# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is (C) The Royal Society of Chemistry 2006 data_global _journal_name_full J.Mater.Chem. _journal_coden_cambridge 1145 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_name 'Fangfang Jian' _publ_contact_author_address ; New Materials & Function Coordination Chemistry Lab. Institute of Coordination Chemistry Qingdao Shandong Province 266042 CHINA ; _publ_contact_author_email FFJ2003@163169.NET _publ_section_title ; Synthesis, characterization and nonlinear optical effects of M4(\m4-O) Core Complexes with Large Two-Photon Absorption Cross-Section ; loop_ _publ_author_name 'Fangfang Jian' 'Zhengshuai Bai' 'Hailian Xiao' 'Pu-su Zhao' # Attachment 'NewCIF.doc' #======================================================================= data_compound_[Fe4(C7H4NS2)6] _database_code_depnum_ccdc_archive 'CCDC 257276' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C42 H24 Fe4 N6 O S12' _chemical_formula_weight 1236.79 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.217(6) _cell_length_b 18.217(6) _cell_length_c 24.865(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7146(4) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour brown _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.724 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3732 _exptl_absorpt_coefficient_mu 1.763 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 8955 _diffrn_reflns_av_R_equivalents 0.2066 _diffrn_reflns_av_sigmaI/netI 0.1572 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 21 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.53 _diffrn_reflns_theta_max 24.49 _reflns_number_total 2507 _reflns_number_gt 1784 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction SHELXTL _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0084P)^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 SHELXL _refine_ls_extinction_coef 0.00082(11) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2507 _refine_ls_number_parameters 197 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1167 _refine_ls_R_factor_gt 0.0755 _refine_ls_wR_factor_ref 0.1483 _refine_ls_wR_factor_gt 0.1298 _refine_ls_goodness_of_fit_ref 1.023 _refine_ls_restrained_S_all 1.023 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.10344(7) 0.01202(7) 0.25666(5) 0.0311(4) Uani 1 1 d . . . Fe2 Fe 0.0000 0.0000 0.14941(7) 0.0263(5) Uani 1 3 d S . . S1 S 0.25046(14) 0.27965(15) 0.31129(10) 0.0508(7) Uani 1 1 d . . . S2 S 0.13247(15) 0.09472(14) 0.33296(9) 0.0464(7) Uani 1 1 d . . . S3 S 0.24580(14) 0.24771(14) 0.13932(10) 0.0464(7) Uani 1 1 d . . . S4 S 0.20755(15) 0.08829(16) 0.19367(10) 0.0548(8) Uani 1 1 d . . . O1 O 0.0000 0.0000 0.2260(4) 0.039(2) Uani 1 3 d S . . N1 N 0.1021(4) 0.1964(4) 0.2697(3) 0.0366(17) Uani 1 1 d . . . N2 N 0.1013(4) 0.1139(4) 0.1298(3) 0.0360(17) Uani 1 1 d . . . C1 C 0.1002(6) 0.3105(5) 