.4 . . ? C25 C19 H19A 109.5 . . ? C25 C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C25 C19 H19C 109.5 . . ? H19A C19 H19C 109.5 . . ? H19B C19 H19C 109.5 . . ? N6 C20 C26 115.7(12) . . ? N6 C20 H20A 108.4 . . ? C26 C20 H20A 108.4 . . ? N6 C20 H20B 108.4 . . ? C26 C20 H20B 108.4 . . ? H20A C20 H20B 107.4 . . ? C27 C21 H21A 109.5 . . ? C27 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C27 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C27 C22 C23 119.2(10) . . ? C27 C22 C16 120.7(9) . . ? C23 C22 C16 119.6(10) . . ? C24 C23 C22 121.1(10) . . ? C24 C23 C17 118.5(9) . . ? C22 C23 C17 120.4(10) . . ? C23 C24 C25 119.4(9) . . ? C23 C24 C18 119.4(10) . . ? C25 C24 C18 120.2(9) . . ? C24 C25 C26 120.5(10) . . ? C24 C25 C19 120.2(10) . . ? C26 C25 C19 119.3(10) . . ? C25 C26 C27 119.2(10) . . ? C25 C26 C20 119.6(10) . . ? C27 C26 C20 121.0(10) . . ? C22 C27 C26 119.7(9) . . ? C22 C27 C21 122.2(10) . . ? C26 C27 C21 118.1(10) . . ? O1 C30 N7 134(3) . . ? O2 C33 N8 123(2) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 1.023 _refine_diff_density_min -1.373 _refine_diff_density_rms 0.190 # Attachment 'Compound_4.cif' data_2 _database_code_depnum_ccdc_archive 'CCDC 702179' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H22 Cu10 I12 N4 S8 W2, 2(C8 H20 N), 2(C8 H20 N), 2(C8 H20 N)' _chemical_formula_sum 'C62 H144 Cu10 I12 N10 S8 W2' _chemical_formula_weight 3812.40 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' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'I b a m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-x+1, y+1, -z+1/2' 'x+1, -y+1, -z+1/2' '-x, -y, -z' 'x, y, -z' 'x-1/2, -y-1/2, z' '-x-1/2, y-1/2, z' '-x+1/2, -y+1/2, -z+1/2' 'x+1/2, y+1/2, -z+1/2' 'x, -y, z+1/2' '-x, y, z+1/2' _cell_length_a 36.551(15) _cell_length_b 13.029(4) _cell_length_c 26.208(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 12481(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.24 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.921 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 6536 _exptl_absorpt_coefficient_mu 6.629 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.2677 _exptl_absorpt_correction_T_max 0.2991 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 25136 _diffrn_reflns_av_R_equivalents 0.0885 _diffrn_reflns_av_sigmaI/netI 0.0967 _diffrn_reflns_limit_h_min -43 _diffrn_reflns_limit_h_max 27 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 25.10 _reflns_number_total 5659 _reflns_number_gt 2604 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.0511P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5659 _refine_ls_number_parameters 222 _refine_ls_number_restraints 24 _refine_ls_R_factor_all 0.1217 _refine_ls_R_factor_gt 0.0556 _refine_ls_wR_factor_ref 0.1424 _refine_ls_wR_factor_gt 0.1321 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.085 _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 W1 W 0.151795(18) 0.90932(6) 0.5000 0.0510(2) Uani 1 2 d S . . Cu1 Cu 0.12210(5) 1.01024(14) 0.58062(7) 0.0827(6) Uani 1 1 d . . . Cu2 Cu 0.16366(5) 0.78780(14) 0.41719(7) 0.0816(6) Uani 1 1 d . . . Cu3 Cu 0.08787(7) 0.8098(2) 0.5000 0.1132(12) Uani 1 2 d S . . I1 I 0.10714(3) 1.17493(9) 0.62398(4) 0.0991(4) Uani 1 1 d . . . I2 I 0.20156(3) 0.66206(9) 0.36901(4) 0.0957(4) Uani 1 1 d . . . I3 I 0.09549(3) 0.83006(9) 0.36954(4) 0.0968(4) Uani 1 1 d . . . S1 S 0.18258(9) 0.9571(3) 0.43031(12) 0.0627(9) Uani 1 1 d . . . S2 S 0.09590(11) 0.9839(3) 0.5000 0.0582(13) Uani 1 2 d S . . S3 S 0.14440(12) 0.7362(3) 0.5000 0.0594(13) Uani 1 2 d S . . N1 N 0.0420(5) 0.7314(16) 0.5000 0.118(7) Uiso 1 2 d SD . . N2 N 0.0088(4) 0.7668(14) 0.5000 0.073(5) Uani 1 2 d SD . . N3 