# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_woe6 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C12 H16 Fe N6 O2 S2' _chemical_formula_sum 'C12 H16 Fe N6 O2 S2' _chemical_formula_weight 396.28 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' 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 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 6.9323(5) _cell_length_b 8.1273(6) _cell_length_c 9.2839(6) _cell_angle_alpha 108.530(10) _cell_angle_beta 111.800(10) _cell_angle_gamma 99.190(10) _cell_volume 436.96(5) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 6806 _cell_measurement_theta_min 2.59 _cell_measurement_theta_max 26.99 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.1240 _exptl_crystal_size_mid 0.0964 _exptl_crystal_size_min 0.0854 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.506 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 204 _exptl_absorpt_coefficient_mu 1.118 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.8078 _exptl_absorpt_correction_T_max 0.8706 _exptl_absorpt_process_details 'X-Shape and X-Red32 (Stoe, 2008)' _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 'STOE IPDS-2' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 6806 _diffrn_reflns_av_R_equivalents 0.0170 _diffrn_reflns_av_sigmaI/netI 0.0132 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 26.99 _reflns_number_total 1886 _reflns_number_gt 1700 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-Area (Stoe, 2008)' _computing_cell_refinement 'X-Area (Stoe, 2008)' _computing_data_reduction 'X-Area (Stoe, 2008)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; XP in SHELXTL (Sheldrick, 2008) and Diamond (Brandenburg, 2011) ; _computing_publication_material 'XCIF in SHELXTL (Sheldrick, 2008)' _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^)+(0.0379P)^2^+0.0709P] 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 1886 _refine_ls_number_parameters 109 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0284 _refine_ls_R_factor_gt 0.0243 _refine_ls_wR_factor_ref 0.0660 _refine_ls_wR_factor_gt 0.0645 _refine_ls_goodness_of_fit_ref 1.084 _refine_ls_restrained_S_all 1.084 _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 Fe1 Fe 0.0000 0.0000 0.5000 0.03445(11) Uani 1 2 d S . . N1 N 0.0288(3) -0.1318(2) 0.27659(19) 0.0509(3) Uani 1 1 d . . . C1 C 0.1073(3) -0.1867(2) 0.18880(19) 0.0403(3) Uani 1 1 d . . . S1 S 0.21706(8) -0.26551(7) 0.06453(6) 0.05869(15) Uani 1 1 d . . . N10 N 0.3364(2) 0.62168(17) 0.55514(17) 0.0398(3) Uani 1 1 d . . . C10 C 0.4010(2) 0.5779(2) 0.68938(19) 0.0377(3) Uani 1 1 d . . . C11 C 0.3105(2) 0.4028(2) 0.6702(2) 0.0398(3) Uani 1 1 d . . . H11 H 0.3548 0.3764 0.7656 0.048 Uiso 1 1 calc R . . C12 C 0.1053(2) 0.3139(2) 0.38605(19) 0.0382(3) Uani 1 1 d . . . H12 H 0.0068 0.2245 0.2786 0.046 Uiso 1 1 calc R . . C13 C 0.1900(3) 0.4882(2) 0.4044(2) 0.0401(3) Uani 1 1 d . . . H13 H 0.1442 0.5144 0.3089 0.048 Uiso 1 1 calc R . . C14 C 0.5702(3) 0.7229(2) 0.8586(2) 0.0526(4) Uani 1 1 d . . . H14A H 0.6806 0.7929 0.8433 0.079 Uiso 1 1 calc R . . H14B H 0.6363 0.6665 0.9323 0.079 Uiso 1 1 calc R . . H14C H 0.5021 0.8021 0.9084 0.079 Uiso 1 1 calc R . . N11 N 0.1623(2) 0.27083(17) 0.52053(16) 0.0372(3) Uani 1 1 d . . . O1 O 0.30752(19) -0.02233(16) 0.64329(17) 0.0547(3) Uani 1 1 d . . . H1O1 H 0.4237 0.0568 0.7160 0.075(7) Uiso 1 1 d R . . H2O1 H 0.3349 -0.1172 0.6072 0.067(7) Uiso 1 1 d 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 Fe1 0.03145(16) 0.03353(16) 0.03511(16) 0.01390(12) 0.01268(12) 0.00838(11) N1 0.0538(8) 0.0505(8) 0.0457(8) 0.0149(6) 0.0249(7) 0.0134(7) C1 0.0360(7) 0.0396(7) 0.0347(7) 0.0132(6) 0.0098(6) 0.0049(6) S1 0.0430(2) 0.0712(3) 0.0437(2) 0.0062(2) 0.0196(2) 0.0088(2) N10 0.0371(6) 0.0386(6) 0.0453(7) 0.0179(5) 0.0194(6) 0.0127(5) C10 0.0296(7) 0.0408(7) 0.0393(8) 0.0130(6) 0.0149(6) 0.0113(6) C11 0.0352(7) 0.0453(8) 0.0376(8) 0.0198(6) 0.0130(6) 0.0121(6) C12 0.0342(7) 0.0412(7) 0.0353(7) 0.0142(6) 0.0135(6) 0.0107(6) C13 0.0389(8) 0.0447(8) 0.0407(8) 0.0212(7) 0.0181(6) 0.0151(6) C14 0.0452(9) 0.0499(9) 0.0439(9) 0.0094(7) 0.0141(7) 0.0033(7) N11 0.0339(6) 0.0376(6) 0.0393(6) 0.0165(5) 0.0152(5) 0.0104(5) O1 0.0353(6) 0.0382(6) 0.0643(8) 0.0130(5) 0.0033(6) 0.0108(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 Fe1 N1 2.1104(15) 2_556 ? Fe1 N1 2.1104(15) . ? Fe1 O1 2.1256(12) 2_556 ? Fe1 O1 2.1256(12) . ? Fe1 N11 2.2203(13) . ? Fe1 N11 2.2203(13) 2_556 ? N1 C1 1.156(2) . ? C1 S1 1.6302(18) . ? N10 C13 1.339(2) . ? N10 C10 1.341(2) . ? C10 C11 1.386(2) . ? C10 C14 1.498(2) . ? C11 N11 1.333(2) . ? C11 H11 0.9300 . ? C12 N11 1.339(2) . ? C12 C13 1.373(2) . ? C12 H12 0.9300 . ? C13 H13 0.9300 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? O1 H1O1 0.8200 . ? O1 H2O1 0.8200 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Fe1 N1 180.000(1) 2_556 . ? N1 Fe1 O1 88.61(6) 2_556 2_556 ? N1 Fe1 O1 91.39(6) . 