0.2161(3) 0.046(2) Uani 1 1 d . . . H1A H 0.0463 0.2742 0.2025 0.055 Uiso 1 1 calc R . . C2 C 0.1423(6) 0.3943(5) 0.2013(4) 0.051(2) Uani 1 1 d . . . H2A H 0.1171 0.4149 0.1778 0.061 Uiso 1 1 calc R . . C3 C 0.2222(6) 0.4479(6) 0.2214(4) 0.058(3) Uani 1 1 d . . . H3A H 0.2502 0.5047 0.2113 0.069 Uiso 1 1 calc R . . C4 C 0.2616(6) 0.4194(5) 0.2561(4) 0.051(3) Uani 1 1 d . . . H4A H 0.3152 0.4563 0.2698 0.061 Uiso 1 1 calc R . . C5 C 0.2194(5) 0.3346(5) 0.2698(3) 0.036(2) Uani 1 1 d . . . C6 C 0.1378(5) 0.2798(5) 0.2513(3) 0.034(2) Uani 1 1 d . . . C7 C 0.1563(5) 0.1886(5) 0.3021(3) 0.041(2) Uani 1 1 d . . . C8 C 0.0331(5) 0.1620(6) 0.0626(3) 0.048(2) Uani 1 1 d . . . H8A H -0.0169 0.1100 0.0618 0.058 Uiso 1 1 calc R . . C9 C 0.0424(6) 0.2270(6) 0.0308(4) 0.056(3) Uani 1 1 d . . . H9A H -0.0010 0.2190 0.0076 0.067 Uiso 1 1 calc R . . C10 C 0.1162(7) 0.3046(6) 0.0327(4) 0.060(3) Uani 1 1 d . . . H10A H 0.1207 0.3483 0.0110 0.072 Uiso 1 1 calc R . . C11 C 0.1825(6) 0.3198(5) 0.0652(3) 0.042(2) Uani 1 1 d . . . H11A H 0.2318 0.3724 0.0662 0.050 Uiso 1 1 calc R . . C12 C 0.1722(5) 0.2528(5) 0.0965(3) 0.040(2) Uani 1 1 d . . . C13 C 0.0982(5) 0.1744(5) 0.0957(3) 0.038(2) Uani 1 1 d . . . C14 C 0.1746(5) 0.1423(5) 0.1538(3) 0.034(2) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Fe1 0.0253(7) 0.0250(7) 0.0447(8) 0.0029(5) -0.0028(6) 0.0140(6) Fe2 0.0206(7) 0.0206(7) 0.0378(12) 0.000 0.000 0.0103(3) S1 0.0356(14) 0.0372(14) 0.0702(18) -0.0036(12) -0.0164(12) 0.0112(12) S2 0.0478(15) 0.0341(14) 0.0537(15) 0.0000(11) -0.0137(12) 0.0177(12) S3 0.0314(13) 0.0332(13) 0.0625(16) 0.0103(11) 0.0033(11) 0.0069(11) S4 0.0305(13) 0.0608(17) 0.0767(18) 0.0312(14) 0.0087(12) 0.0256(13) O1 0.028(3) 0.028(3) 0.060(7) 0.000 0.000 0.0138(17) N1 0.030(4) 0.025(4) 0.048(5) 0.000(3) -0.004(3) 0.009(3) N2 0.036(4) 0.022(4) 0.046(4) 0.005(3) -0.008(3) 0.012(3) C1 0.048(6) 0.038(6) 0.048(6) 0.000(4) -0.005(5) 0.019(5) C2 0.054(7) 0.032(5) 0.072(7) 0.013(5) 0.007(5) 0.026(5) C3 0.063(7) 0.028(6) 0.078(8) 0.007(5) 0.013(6) 0.019(5) C4 0.033(5) 0.030(5) 0.080(7) 0.000(5) -0.001(5) 0.009(5) C5 0.030(5) 0.024(5) 0.047(5) 0.003(4) -0.001(4) 0.008(4) C6 0.035(5) 0.024(5) 0.046(5) 0.000(4) -0.001(4) 0.017(4) C7 0.044(6) 0.037(5) 0.051(6) -0.004(4) -0.004(4) 0.025(5) C8 0.039(6) 0.043(6) 0.058(6) 0.002(5) -0.011(5) 0.017(5) C9 0.067(7) 0.046(6) 0.051(6) 0.001(5) -0.014(5) 0.024(6) C10 0.093(9) 0.063(7) 0.057(7) 0.018(5) 0.000(6) 0.064(7) C11 0.046(6) 0.030(5) 0.045(6) 0.011(4) 0.011(5) 0.016(5) C12 0.030(5) 0.044(6) 0.047(5) 0.012(4) 0.006(4) 0.018(5) C13 0.044(6) 0.034(5) 0.039(5) 0.005(4) 0.005(4) 0.022(5) C14 0.026(5) 0.032(5) 0.046(5) -0.003(4) -0.001(4) 0.016(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 Fe1 O1 1.941(4) . ? Fe1 N1 2.027(6) 3 ? Fe1 S4 2.312(3) . ? Fe1 S2 2.314(3) . ? Fe2 O1 1.904(9) . ? Fe2 N2 2.030(6) 2 ? Fe2 N2 2.030(6) . ? Fe2 N2 2.030(6) 3 ? S1 