N 0.1969(4) 1.0000 0.2500 0.083(5) Uiso 1 2 d SD . . N4 N 0.1993(4) 1.3274(12) 0.5000 0.066(4) Uani 1 2 d S . . N5 N 0.0000 1.0000 0.2500 0.100(9) Uani 1 4 d SD . . C1 C 0.0366(6) 0.652(2) 0.4655(8) 0.100(11) Uani 0.50 1 d PD . . C2 C 0.0002(7) 0.624(2) 0.4695(9) 0.093(10) Uani 0.50 1 d PD . . C3 C -0.0184(6) 0.6954(18) 0.5000 0.110(9) Uani 1 2 d SD . . C4 C 0.0658(7) 0.586(2) 0.4423(11) 0.100 Uiso 0.50 1 d PD . . H4A H 0.0552 0.5411 0.4173 0.150 Uiso 0.50 1 calc PR . . H4B H 0.0773 0.5457 0.4685 0.150 Uiso 0.50 1 calc PR . . H4C H 0.0838 0.6289 0.4262 0.150 Uiso 0.50 1 calc PR . . C5 C -0.0561(5) 0.7074(19) 0.5000 0.134(11) Uani 1 2 d S . . C6 C 0.0066(7) 0.862(2) 0.4732(10) 0.068(8) Uani 0.50 1 d P . . C7 C 0.0007(5) 0.944(2) 0.5000 0.121(10) Uani 1 2 d S . . C8 C 0.1978(4) 0.9248(12) 0.2082(5) 0.100 Uiso 1 1 d D . . C9 C 0.1983(5) 0.8119(13) 0.2277(7) 0.131(7) Uani 1 1 d . . . H9A H 0.1989 0.7660 0.1991 0.197 Uiso 1 1 calc R . . H9B H 0.1767 0.7991 0.2475 0.197 Uiso 1 1 calc R . . H9C H 0.2195 0.8011 0.2485 0.197 Uiso 1 1 calc R . . C10 C 0.2322(8) 0.967(3) 0.2862(12) 0.105(11) Uiso 0.50 1 d PD . . C11 C 0.2658(9) 1.0000 0.2500 0.169(12) Uiso 1 2 d SD . . C12 C 0.1652(5) 0.9767(19) 0.2834(8) 0.066(7) Uiso 0.50 1 d PD . . C13 C 0.1296(6) 1.0000 0.2500 0.117(8) Uiso 1 2 d SD . . C14 C 0.1587(6) 1.3474(18) 0.5000 0.099(7) Uiso 1 2 d S . . C15 C 0.1549(7) 1.471(2) 0.5000 0.141(10) Uiso 1 2 d S . . C16 C 0.2186(4) 1.3728(12) 0.4546(7) 0.107(6) Uani 1 1 d . . . H16A H 0.2446 1.3590 0.4579 0.128 Uiso 1 1 calc R . . H16B H 0.2154 1.4467 0.4554 0.128 Uiso 1 1 calc R . . C17 C 0.2052(5) 1.3315(16) 0.4003(8) 0.142(7) Uani 1 1 d . . . H17A H 0.2188 1.3652 0.3737 0.212 Uiso 1 1 calc R . . H17B H 0.1796 1.3456 0.3961 0.212 Uiso 1 1 calc R . . H17C H 0.2093 1.2588 0.3983 0.212 Uiso 1 1 calc R . . C18 C 0.2008(6) 1.2132(18) 0.5000 0.091(7) Uiso 1 2 d S . . H18A H 0.1793 1.1750 0.5000 0.110 Uiso 1 2 calc SR . . C19 C 0.2399(6) 1.1561(18) 0.5000 0.097(7) Uiso 1 2 d S . . C20 C 0.0222(4) 1.0921(11) 0.2661(6) 0.100 Uiso 1 1 d D . 2 C21 C 0.0000 1.1834(17) 0.2500 0.100 Uiso 1 2 d SD . 2 C22 C 0.0258(4) 1.0013(12) 0.2937(5) 0.100 Uiso 1 1 d D . 1 C23 C 0.0000 1.0000 0.3424(8) 0.100 Uiso 1 2 d SD . 1 N6 N 0.0939(9) 0.5000 0.2500 0.100 Uiso 0.50 2 d SPD . . C27 C 0.1248(14) 0.335(3) 0.242(2) 0.100 Uiso 0.25 1 d PD . . C25 C 0.1041(17) 0.481(4) 0.3414(8) 0.100 Uiso 0.25 1 d PD . . C26 C 0.0897(11) 0.3925(15) 0.249(2) 0.100 Uiso 0.25 1 d PD . . C24 C 0.1011(16) 0.551(3) 0.2963(10) 0.100 Uiso 0.25 1 d PD . . 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 W1 0.0418(4) 0.0522(5) 0.0588(5) 0.000 0.000 0.0064(4) Cu1 0.0706(12) 0.0899(14) 0.0875(13) -0.0218(11) 0.0037(10) 0.0165(10) Cu2 0.0910(14) 0.0753(14) 0.0785(12) -0.0131(10) 0.0136(10) 0.0082(10) Cu3 0.0494(16) 0.0530(18) 0.237(4) 0.000 0.000 -0.0004(13) I1 0.1199(9) 0.0805(8) 0.0970(8) -0.0180(6) 0.0007(7) 0.0246(7) I2 0.1025(8) 0.1050(9) 0.0797(7) -0.0268(6) 0.0068(6) 0.0271(7) I3 0.0865(8) 0.0914(8) 0.1127(9) -0.0163(7) -0.0419(7) 0.0101(6) S1 0.0518(19) 0.074(2) 0.063(2) 0.0036(19) 0.0052(17) 0.0073(18) S2 0.042(3) 0.055(3) 0.078(3) 0.000 0.000 0.004(2) S3 0.060(3) 0.046(3) 0.072(3) 0.000 0.000 0.014(2) N2 0.049(10) 0.057(12) 0.112(14) 0.000 0.000 0.000(9) N4 0.046(9) 0.057(11) 0.095(12) 0.000 0.000 -0.014(8) N5 0.041(13) 0.15(3) 0.11(2) 0.000 0.000 0.000 C1 0.055(18) 0.20(4) 0.047(17) -0.03(2) 0.015(14) 0.01(2) C2 0.08(2) 0.07(2) 0.12(3) -0.012(19) -0.023(19) 0.001(18) C3 0.079(19) 0.058(17) 0.19(3) 0.000 0.000 -0.008(15) C5 0.027(12) 0.12(2) 0.25(3) 0.000 0.000 0.003(13) C6 0.08(2) 0.043(17) 0.083(19) -0.018(16) -0.004(15) -0.021(16) C7 0.037(12) 0.09(2) 0.24(3) 0.000 0.000 -0.017(16) C9 0.160(18) 0.105(16) 0.128(16) 0.011(12) -0.035(14) 0.029(12) C16 0.070(10) 0.088(13) 0.163(18) 0.013(12) -0.005(12) -0.020(9) C17 0.118(16) 0.16(2) 0.145(19) 0.012(16) -0.023(14) -0.002(14) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag W1 S1 2.234(3) . ? W1 S1 2.234(3) 10_556 ? W1 S2 2.262(4) . ? W1 S3 2.271(5) . ? W1 Cu3 2.672(3) . ? W1 Cu1 2.7152(18) 10_556 ? W1 Cu1 2.7152(18) . ? W1 Cu2 2.7212(18) . ? W1 Cu2 2.7212(18) 10_556 ? Cu1 S1 2.334(4) 10_556 ? Cu1 S2 2.345(3) . ? Cu1 I1 2.489(2) . ? Cu1 I3 2.857(2) 10_556 ? Cu2 S1 2.337(4) . ? Cu2 S3 2.378(3) . ? Cu2 I2 2.489(2) . ? Cu2 I3 2.841(2) . ? Cu3 N1 1.96(2) . ? Cu3 S3 2.278(5) . ? Cu3 S2 2.287(5) . ? I3 Cu1 2.857(2) 10_556 ? S1 Cu1 2.334(4) 10_556 ? S2 Cu1 2.345(3) 10_556 ? S3 Cu2 2.378(3) 10_556 ? N1 N2 1.299(15) . ? N1 C1 1.393(17) . ? N1 C1 1.393(17) 10_556 ? N2 C3 1.362(16) . ? N2 C6 1.43(3) 10_556 ? N2 C6 1.43(3) . ? N3 C8 1.470(13) . ? N3 C8 1.470(13) 8_465 ? N3 C12 1.483(16) 8_465 ? N3 C12 1.483(16) . ? N3 C10 1.66(3) . ? N3 C10 1.66(3) 8_465 ? N4 C18 1.49(2) . ? N4 C16 1.504(17) . ? N4 C16 1.504(17) 10_556 ? N4 C14 1.51(2) . ? N5 C22 1.485(13) 7_445 ? N5 C22 1.485(13) 2_575 ? N5 C22 1.485(13) . ? N5 C22 1.485(13) 8_465 ? N5 C20 1.508(13) 2_575 ? N5 C20 1.508(13) 7_445 ? N5 C20 1.508(13) . ? N5 C20 1.508(13) 8_465 ? C1 C2 1.381(18) . ? C1 C4 1.499(18) . ? C1 C1 1.81(4) 10_556 ? C2 C3 1.403(17) . ? C2 C2 1.60(4) 10_556 ? C3 C5 1.39(3) . ? C3 C2 1.403(17) 10_556 ? C4 H4A 0.9600 . ? C4 H4B 0.9600 . ? C4 H4C 0.9600 . ? C6 C7 1.30(3) . ? C6 C6 1.40(5) 10_556 ? C7 C6 1.30(3) 10_556 ? C7 C7 1.47(5) 9_576 ? C8 C9 1.56(2) . ? C8 C12 1.77(3) 8_465 ? C8 C10 1.89(3) 8_465 ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 C11 1.611(18) . ? C10 C8 1.89(3) 8_465 ? C11 C10 1.611(18) 8_465 ? C12 C13 1.596(17) . ? C12 C8 1.77(3) 8_465 ? C12 C12 1.85(4) 8_465 ? C13 C12 1.596(17) 8_465 ? C14 C15 1.61(3) . ? C16 C17 1.60(2) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 H17A 0.9600 . ? C17 H17B 0.9600 . ? C17 H17C 0.9600 . ? C18 C19 1.61(3) . ? C18 H18A 0.9300 . ? C20 C21 1.500(15) . ? C20 C20 1.83(3) 7_445 ? C21 C20 1.500(15) 7_445 ? C22 C23 1.587(15) . ? C22 C22 1.89(3) 2_575 ? C23 C22 1.587(15) 2_575 ? N6 C24 1.41(2) . ? N6 C24 1.41(2) 8_455 ? N6 C26 1.41(2) . ? N6 C26 1.41(2) 8_455 ? C27 C26 1.494(16) . ? C27 C24 1.99(6) 8_455 ? C25 C24 1.498(16) . ? C26 C24 1.46(6) 8_455 ? C24 C26 1.46(6) 8_455 ? C24 C27 1.99(6) 8_455 ? 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 S1 W1 S1 109.71(18) . 10_556 ? S1 W1 S2 109.58(10) . . ? S1 W1 S2 109.58(10) 10_556 . ? S1 W1 S3 109.67(11) . . ? S1 W1 S3 109.67(11) 10_556 . ? S2 W1 S3 108.60(16) . . ? S1 W1 Cu3 125.15(9) . . ? S1 W1 Cu3 125.15(9) 10_556 . ? S2 W1 Cu3 54.45(13) . . ? S3 W1 Cu3 54.15(12) . . ? S1 W1 Cu1 55.25(9) . 10_556 ? S1 W1 Cu1 134.65(11) 10_556 10_556 ? S2 W1 Cu1 55.32(5) . 10_556 ? S3 W1 Cu1 115.68(7) . 10_556 ? Cu3 W1 Cu1 83.41(6) . 10_556 ? S1 W1 Cu1 134.65(11) . . ? S1 W1 Cu1 55.25(9) 10_556 . ? S2 W1 Cu1 55.32(5) . . ? S3 W1 Cu1 115.68(7) . . ? Cu3 W1 Cu1 83.41(6) . . ? Cu1 W1 Cu1 102.19(8) 10_556 . ? S1 W1 Cu2 55.23(10) . . ? S1 W1 Cu2 137.23(10) 10_556 . ? S2 W1 Cu2 113.19(7) . . ? S3 W1 Cu2 56.03(5) . . ? Cu3 W1 Cu2 81.79(5) . . ? Cu1 W1 Cu2 74.03(6) 10_556 . ? Cu1 W1 Cu2 165.05(6) . . ? S1 W1 Cu2 137.23(10) . 10_556 ? S1 W1 Cu2 55.23(10) 10_556 10_556 ? S2 W1 Cu2 113.19(7) . 10_556 ? S3 W1 Cu2 56.03(5) . 10_556 ? Cu3 W1 Cu2 81.79(5) . 10_556 ? Cu1 W1 Cu2 165.05(6) 10_556 10_556 ? Cu1 W1 Cu2 74.03(6) . 10_556 ? Cu2 W1 Cu2 105.79(8) . 10_556 ? S1 Cu1 S2 103.45(14) 10_556 . ? S1 Cu1 I1 121.32(12) 10_556 . ? S2 Cu1 I1 116.62(13) . . ? S1 Cu1 W1 51.84(9) 10_556 . ? S2 Cu1 W1 52.49(10) . . ? I1 Cu1 W1 149.39(9) . . ? S1 Cu1 I3 97.74(11) 10_556 10_556 ? S2 Cu1 I3 98.78(12) . 