C7 1.703(9) . ? S1 C5 1.718(8) . ? S2 C7 1.720(8) . ? S3 C14 1.735(8) . ? S3 C12 1.749(8) . ? S4 C14 1.704(8) . ? O1 Fe1 1.941(4) 2 ? O1 Fe1 1.941(4) 3 ? N1 C7 1.336(9) . ? N1 C6 1.398(9) . ? N1 Fe1 2.027(6) 2 ? N2 C14 1.309(9) . ? N2 C13 1.412(9) . ? C1 C2 1.372(11) . ? C1 C6 1.390(11) . ? C2 C3 1.378(12) . ? C3 C4 1.379(12) . ? C4 C5 1.381(11) . ? C5 C6 1.391(11) . ? C8 C9 1.361(11) . ? C8 C13 1.367(11) . ? C9 C10 1.381(12) . ? C10 C11 1.361(12) . ? C11 C12 1.381(11) . ? C12 C13 1.390(11) . ? 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 O1 Fe1 N1 111.70(19) . 3 ? O1 Fe1 S4 105.1(2) . . ? N1 Fe1 S4 110.3(2) 3 . ? O1 Fe1 S2 106.8(2) . . ? N1 Fe1 S2 114.30(19) 3 . ? S4 Fe1 S2 108.21(10) . . ? O1 Fe2 N2 103.93(19) . 2 ? O1 Fe2 N2 103.93(19) . . ? N2 Fe2 N2 114.40(14) 2 . ? O1 Fe2 N2 103.93(19) . 3 ? N2 Fe2 N2 114.40(14) 2 3 ? N2 Fe2 N2 114.40(14) . 3 ? C7 S1 C5 91.3(4) . . ? C7 S2 Fe1 98.3(3) . . ? C14 S3 C12 90.9(4) . . ? C14 S4 Fe1 108.7(3) . . ? Fe2 O1 Fe1 113.1(2) . 2 ? Fe2 O1 Fe1 113.1(2) . 3 ? Fe1 O1 Fe1 105.6(3) 2 3 ? Fe2 O1 Fe1 113.1(2) . . ? Fe1 O1 Fe1 105.6(3) 2 . ? Fe1 O1 Fe1 105.6(3) 3 . ? C7 N1 C6 110.3(7) . . ? C7 N1 Fe1 117.4(6) . 2 ? C6 N1 Fe1 132.3(6) . 2 ? C14 N2 C13 113.3(7) . . ? C14 N2 Fe2 121.4(5) . . ? C13 N2 Fe2 124.8(5) . . ? C2 C1 C6 120.1(8) . . ? C1 C2 C3 119.7(9) . . ? C2 C3 C4 121.6(8) . . ? C3 C4 C5 118.2(8) . . ? C4 C5 C6 121.2(8) . . ? C4 C5 S1 129.7(7) . . ? C6 C5 S1 109.0(6) . . ? C1 C6 C5 119.0(7) . . ? C1 C6 N1 126.1(7) . . ? C5 C6 N1 114.8(7) . . ? N1 C7 S1 114.5(6) . . ? N1 C7 S2 122.8(7) . . ? S1 C7 S2 122.6(5) . . ? C9 C8 C13 119.1(9) . . ? C8 C9 C10 120.3(9) . . ? C11 C10 C9 122.6(9) . . ? C10 C11 C12 116.2(9) . . ? C11 C12 C13 122.2(8) . . ? C11 C12 S3 128.4(7) . . ? C13 C12 S3 109.2(6) . . ? C8 C13 C12 119.6(8) . . ? C8 C13 N2 127.1(8) . . ? C12 C13 N2 113.3(7) . . ? N2 C14 S4 128.4(6) . . ? N2 C14 S3 113.2(6) . . ? S4 C14 S3 118.4(5) . . ? _diffrn_measured_fraction_theta_max 0.947 _diffrn_reflns_theta_full 24.49 _diffrn_measured_fraction_theta_full 0.947 _refine_diff_density_max 0.503 _refine_diff_density_min -0.582 _refine_diff_density_rms 0.116 #=============================================================== data_compound_Co _database_code_depnum_ccdc_archive 'CCDC 257277' #=========================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C42 H24 Co4 N6 O S12' _chemical_formula_weight 1249.11 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.264(3) _cell_length_b 18.264(3) _cell_length_c 24.878(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7187(2) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.732 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3756 _exptl_absorpt_coefficient_mu 1.926 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 9648 _diffrn_reflns_av_R_equivalents 0.1031 _diffrn_reflns_av_sigmaI/netI 0.0949 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 