10_556 ? I1 Cu1 I3 115.15(8) . 10_556 ? W1 Cu1 I3 95.39(6) . 10_556 ? S1 Cu2 S3 102.71(15) . . ? S1 Cu2 I2 122.08(11) . . ? S3 Cu2 I2 116.20(13) . . ? S1 Cu2 W1 51.73(9) . . ? S3 Cu2 W1 52.37(11) . . ? I2 Cu2 W1 151.18(8) . . ? S1 Cu2 I3 98.12(10) . . ? S3 Cu2 I3 101.32(12) . . ? I2 Cu2 I3 113.12(7) . . ? W1 Cu2 I3 95.63(6) . . ? N1 Cu3 S3 123.7(6) . . ? N1 Cu3 S2 128.8(6) . . ? S3 Cu3 S2 107.51(18) . . ? N1 Cu3 W1 177.6(6) . . ? S3 Cu3 W1 53.91(13) . . ? S2 Cu3 W1 53.60(12) . . ? Cu2 I3 Cu1 70.11(6) . 10_556 ? W1 S1 Cu1 72.90(11) . 10_556 ? W1 S1 Cu2 73.03(11) . . ? Cu1 S1 Cu2 88.95(13) 10_556 . ? W1 S2 Cu3 71.95(14) . . ? W1 S2 Cu1 72.19(11) . . ? Cu3 S2 Cu1 101.40(13) . . ? W1 S2 Cu1 72.19(11) . 10_556 ? Cu3 S2 Cu1 101.40(13) . 10_556 ? Cu1 S2 Cu1 128.6(2) . 10_556 ? W1 S3 Cu3 71.94(15) . . ? W1 S3 Cu2 71.60(12) . . ? Cu3 S3 Cu2 98.60(12) . . ? W1 S3 Cu2 71.60(12) . 10_556 ? Cu3 S3 Cu2 98.60(12) . 10_556 ? Cu2 S3 Cu2 131.7(2) . 10_556 ? N2 N1 C1 97.5(16) . . ? N2 N1 C1 97.5(16) . 10_556 ? C1 N1 C1 81(2) . 10_556 ? N2 N1 Cu3 127.9(16) . . ? C1 N1 Cu3 120.7(14) . . ? C1 N1 Cu3 120.7(14) 10_556 . ? N1 N2 C3 116.2(19) . . ? N1 N2 C6 111.1(17) . 10_556 ? C3 N2 C6 123.5(16) . 10_556 ? N1 N2 C6 111.1(17) . . ? C3 N2 C6 123.5(16) . . ? C6 N2 C6 59(2) 10_556 . ? C8 N3 C8 177.3(18) . 8_465 ? C8 N3 C12 73.5(12) . 8_465 ? C8 N3 C12 108.7(14) 8_465 8_465 ? C8 N3 C12 108.7(14) . . ? C8 N3 C12 73.5(12) 8_465 . ? C12 N3 C12 77.2(18) 8_465 . ? C8 N3 C10 103.5(15) . . ? C8 N3 C10 74.3(13) 8_465 . ? C12 N3 C10 176.6(15) 8_465 . ? C12 N3 C10 102.5(12) . . ? C8 N3 C10 74.3(13) . 8_465 ? C8 N3 C10 103.5(15) 8_465 8_465 ? C12 N3 C10 102.5(12) 8_465 8_465 ? C12 N3 C10 176.6(15) . 8_465 ? C10 N3 C10 78(2) . 8_465 ? C18 N4 C16 112.1(11) . . ? C18 N4 C16 112.1(11) . 10_556 ? C16 N4 C16 104.5(16) . 10_556 ? C18 N4 C14 102.0(15) . . ? C16 N4 C14 113.2(10) . . ? C16 N4 C14 113.2(10) 10_556 . ? C22 N5 C22 101.0(11) 7_445 2_575 ? C22 N5 C22 178.7(13) 7_445 . ? C22 N5 C22 79.0(11) 2_575 . ? C22 N5 C22 79.0(11) 7_445 8_465 ? C22 N5 C22 178.7(13) 2_575 8_465 ? C22 N5 C22 101.0(11) . 8_465 ? C22 N5 C20 83.4(8) 7_445 2_575 ? C22 N5 C20 55.5(7) 2_575 2_575 ? C22 N5 C20 97.7(9) . 2_575 ? C22 N5 C20 123.3(10) 8_465 2_575 ? C22 N5 C20 55.5(7) 7_445 7_445 ? C22 N5 C20 83.4(8) 2_575 7_445 ? C22 N5 C20 123.3(10) . 7_445 ? C22 N5 C20 97.7(9) 8_465 7_445 ? C20 N5 C20 115.0(12) 2_575 7_445 ? C22 N5 C20 123.3(10) 7_445 . ? C22 N5 C20 97.7(9) 2_575 . ? C22 N5 C20 55.5(7) . . ? C22 N5 C20 83.4(8) 8_465 . ? C20 N5 C20 147.4(12) 2_575 . ? C20 N5 C20 74.6(13) 7_445 . ? C22 N5 C20 97.7(9) 7_445 8_465 ? C22 N5 C20 123.3(10) 2_575 8_465 ? C22 N5 C20 83.4(8) . 8_465 ? C22 N5 C20 55.5(7) 8_465 8_465 ? C20 N5 C20 74.6(13) 2_575 8_465 ? C20 N5 C20 147.4(12) 7_445 8_465 ? C20 N5 C20 115.0(12) . 8_465 ? C2 C1 N1 106.4(19) . . ? C2 C1 C4 125(2) . . ? N1 C1 C4 126(2) . . ? C2 C1 C1 85.6(10) . 10_556 ? N1 C1 C1 49.5(11) . 10_556 ? C4 C1 C1 113.9(14) . 10_556 ? C1 C2 C3 110(2) . . ? C1 C2 C2 94.4(10) . 10_556 ? C3 C2 C2 55.3(10) . 10_556 ? N2 C3 C5 130(2) . . ? N2 C3 C2 95.7(18) . . ? C5 C3 C2 123.8(17) . . ? N2 C3 C2 95.7(18) . 10_556 ? C5 C3 C2 123.8(17) . 10_556 ? C2 C3 C2 69(2) . 10_556 ? C1 C4 H4A 109.5 . . ? C1 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C1 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C7 C6 C6 57.2(14) . 10_556 ? C7 C6 N2 117(2) . . ? C6 C6 N2 60.5(11) 10_556 . ? C6 C7 C6 66(3) . 10_556 ? C6 C7 C7 146.0(15) . 9_576 ? C6 C7 C7 146.0(15) 10_556 9_576 ? N3 C8 C9 112.7(12) . . ? N3 C8 C12 53.6(8) . 8_465 ? C9 C8 C12 130.7(14) . 8_465 ? N3 C8 C10 57.4(12) . 8_465 ? C9 C8 C10 132.2(15) . 8_465 ? C12 C8 C10 84.0(13) 8_465 8_465 ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C11 C10 N3 101(2) . . ? C11 C10 C8 111(2) . 8_465 ? N3 C10 C8 48.3(9) . 8_465 ? C10 C11 C10 81(3) 8_465 . ? N3 C12 C13 105.9(16) . . ? N3 C12 C8 52.9(8) . 8_465 ? C13 C12 C8 118.8(16) . 8_465 ? N3 C12 C12 51.4(9) . 8_465 ? C13 C12 C12 54.6(9) . 8_465 ? C8 C12 C12 83.1(14) 8_465 8_465 ? C12 C13 C12 70.9(17) . 8_465 ? N4 C14 C15 104.8(18) . . ? N4 C16 C17 115.4(12) . . ? N4 C16 H16A 108.4 . . ? C17 C16 H16A 108.4 . . ? N4 C16 H16B 108.4 . . ? C17 C16 H16B 108.4 . . ? H16A C16 H16B 107.5 . . ? C16 C17 H17A 109.5 . . ? C16 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C16 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? N4 C18 C19 119.5(18) . . ? N4 C18 H18A 120.2 . . ? C19 C18 H18A 120.2 . . ? C21 C20 N5 105.2(12) . . ? C21 C20 C20 52.5(7) . 7_445 ? N5 C20 C20 52.7(6) . 7_445 ? C20 C21 C20 75.1(15) 7_445 . ? N5 C22 C23 104.0(11) . . ? N5 C22 C22 50.5(6) . 2_575 ? C23 C22 C22 53.5(7) . 2_575 ? C22 C23 C22 73.0(13) 2_575 . ? C24 N6 C24 158(6) . 8_455 ? C24 N6 C26 120(3) . . ? C24 N6 C26 62(3) 8_455 . ? C24 N6 C26 62(3) . 8_455 ? C24 N6 C26 120(3) 8_455 8_455 ? C26 N6 C26 168(4) . 8_455 ? C26 C27 C24 47(3) . 8_455 ? N6 C26 C24 58.8(17) . 8_455 ? N6 C26 C27 113.8(19) . . ? C24 C26 C27 85(4) 8_455 . ? N6 C24 C26 58.8(16) . 8_455 ? N6 C24 C25 113.9(19) . . ? C26 C24 C25 166(5) 8_455 . ? N6 C24 C27 90(2) . 8_455 ? C26 C24 C27 48.4(18) 8_455 8_455 ? C25 C24 C27 145(4) . 8_455 ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 25.10 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 1.128 _refine_diff_density_min -1.123 _refine_diff_density_rms 0.173 # Attachment 'Compound_5.cif' data_3 _database_code_depnum_ccdc_archive 'CCDC 702180' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety '2(C21 H24 Cu2 N6 S4 W), H2 O' _chemical_formula_sum 'C42 H50 Cu4 N12 O S8 W2' _chemical_formula_weight 1617.28 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' 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' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting hexagonal _symmetry_space_group_name_H-M 'P 31 2 1' _symmetry_space_group_name_Hall 'P 31 2' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z+1/3' '-x+y, -x, z+2/3' 'y, x, -z' 'x-y, -y, -z+2/3' '-x, -x+y, -z+1/3' _cell_length_a 11.9875(17) _cell_length_b 11.9875(17) _cell_length_c 32.248(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 4013.2(11) _cell_formula_units_Z 3 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 11222 _cell_measurement_theta_min 3.15 _cell_measurement_theta_max 25.35 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.28 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.008 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2358 _exptl_absorpt_coefficient_mu 6.201 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.175 _exptl_absorpt_correction_T_max 0.176 _exptl_absorpt_process_details 'Jacobson R. (1998) Private communication' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 29323 _diffrn_reflns_av_R_equivalents 0.0863 _diffrn_reflns_av_sigmaI/netI 0.0697 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -38 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 3.20 _diffrn_reflns_theta_max 25.35 _reflns_number_total 4857 _reflns_number_gt 4315 _reflns_threshold_expression >2sigma(I) _computing_data_collection CrystalClear _computing_cell_refinement CrystalClear _computing_data_reduction CrystalStructure _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Shelxl-97 (Sheldrick, 1997)' _computing_publication_material 'Shelxl-97 (Sheldrick, 