22 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.53 _diffrn_reflns_theta_max 25.97 _reflns_number_total 3086 _reflns_number_gt 1744 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction SHELXTL _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0271P)^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 3086 _refine_ls_number_parameters 196 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1131 _refine_ls_R_factor_gt 0.0423 _refine_ls_wR_factor_ref 0.0820 _refine_ls_wR_factor_gt 0.0681 _refine_ls_goodness_of_fit_ref 0.982 _refine_ls_restrained_S_all 0.982 _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 Co1 Co 0.01196(3) 0.10332(3) -0.25663(2) 0.03589(18) Uani 1 1 d . . . Co2 Co 0.0000 0.0000 -0.14942(4) 0.0319(3) Uani 1 3 d S . . S1 S 0.27966(7) 0.25062(7) -0.31115(5) 0.0506(3) Uani 1 1 d . . . S2 S 0.09466(7) 0.13262(7) -0.33272(5) 0.0452(3) Uani 1 1 d . . . S3 S 0.24791(7) 0.24579(7) -0.13955(5) 0.0459(3) Uani 1 1 d . . . S4 S 0.08886(8) 0.20771(7) -0.19366(6) 0.0541(4) Uani 1 1 d . . . O1 O 0.0000 0.0000 -0.22641(18) 0.0308(12) Uani 1 3 d S . . N1 N 0.1972(2) 0.1023(2) -0.26965(14) 0.0354(9) Uani 1 1 d . . . N2 N 0.1137(2) 0.1006(2) -0.12960(14) 0.0354(9) Uani 1 1 d . . . C1 C 0.3100(3) 0.0993(3) -0.21582(18) 0.0434(12) Uani 1 1 d . . . H1A H 0.2740 0.0454 -0.2023 0.052 Uiso 1 1 calc R . . C2 C 0.3940(3) 0.1428(3) -0.2015(2) 0.0544(14) Uani 1 1 d . . . H2A H 0.4147 0.1181 -0.1778 0.065 Uiso 1 1 calc R . . C3 C 0.4480(3) 0.2221(3) -0.2215(2) 0.0565(14) Uani 1 1 d . . . H3A H 0.5046 0.2500 -0.2115 0.068 Uiso 1 1 calc R . . C4 C 0.4194(3) 0.2603(3) -0.2559(2) 0.0509(13) Uani 1 1 d . . . H4A H 0.4562 0.3139 -0.2694 0.061 Uiso 1 1 calc R . . C5 C 0.3347(3) 0.2181(3) -0.27053(19) 0.0435(12) Uani 1 1 d . . . C6 C 0.2801(3) 0.1373(3) -0.25078(17) 0.0357(11) Uani 1 1 d . . . C7 C 0.1880(2) 0.1552(2) -0.30119(17) 0.0358(11) Uani 1 1 d . . . C8 C 0.1617(3) 0.0333(3) -0.06260(19) 0.0509(13) Uani 1 1 d . . . H8A H 0.1097 -0.0164 -0.0615 0.061 Uiso 1 1 calc R . . C9 C 0.2281(3) 0.0430(3) -0.0307(2) 0.0606(15) Uani 1 1 d . . . H9A H 0.2205 -0.0005 -0.0078 0.073 Uiso 1 1 calc R . . C10 C 0.3057(3) 0.1166(3) -0.0327(2) 0.0575(15) Uani 1 1 d . . . H10A H 0.3495 0.1217 -0.0109 0.069 Uiso 1 1 calc R . . C11 C 0.3196(3) 0.1818(3) -0.06571(19) 0.0474(13) Uani 1 1 d . . . H11A H 0.3723 0.2306 -0.0673 0.057 Uiso 1 1 calc R . . C12 C 0.2529(3) 0.1735(3) -0.09693(17) 0.0360(11) Uani 1 1 d . . . C13 C 0.1745(3) 0.0993(3) -0.09621(17) 0.0363(11) Uani 1 1 d . . . C14 C 0.1427(3) 0.1740(3) -0.15415(17) 0.0359(11) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Co1 0.0288(3) 0.0289(3) 0.0514(4) 0.0022(3) -0.0040(3) 0.0155(3) Co2 0.0246(3) 0.0246(3) 0.0467(7) 0.000 0.000 0.01228(17) S1 0.0366(7) 0.0338(7) 0.0711(10) 0.0163(6) 0.0031(6) 0.0099(6) S2 0.0348(7) 0.0450(7) 0.0527(8) 0.0129(6) -0.0006(6) 0.0176(6) S3 