1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0372P)^2^+9.8798P] 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_abs_structure_details '2034 Friedel Pairs' _refine_ls_abs_structure_Flack 0.013(13) _refine_ls_number_reflns 4857 _refine_ls_number_parameters 310 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0625 _refine_ls_R_factor_gt 0.0526 _refine_ls_wR_factor_ref 0.1108 _refine_ls_wR_factor_gt 0.1061 _refine_ls_goodness_of_fit_ref 1.133 _refine_ls_restrained_S_all 1.133 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group W1 W 0.29454(4) 1.11494(5) 1.218339(14) 0.03497(14) Uani 1 1 d . . . Cu1 Cu 0.45566(14) 1.25222(15) 1.15761(5) 0.0434(4) Uani 1 1 d . . . Cu2 Cu 0.10567(16) 0.96560(18) 1.26702(6) 0.0615(5) Uani 1 1 d . . . S1 S 0.3332(3) 1.0336(3) 1.16211(10) 0.0485(8) Uani 1 1 d . . . S2 S 0.4362(3) 1.3226(3) 1.22195(10) 0.0472(8) Uani 1 1 d . . . S3 S 0.0969(3) 1.0840(5) 1.21560(12) 0.0687(11) Uani 1 1 d . . . S4 S 0.3085(3) 1.0128(3) 1.27424(9) 0.0446(7) Uani 1 1 d . . . O1 O 1.0000 1.7847(19) 1.1667 0.124 Uiso 1 2 d S . . H1O1 H 1.0553 1.7782 1.1802 0.186 Uiso 0.50 1 d PR . . H2O1 H 1.0162 1.8604 1.1686 0.186 Uiso 0.50 1 d PR . . N1 N 0.8164(9) 1.4506(9) 1.1067(3) 0.041(2) Uani 1 1 d . . . N2 N 0.6292(10) 1.3188(9) 1.1327(3) 0.039(2) Uani 1 1 d . . . N3 N 1.3054(9) 1.4373(9) 1.0808(3) 0.045(2) Uani 1 1 d . . . N4 N 1.3582(9) 1.3182(10) 1.1187(3) 0.045(3) Uani 1 1 d . . . N5 N 0.9093(11) 1.2389(9) 0.9670(3) 0.046(2) Uani 1 1 d . . . N6 N 0.8749(12) 1.0451(11) 0.9594(3) 0.059(3) Uani 1 1 d . . . C1 C 1.0064(10) 1.5490(10) 1.0598(3) 0.032(2) Uani 1 1 d . . . C2 C 1.1306(11) 1.5691(10) 1.0714(3) 0.035(3) Uani 1 1 d . . . C3 C 1.1986(10) 1.5376(10) 1.0430(4) 0.037(3) Uani 1 1 d . . . C4 C 1.1428(12) 1.4800(11) 1.0049(4) 0.041(3) Uani 1 1 d . . . C5 C 1.0214(10) 1.4566(9) 0.9954(3) 0.032(2) Uani 1 1 d . . . C6 C 0.9570(9) 1.4974(9) 1.0214(3) 0.030(3) Uani 1 1 d . . . C7 C 0.9283(13) 1.5742(12) 1.0905(4) 0.050(3) Uani 1 1 d . . . H7A H 0.8960 1.6254 1.0775 0.061 Uiso 1 1 calc R . . H7B H 0.9828 1.6234 1.1135 0.061 Uiso 1 1 calc R . . C8 C 1.1831(15) 1.6253(16) 1.1139(4) 0.073(5) Uani 1 1 d . . . H8A H 1.2541 1.6126 1.1204 0.110 Uiso 1 1 calc R . . H8B H 1.1166 1.5831 1.1343 0.110 Uiso 1 1 calc R . . H8C H 1.2120 1.7158 1.1137 0.110 Uiso 1 1 calc R . . C9 C 1.3239(12) 1.5519(12) 1.0576(4) 0.050(3) Uani 1 1 d . . . H9A H 1.3788 1.5655 1.0338 0.060 Uiso 1 1 calc R . . H9B H 1.3670 1.6272 1.0753 0.060 Uiso 1 1 calc R . . C10 C 1.2150(16) 1.4367(16) 0.9765(5) 0.080(5) Uani 1 1 d . . . H10A H 1.1548 1.3578 0.9630 0.119 Uiso 1 1 calc R . . H10B H 1.2746 1.4232 0.9925 0.119 Uiso 1 1 calc R . . H10C H 1.2612 1.5019 0.9560 0.119 Uiso 1 1 calc R . . C11 C 0.9556(16) 1.3760(12) 0.9572(4) 0.066(5) Uani 1 1 d . . . H11A H 0.8836 1.3870 0.9493 0.079 Uiso 1 1 calc R . . H11B H 1.0159 1.4035 0.9342 0.079 Uiso 1 1 calc R . . C12 C 0.8241(13) 1.4745(14) 1.0097(4) 0.059(4) Uani 1 1 d . . . H12A H 0.7939 1.5092 1.0309 0.088 Uiso 1 1 calc R . . H12B H 0.7655 1.3837 1.0071 0.088 Uiso 1 1 calc R . . H12C H 0.8292 1.5162 0.9838 0.088 Uiso 1 1 calc R . . C13 C 0.7072(11) 1.4394(12) 1.1201(4) 0.041(3) Uani 1 1 d . . . H13A H 0.6877 1.5054 1.1207 0.050 Uiso 1 1 calc R . . C14 C 0.6968(14) 1.2539(14) 1.1269(4) 0.052(3) Uani 1 1 d . . . H14A H 0.6663 1.1677 1.1331 0.062 Uiso 1 1 calc R . . C15 C 0.8134(12) 1.3357(12) 1.1109(4) 0.052(3) Uani 1 1 d . . . H15A H 0.8782 1.3178 1.1041 0.062 Uiso 1 1 calc R . . C16 C 1.3981(12) 1.4277(12) 1.1009(4) 0.050(3) Uani 1 1 d . . . H16A H 1.4833 1.4941 1.1019 0.060 Uiso 1 1 calc R . . C17 C 1.2290(12) 1.2500(13) 1.1084(5) 0.063(4) Uani 1 1 d . . . H17A H 1.1716 1.1666 1.1171 0.075 Uiso 1 1 calc R . . C18 C 1.1987(12) 1.3194(14) 1.0846(5) 0.073(5) Uani 1 1 d . . . H18A H 1.1189 1.2927 1.0725 0.088 Uiso 1 1 calc R . . C19 C 0.9221(15) 1.1572(14) 0.9427(4) 0.060(4) Uani 1 1 d . . . H19A H 0.9606 1.1782 0.9167 0.073 Uiso 1 1 calc R . . C20 C 0.8274(15) 1.0556(12) 0.9972(4) 0.059(4) Uani 1 1 d . . . H20A H 0.7875 0.9899 1.0166 0.070 Uiso 1 1 calc R . . C21 C 0.8478(13) 1.1759(12) 1.0017(4) 0.053(4) Uani 1 1 d . . . H21A H 0.8243 1.2087 1.0240 0.064 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 W1 0.0270(3) 0.0361(3) 0.0387(2) 0.0006(2) 0.0002(2) 0.0134(2) Cu1 0.0339(8) 0.0445(9) 0.0477(9) 0.0091(7) 0.0038(6) 0.0166(7) Cu2 0.0370(9) 0.0572(11) 0.0707(11) 0.0029(9) 0.0158(8) 0.0089(8) S1 0.060(2) 0.0386(18) 0.0415(18) -0.0015(13) 0.0046(15) 0.0206(17) S2 0.050(2) 0.0339(17) 0.0522(19) -0.0037(14) -0.0024(15) 0.0173(15) S3 0.0320(18) 0.097(3) 0.076(3) 0.004(2) -0.0037(17) 0.032(2) S4 0.0409(18) 0.0494(18) 0.0403(18) 0.0102(13) 0.0076(14) 0.0201(16) N1 0.030(6) 0.030(5) 0.047(6) -0.002(4) 0.007(4) 0.004(4) N2 0.039(6) 0.046(6) 0.039(5) 0.003(4) 0.003(5) 0.026(5) N3 0.027(5) 0.031(5) 0.079(7) 0.010(5) -0.007(5) 0.017(5) N4 0.039(6) 0.046(7) 0.053(6) 0.018(5) 0.003(5) 0.023(5) N5 0.076(7) 0.028(5) 0.037(5) -0.010(4) -0.008(5) 0.028(5) N6 0.075(9) 0.046(7) 0.050(7) -0.012(6) -0.007(6) 0.025(7) C1 0.028(6) 0.031(6) 0.039(6) -0.002(5) -0.002(5) 0.017(5) C2 0.027(6) 0.026(6) 0.038(7) 0.007(5) -0.002(5) 0.004(5) C3 0.025(6) 0.032(6) 0.047(7) 0.019(5) 0.009(5) 0.009(5) C4 0.049(7) 0.029(6) 0.046(8) 0.004(5) 0.013(6) 0.021(6) C5 0.034(6) 0.030(6) 0.033(6) -0.010(4) -0.012(5) 0.017(6) C6 0.027(6) 0.022(5) 0.041(6) -0.010(5) -0.013(4) 0.012(5) C7 0.047(8) 0.041(7) 0.058(8) -0.018(6) -0.002(6) 0.018(6) C8 0.060(10) 0.085(12) 0.060(10) -0.006(9) -0.005(8) 0.026(9) C9 0.038(7) 0.040(7) 0.069(9) 0.011(6) -0.006(6) 0.017(6) C10 0.076(11) 0.069(11) 0.097(12) -0.009(9) 0.033(9) 0.039(9) C11 0.108(13) 0.036(7) 0.042(8) -0.005(6) -0.002(7) 0.027(8) C12 0.055(9) 0.049(8) 0.066(9) -0.014(7) -0.024(7) 0.022(7) C13 0.035(7) 0.046(7) 0.048(7) -0.001(6) 0.005(6) 0.024(6) C14 0.060(9) 0.047(8) 0.059(9) 0.017(7) 0.009(7) 0.034(7) C15 0.035(7) 0.032(7) 0.078(10) 0.009(6) 0.015(7) 0.009(6) C16 0.034(7) 0.032(7) 0.074(9) 0.016(7) 0.004(6) 0.009(6) C17 0.035(8) 0.045(8) 0.094(11) 0.038(7) 0.000(7) 0.010(7) C18 0.020(6) 0.048(9) 0.119(12) 0.039(9) -0.027(7) -0.008(6) C19 0.073(10) 0.047(9) 0.053(9) 0.005(7) 0.009(7) 0.024(7) C20 0.076(10) 0.034(7) 0.053(8) -0.008(6) -0.012(8) 0.018(7) C21 0.073(10) 0.038(7) 0.046(8) 0.002(6) -0.003(6) 0.026(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 W1 S2 2.206(3) . ? W1 S3 2.209(3) . ? W1 S1 2.214(3) . ? W1 S4 2.232(3) . ? W1 Cu2 2.5965(18) . ? W1 Cu1 2.6637(16) . ? Cu1 N2 1.987(10) . ? Cu1 N4 2.118(9) 1_455 ? Cu1 S1 2.280(4) . ? Cu1 S2 2.295(4) . ? Cu2 N6 1.914(11) 2_665 ? Cu2 S4 2.216(4) . ? Cu2 S3 2.219(5) . ? O1 H1O1 0.8301 . ? O1 H2O1 0.8300 . ? N1 C13 1.321(15) . ? N1 C15 1.366(16) . ? N1 C7 1.510(16) . ? N2 C13 1.333(15) . ? N2 C14 1.388(16) . ? N3 C16 1.341(15) . ? N3 C18 1.357(16) . ? N3 C9 1.481(15) . ? N4 C16 1.287(15) . ? N4 C17 1.383(16) . ? N4 Cu1 2.118(9) 1_655 ? N5 C19 1.321(16) . ? N5 C21 1.345(15) . ? N5 C11 1.482(15) . ? N6 C19 1.286(17) . ? N6 C20 1.379(17) . ? N6 Cu2 1.914(11) 3_564 ? C1 C6 1.380(14) . ? C1 C2 1.434(15) . ? C1 C7 1.492(16) . ? C2 C3 1.398(16) . ? C2 C8 1.516(17) . ? C3 C4 1.406(17) . ? C3 C9 1.499(16) . ? C4 C5 1.371(16) . ? C4 C10 1.518(17) . ? C5 C6 1.383(14) . ? C5 C11 1.521(15) . ? C6 C12 1.522(16) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? C13 H13A 0.9300 . ? C14 C15 1.346(17) . ? C14 H14A 0.9300 . ? C15 H15A 0.9300 . ? C16 H16A 0.9300 . ? C17 C18 1.309(17) . ? C17 