0.0337(7) 0.0319(6) 0.0614(9) -0.0018(6) -0.0089(6) 0.0083(5) S4 0.0576(8) 0.0320(7) 0.0754(10) -0.0085(6) -0.0283(7) 0.0245(6) O1 0.0242(16) 0.0242(16) 0.044(3) 0.000 0.000 0.0121(8) N1 0.026(2) 0.031(2) 0.047(2) 0.0058(18) 0.0028(17) 0.0133(17) N2 0.0270(19) 0.029(2) 0.047(2) -0.0014(18) -0.0100(18) 0.0119(17) C1 0.036(3) 0.039(3) 0.053(3) 0.006(2) -0.003(2) 0.017(2) C2 0.043(3) 0.053(3) 0.071(4) 0.001(3) -0.009(3) 0.027(3) C3 0.032(3) 0.054(3) 0.076(4) -0.011(3) -0.009(3) 0.015(3) C4 0.032(3) 0.039(3) 0.065(4) -0.001(3) 0.003(3) 0.005(2) C5 0.036(3) 0.036(3) 0.057(3) 0.003(2) 0.003(2) 0.017(2) C6 0.029(2) 0.036(3) 0.042(3) 0.000(2) 0.002(2) 0.016(2) C7 0.032(2) 0.031(2) 0.041(3) 0.006(2) 0.005(2) 0.013(2) C8 0.041(3) 0.042(3) 0.065(4) 0.011(3) -0.003(3) 0.017(2) C9 0.057(4) 0.060(3) 0.074(4) 0.006(3) -0.012(3) 0.036(3) C10 0.047(3) 0.075(4) 0.065(4) -0.011(3) -0.024(3) 0.041(3) C11 0.033(3) 0.052(3) 0.053(3) -0.012(3) -0.010(2) 0.018(2) C12 0.030(2) 0.034(2) 0.043(3) -0.007(2) -0.007(2) 0.015(2) C13 0.035(3) 0.038(3) 0.040(3) 0.000(2) -0.003(2) 0.021(2) C14 0.030(2) 0.029(2) 0.047(3) -0.004(2) -0.004(2) 0.013(2) _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 Co1 O1 1.9395(19) . ? Co1 N1 2.040(3) 2 ? Co1 S2 2.3116(14) . ? Co1 S4 2.3201(14) . ? Co2 O1 1.916(5) . ? Co2 N2 2.029(3) . ? Co2 N2 2.029(3) 2 ? Co2 N2 2.029(3) 3 ? S1 C5 1.727(5) . ? S1 C7 1.728(4) . ? S2 C7 1.728(4) . ? S3 C12 1.731(4) . ? S3 C14 1.739(4) . ? S4 C14 1.708(4) . ? O1 Co1 1.9395(19) 2 ? O1 Co1 1.9395(19) 3 ? N1 C7 1.319(5) . ? N1 C6 1.398(5) . ? N1 Co1 2.040(3) 3 ? N2 C14 1.319(5) . ? N2 C13 1.396(5) . ? C1 C2 1.377(6) . ? C1 C6 1.385(6) . ? C1 H1A 0.9300 . ? C2 C3 1.375(6) . ? C2 H2A 0.9300 . ? C3 C4 1.361(6) . ? C3 H3A 0.9300 . ? C4 C5 1.388(6) . ? C4 H4A 0.9300 . ? C5 C6 1.393(6) . ? C8 C9 1.384(6) . ? C8 C13 1.388(6) . ? C8 H8A 0.9300 . ? C9 C10 1.384(6) . ? C9 H9A 0.9300 . ? C10 C11 1.363(6) . ? C10 H10A 0.9300 . ? C11 C12 1.388(6) . ? C11 H11A 0.9300 . ? C12 C13 1.395(5) . ? 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 O1 Co1 N1 112.00(9) . 2 ? O1 Co1 S2 106.57(11) . . ? N1 Co1 S2 114.38(11) 2 . ? O1 Co1 S4 105.38(12) . . ? N1 Co1 S4 110.21(10) 2 . ? S2 Co1 S4 107.80(5) . . ? O1 Co2 N2 104.06(10) . . ? O1 Co2 N2 104.06(10) . 2 ? N2 Co2 N2 114.30(8) . 2 ? O1 Co2 N2 104.06(10) . 3 ? N2 Co2 N2 114.30(8) . 3 ? N2 Co2 N2 114.30(8) 2 3 ? C5 S1 C7 90.4(2) . . ? C7 S2 Co1 97.81(15) . . ? C12 S3 C14 90.7(2) . . ? C14 S4 Co1 108.26(15) . . ? Co2 O1 Co1 112.80(12) . 2 ? Co2 O1 Co1 112.80(12) . . ? Co1 O1 Co1 105.95(14) 2 . ? Co2 O1 Co1 112.80(12) . 3 ? Co1 O1 Co1 105.95(14) 2 3 ? Co1 O1 Co1 105.95(14) . 3 ? C7 N1 C6 111.7(3) . . ? C7 N1 Co1 116.2(3) . 3 ? C6 N1 Co1 132.1(3) . 