H17A 0.9300 . ? C18 H18A 0.9300 . ? C19 H19A 0.9300 . ? C20 C21 1.344(17) . ? C20 H20A 0.9300 . ? C21 H21A 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 S2 W1 S3 110.32(16) . . ? S2 W1 S1 109.12(12) . . ? S3 W1 S1 109.64(15) . . ? S2 W1 S4 110.49(12) . . ? S3 W1 S4 107.97(14) . . ? S1 W1 S4 109.28(12) . . ? S2 W1 Cu2 131.30(10) . . ? S3 W1 Cu2 54.28(12) . . ? S1 W1 Cu2 119.58(10) . . ? S4 W1 Cu2 53.99(9) . . ? S2 W1 Cu1 55.28(9) . . ? S3 W1 Cu1 117.37(11) . . ? S1 W1 Cu1 54.79(9) . . ? S4 W1 Cu1 134.64(9) . . ? Cu2 W1 Cu1 169.54(6) . . ? N2 Cu1 N4 105.9(4) . 1_455 ? N2 Cu1 S1 115.5(3) . . ? N4 Cu1 S1 108.0(3) 1_455 . ? N2 Cu1 S2 119.7(3) . . ? N4 Cu1 S2 102.8(3) 1_455 . ? S1 Cu1 S2 103.86(13) . . ? N2 Cu1 W1 146.6(3) . . ? N4 Cu1 W1 107.5(3) 1_455 . ? S1 Cu1 W1 52.53(9) . . ? S2 Cu1 W1 52.19(9) . . ? N6 Cu2 S4 128.4(4) 2_665 . ? N6 Cu2 S3 122.8(4) 2_665 . ? S4 Cu2 S3 108.19(14) . . ? N6 Cu2 W1 167.3(4) 2_665 . ? S4 Cu2 W1 54.58(8) . . ? S3 Cu2 W1 53.92(10) . . ? W1 S1 Cu1 72.69(10) . . ? W1 S2 Cu1 72.53(10) . . ? W1 S3 Cu2 71.80(12) . . ? Cu2 S4 W1 71.43(11) . . ? H1O1 O1 H2O1 107.7 . . ? C13 N1 C15 109.9(11) . . ? C13 N1 C7 124.2(11) . . ? C15 N1 C7 125.9(11) . . ? C13 N2 C14 106.1(10) . . ? C13 N2 Cu1 125.8(8) . . ? C14 N2 Cu1 128.0(8) . . ? C16 N3 C18 104.9(10) . . ? C16 N3 C9 125.4(10) . . ? C18 N3 C9 129.6(10) . . ? C16 N4 C17 103.3(10) . . ? C16 N4 Cu1 130.7(9) . 1_655 ? C17 N4 Cu1 125.9(8) . 1_655 ? C19 N5 C21 108.1(11) . . ? C19 N5 C11 125.4(11) . . ? C21 N5 C11 126.5(10) . . ? C19 N6 C20 105.1(11) . . ? C19 N6 Cu2 126.1(10) . 3_564 ? C20 N6 Cu2 128.4(9) . 3_564 ? C6 C1 C2 119.1(10) . . ? C6 C1 C7 121.0(10) . . ? C2 C1 C7 119.8(10) . . ? C3 C2 C1 118.7(10) . . ? C3 C2 C8 122.9(11) . . ? C1 C2 C8 118.4(11) . . ? C2 C3 C4 120.5(10) . . ? C2 C3 C9 116.7(11) . . ? C4 C3 C9 122.3(11) . . ? C5 C4 C3 119.4(10) . . ? C5 C4 C10 121.7(12) . . ? C3 C4 C10 118.8(12) . . ? C4 C5 C6 121.1(9) . . ? C4 C5 C11 118.0(11) . . ? C6 C5 C11 120.7(11) . . ? C1 C6 C5 120.9(9) . . ? C1 C6 C12 118.5(10) . . ? C5 C6 C12 120.4(10) . . ? C1 C7 N1 111.7(9) . . ? C1 C7 H7A 109.3 . . ? N1 C7 H7A 109.3 . . ? C1 C7 H7B 109.3 . . ? N1 C7 H7B 109.3 . . ? H7A C7 H7B 107.9 . . ? C2 C8 H8A 109.5 . . ? C2 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C2 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? N3 C9 C3 112.1(10) . . ? N3 C9 H9A 109.2 . . ? C3 C9 H9A 109.2 . . ? N3 C9 H9B 109.2 . . ? C3 C9 H9B 109.2 . . ? H9A C9 H9B 107.9 . . ? C4 C10 H10A 109.5 . . ? C4 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C4 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? N5 C11 C5 108.7(10) . . ? N5 C11 H11A 110.0 . . ? C5 C11 H11A 110.0 . . ? N5 C11 H11B 110.0 . . ? C5 C11 H11B 110.0 . . ? H11A C11 H11B 108.3 . . ? C6 C12 H12A 109.5 . . ? C6 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C6 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? N1 C13 N2 109.4(11) . . ? N1 C13 H13A 125.3 . . ? N2 C13 H13A 125.3 . . ? C15 C14 N2 109.2(12) . . ? C15 C14 H14A 125.4 . . ? N2 C14 H14A 125.4 . . ? C14 C15 N1 105.5(12) . . ? C14 C15 H15A 127.3 . . ? N1 C15 H15A 127.3 . . ? N4 C16 N3 113.7(11) . . ? N4 C16 H16A 123.1 . . ? N3 C16 H16A 123.1 . . ? C18 C17 N4 110.5(11) . . ? C18 C17 H17A 124.7 . . ? N4 C17 H17A 124.7 . . ? C17 C18 N3 107.4(11) . . ? C17 C18 H18A 126.3 . . ? N3 C18 H18A 126.3 . . ? N6 C19 N5 112.0(12) . . ? N6 C19 H19A 124.0 . . ? N5 C19 H19A 124.0 . . ? C21 C20 N6 109.3(12) . . ? C21 C20 H20A 125.4 . . ? N6 C20 H20A 125.4 . . ? N5 C21 C20 105.6(12) . . ? N5 C21 H21A 127.2 . . ? C20 C21 H21A 127.2 . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.779 _refine_diff_density_min -1.326 _refine_diff_density_rms 0.153