3 ? C14 N2 C13 112.0(3) . . ? C14 N2 Co2 121.1(3) . . ? C13 N2 Co2 126.3(3) . . ? C2 C1 C6 118.6(4) . . ? C2 C1 H1A 120.7 . . ? C6 C1 H1A 120.7 . . ? C3 C2 C1 121.3(5) . . ? C3 C2 H2A 119.3 . . ? C1 C2 H2A 119.3 . . ? C4 C3 C2 120.7(4) . . ? C4 C3 H3A 119.6 . . ? C2 C3 H3A 119.6 . . ? C3 C4 C5 119.1(4) . . ? C3 C4 H4A 120.4 . . ? C5 C4 H4A 120.4 . . ? C4 C5 C6 120.3(4) . . ? C4 C5 S1 129.9(4) . . ? C6 C5 S1 109.8(3) . . ? C1 C6 C5 120.0(4) . . ? C1 C6 N1 126.1(4) . . ? C5 C6 N1 113.9(4) . . ? N1 C7 S1 114.2(3) . . ? N1 C7 S2 124.6(3) . . ? S1 C7 S2 121.2(2) . . ? C9 C8 C13 118.6(4) . . ? C9 C8 H8A 120.7 . . ? C13 C8 H8A 120.7 . . ? C8 C9 C10 120.7(5) . . ? C8 C9 H9A 119.6 . . ? C10 C9 H9A 119.6 . . ? C11 C10 C9 121.5(5) . . ? C11 C10 H10A 119.2 . . ? C9 C10 H10A 119.2 . . ? C10 C11 C12 118.2(4) . . ? C10 C11 H11A 120.9 . . ? C12 C11 H11A 120.9 . . ? C11 C12 C13 121.2(4) . . ? C11 C12 S3 129.5(4) . . ? C13 C12 S3 109.2(3) . . ? C8 C13 C12 119.8(4) . . ? C8 C13 N2 125.7(4) . . ? C12 C13 N2 114.5(4) . . ? N2 C14 S4 128.5(3) . . ? N2 C14 S3 113.6(3) . . ? S4 C14 S3 117.8(2) . . ? _diffrn_measured_fraction_theta_max 0.983 _diffrn_reflns_theta_full 25.97 _diffrn_measured_fraction_theta_full 0.983 _refine_diff_density_max 0.408 _refine_diff_density_min -0.324 _refine_diff_density_rms 0.080 #========================================================== #======================================================================= data_compound_[Ni4(C7H4NS2)6] _database_code_depnum_ccdc_archive 'CCDC 257278' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C42 H24 N6 Ni4 O S12' _chemical_formula_weight 1248.23 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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M R-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 18.261(3) _cell_length_b 18.261(3) _cell_length_c 24.862(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 7180(2) _cell_formula_units_Z 6 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour purple _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.732 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3780 _exptl_absorpt_coefficient_mu 2.115 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _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 ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 8818 _diffrn_reflns_av_R_equivalents 0.2156 _diffrn_reflns_av_sigmaI/netI 0.1859 _diffrn_reflns_limit_h_min -20 _diffrn_reflns_limit_h_max 20 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.53 _diffrn_reflns_theta_max 23.99 _reflns_number_total 2452 _reflns_number_gt 1464 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Siemens, 1996)' _computing_cell_refinement 'SAINT (Siemens, 1996)' _computing_data_reduction SHELXTL _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0480P)^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 2452 _refine_ls_number_parameters 196 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1551 _refine_ls_R_factor_gt 0.0955 _refine_ls_wR_factor_ref 0.2095 _refine_ls_wR_factor_gt 0.1798 _refine_ls_goodness_of_fit_ref 1.028 _refine_ls_restrained_S_all 1.028 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ni1 Ni 0.01177(9) -0.09156(9) -0.25653(7) 0.0414(5) Uani 1 1 d . . . Ni2 Ni 0.0000 0.0000 -0.14947(12) 0.0373(8) Uani 1 3 d S . . S1 S 0.27932(19) 0.0289(2) -0.31119(16) 0.0501(10) Uani 1 1 d . . . S2 S 0.09489(18) -0.0377(2) -0.33280(14) 0.0459(9) Uani 1 1 d . . . S3 S 0.24785(18) 0.0021(2) -0.13966(15) 0.0452(9) Uani 1 1 d . . . S4 S 0.0888(2) -0.1187(2) -0.19343(16) 0.0525(10) Uani 1 1 d . . . O1 O 0.0000 0.0000 -0.2262(6) 0.033(3) Uani 1 3 d S . . N1 N 0.1968(5) 0.0950(5) -0.2690(4) 0.031(2) Uani 1 1 d . . . N2 N 0.1142(5) 0.0137(5) -0.1300(4) 0.029(2) Uani 1 1 d . . . C1 C 0.3093(8) 0.2103(7) -0.2164(6) 0.054(4) Uani 1 1 d . . . H1A H 0.2730 0.2283 -0.2036 0.065 Uiso 1 1 calc R . . C2 C 0.3928(7) 0.2522(7) -0.2004(6) 0.047(3) Uani 1 1 d . . . H2A H 0.4128 0.2968 -0.1761 0.056 Uiso 1 1 calc R . . C3 C 0.4480(8) 0.2251(8) -0.2220(6) 0.059(4) Uani 1 1 d . . . H3A H 0.5048 0.2539 -0.2123 0.071 Uiso 1 1 calc R . . C4 C 0.4196(7) 0.1589(8) -0.2560(6) 0.058(4) Uani 1 1 d . . . H4A H 0.4563 0.1423 -0.2701 0.069 Uiso 1 1 calc R . . C5 C 0.3351(7) 0.1164(7) -0.2694(5) 0.043(3) Uani 1 1 d . . . C6 C 0.2789(6) 0.1433(7) -0.2508(5) 0.030(3) Uani 1 1 d . . . C7 C 0.1887(7) 0.0339(6) -0.3020(5) 0.040(3) Uani 1 1 d . . . C8 C 0.1603(8) 0.1287(8) -0.0623(5) 0.051(4) Uani 1 1 d . . . H8A H 0.1089 0.1278 -0.0613 0.061 Uiso 1 1 calc R . . C9 C 0.2276(8) 0.1828(8) -0.0303(5) 0.048(3) Uani 1 1 d . . . H9A H 0.2200 0.2167 -0.0057 0.058 Uiso 1 1 calc R . . C10 C 0.3041(9) 0.1884(8) -0.0332(6) 0.067(5) Uani 1 1 d . . . H10A H 0.3480 0.2285 -0.0122 0.081 Uiso 1 1 calc R . . C11 C 0.3201(8) 0.1364(8) -0.0667(6) 0.052(4) Uani 1 1 d . . . H11A H 0.3727 0.1400 -0.0684 0.062 Uiso 1 1 calc R . . C12 C 0.2536(7) 0.0805(7) -0.0965(5) 0.038(3) Uani 1 1 d . . . C13 C 0.1736(7) 0.0757(7) -0.0962(6) 0.045(3) Uani 1 1 d . . . C14 C 0.1422(6) -0.0312(7) -0.1548(5) 0.038(3) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Ni1 0.0345(9) 0.0354(9) 0.0519(11) -0.0074(8) -0.0048(8) 0.0157(8) Ni2 0.0311(9) 0.0311(9) 0.0498(19) 0.000 0.000 0.0155(4) S1 0.0378(18) 0.0488(19) 0.068(3) -0.0121(19) 0.0061(18) 0.0251(16) S2 0.0368(17) 0.0456(18) 0.051(2) -0.0138(17) -0.0018(16) 0.0171(15) S3 0.0337(17) 0.0500(19) 0.058(2) -0.0059(18) -0.0077(16) 0.0251(15) S4 0.060(2) 0.0434(19) 0.067(3) -0.0170(18) -0.026(2) 0.0352(17) O1 0.027(4) 0.027(4) 0.044(9) 0.000 0.000 0.013(2) N1 0.025(5) 0.039(5) 0.028(6) -0.002(5) 0.000(4) 0.015(4) N2 0.012(4) 0.033(5) 0.043(6) -0.010(5) -0.009(5) 0.013(4) C1 0.042(8) 0.036(7) 0.075(11) -0.022(7) -0.005(7) 0.013(6) C2 0.035(7) 0.033(7) 0.065(10) -0.005(7) -0.013(7) 0.011(6) C3 0.035(7) 0.044(8) 0.072(11) 0.002(8) -0.032(8) 0.000(7) C4 0.019(6) 0.057(9) 0.090(12) 0.011(9) 0.003(7) 0.013(6) C5 0.044(7) 0.042(7) 0.046(9) 0.012(6) 0.002(7) 0.024(6) C6 0.026(6) 0.037(6) 0.028(7) 0.015(6) 0.004(6) 0.016(5) C7 0.040(7) 0.024(6) 0.053(9) -0.002(6) 0.009(6) 0.013(5) C8 0.054(8) 0.052(8) 0.053(9) -0.023(7) -0.007(8) 0.031(7) C9 0.048(8) 0.049(8) 0.043(9) -0.013(7) -0.009(7) 0.020(7) C10 0.042(8) 0.033(7) 0.077(12) -0.003(8) -0.017(8) -0.019(6) C11 0.044(8) 0.050(8) 0.064(11) -0.006(8) -0.010(8) 0.024(7) C12 0.036(7) 0.026(6) 0.040(8) 0.006(6) -0.002(6) 0.007(5) C13 0.030(7) 0.040(7) 0.064(10) 0.014(7) 0.005(7) 0.017(6) C14 0.021(6) 0.033(6) 0.059(9) 0.009(6) -0.002(6) 0.013(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 Ni1 O1 1.942(6) . ? Ni1 N1 2.026(8) 3 ? Ni1 S2 2.318(4) . ? Ni1 S4 2.321(4) . ? Ni2 O1 1.907(14) . ? Ni2 N2 2.030(7) 2 ? Ni2 N2 2.030(7) 3 ? Ni2 N2 2.030(7) . ? S1 C7 1.717(11) . ? S1 C5 1.744(13) . ? S2 C7 1.730(12) . ? S3 C14 1.749(10) . ? S3 C12 1.750(12) . ? S4 C14 1.694(12) . ? O1 Ni1 1.942(6) 3 ? O1 Ni1 1.942(6) 2 ? N1 C7 1.333(14) . ? N1 C6 1.381(13) . ? N1 Ni1 2.026(8) 2 ? N2 C14 1.318(14) . ? N2 C13 1.391(14) . ? C1 C6 1.362(16) . ? C1 C2 1.381(16) . ? C2 C3 1.430(18) . ? C3 C4 1.349(19) . ? C4 C5 1.378(16) . ? C5 C6 1.419(15) . ? C8 C9 1.380(16) . ? C8 C13 1.393(17) . ? C9 C10 1.350(17) . ? C10 C11 1.400(19) . ? C11 C12 1.351(16) . ? C12 C13 1.419(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 O1 Ni1 N1 112.0(3) . 3 ? O1 Ni1 S2 106.5(3) . . ? N1 Ni1 S2 114.8(3) 3 . ? O1 Ni1 S4 105.2(3) . . ? N1 Ni1 S4 110.1(3) 3 . ? S2 Ni1 S4 107.76(14) . . ? O1 Ni2 N2 103.8(3) . 2 ? O1 Ni2 N2 103.8(3) . 3 ? N2 Ni2 N2 114.5(2) 2 3 ? O1 Ni2 N2 103.8(3) . . ? N2 Ni2 N2 114.5(2) 2 . ? N2 Ni2 N2 114.5(2) 3 . ? C7 S1 C5 90.5(6) . . ? C7 S2 Ni1 98.6(4) . . ? C14 S3 C12 91.2(6) . . ? C14 S4 Ni1 107.8(4) . . ? Ni2 O1 Ni1 112.9(4) . 3 ? Ni2 O1 Ni1 112.9(4) . 2 ? Ni1 O1 Ni1 105.9(4) 3 2 ? Ni2 O1 Ni1 112.9(4) . . ? Ni1 O1 Ni1 105.9(4) 3 . ? Ni1 O1 Ni1 105.9(4) 2 . ? C7 N1 C6 111.5(9) . . ? C7 N1 Ni1 116.4(7) . 2 ? C6 N1 Ni1 132.0(7) . 2 ? C14 N2 C13 113.7(8) . . ? C14 N2 Ni2 120.4(7) . . ? C13 N2 Ni2 125.4(7) . . ? C6 C1 C2 121.3(12) . . ? C1 C2 C3 118.3(12) . . ? C4 C3 C2 121.6(11) . . ? C3 C4 C5 118.5(13) . . ? C4 C5 C6 121.8(12) . . ? C4 C5 S1 129.5(11) . . ? C6 C5 S1 108.6(8) . . ? C1 C6 N1 127.2(10) . . ? C1 C6 C5 118.4(11) . . ? N1 C6 C5 114.4(10) . . ? N1 C7 S1 114.9(8) . . ? N1 C7 S2 124.0(8) . . ? S1 C7 S2 121.2(7) . . ? C9 C8 C13 116.3(12) . . ? C10 C9 C8 122.7(13) . . ? C9 C10 C11 122.6(12) . . ? C12 C11 C10 115.1(12) . . ? C11 C12 C13 123.6(12) . . ? C11 C12 S3 128.1(10) . . ? C13 C12 S3 108.3(9) . . ? N2 C13 C8 126.5(10) . . ? N2 C13 C12 114.0(11) . . ? C8 C13 C12 119.4(12) . . ? N2 C14 S4 129.3(8) . . ? N2 C14 S3 112.8(8) . . ? S4 C14 S3 117.7(7) . . ? _diffrn_measured_fraction_theta_max 0.973 _diffrn_reflns_theta_full 23.99 _diffrn_measured_fraction_theta_full 0.973 _refine_diff_density_max 0.827 _refine_diff_density_min -0.731 _refine_diff_density_rms 0.146