2_556 ? N1 Fe1 O1 91.39(6) 2_556 . ? N1 Fe1 O1 88.61(6) . . ? O1 Fe1 O1 180.0 2_556 . ? N1 Fe1 N11 89.53(6) 2_556 . ? N1 Fe1 N11 90.47(6) . . ? O1 Fe1 N11 88.90(5) 2_556 . ? O1 Fe1 N11 91.10(5) . . ? N1 Fe1 N11 90.47(6) 2_556 2_556 ? N1 Fe1 N11 89.53(6) . 2_556 ? O1 Fe1 N11 91.10(5) 2_556 2_556 ? O1 Fe1 N11 88.90(5) . 2_556 ? N11 Fe1 N11 180.0 . 2_556 ? C1 N1 Fe1 160.08(14) . . ? N1 C1 S1 179.64(16) . . ? C13 N10 C10 117.12(13) . . ? N10 C10 C11 120.14(14) . . ? N10 C10 C14 118.30(15) . . ? C11 C10 C14 121.56(15) . . ? N11 C11 C10 122.62(14) . . ? N11 C11 H11 118.7 . . ? C10 C11 H11 118.7 . . ? N11 C12 C13 121.03(14) . . ? N11 C12 H12 119.5 . . ? C13 C12 H12 119.5 . . ? N10 C13 C12 122.25(14) . . ? N10 C13 H13 118.9 . . ? C12 C13 H13 118.9 . . ? C10 C14 H14A 109.5 . . ? C10 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C10 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C11 N11 C12 116.76(13) . . ? C11 N11 Fe1 121.29(10) . . ? C12 N11 Fe1 121.79(10) . . ? Fe1 O1 H1O1 130.7 . . ? Fe1 O1 H2O1 119.0 . . ? H1O1 O1 H2O1 107.5 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H1O1 S1 0.82 2.43 3.2491(14) 174.0 2_656 O1 H2O1 N10 0.82 2.02 2.8077(18) 159.7 1_545 _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 26.99 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.307 _refine_diff_density_min -0.263 _refine_diff_density_rms 0.037 _database_code_depnum_ccdc_archive 'CCDC 936136' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_woe31a _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H20 Co N6 O2 S2' _chemical_formula_sum 'C14 H20 Co N6 O2 S2' _chemical_formula_weight 427.41 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' Co Co 0.3494 0.9721 '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 monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.3778(7) _cell_length_b 10.1202(5) _cell_length_c 14.0457(16) _cell_angle_alpha 90.00 _cell_angle_beta 105.909(9) _cell_angle_gamma 90.00 _cell_volume 1008.55(16) _cell_formula_units_Z 2 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 6618 _cell_measurement_theta_min 2.51 _cell_measurement_theta_max 28.07 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.0893 _exptl_crystal_size_mid 0.0615 _exptl_crystal_size_min 0.0549 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.407 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 442 _exptl_absorpt_coefficient_mu 1.077 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.8566 _exptl_absorpt_correction_T_max 0.9279 _exptl_absorpt_process_details 'X-Shape and X-Red32 (Stoe, 2008)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 170(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 'STOE IPDS-1' _diffrn_measurement_method 'phi scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 6618 _diffrn_reflns_av_R_equivalents 0.0369 _diffrn_reflns_av_sigmaI/netI 0.0389 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.51 _diffrn_reflns_theta_max 28.07 _reflns_number_total 2412 _reflns_number_gt 1872 _reflns_threshold_expression >2sigma(I) _computing_cell_refinement 'X-Area (Stoe, 2008)' _computing_data_reduction 'X-Area (Stoe, 2008)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; XP in SHELXTL (Sheldrick, 2008) and Diamond (Brandenburg, 2011) ; _computing_publication_material 'XCIF in SHELXTL (Sheldrick, 2008)' _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^)+(0.0638P)^2^+1.8372P] 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 0.022(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2412 _refine_ls_number_parameters 118 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0702 _refine_ls_R_factor_gt 0.0512 _refine_ls_wR_factor_ref 0.1313 _refine_ls_wR_factor_gt 0.1224 _refine_ls_goodness_of_fit_ref 1.051 _refine_ls_restrained_S_all 1.051 _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 Co1 Co 0.5000 0.5000 0.0000 0.01429(19) Uani 1 2 d S . . S1 S 0.13688(19) 0.14229(14) 0.07766(16) 0.0846(6) Uani 1 1 d . . . C1 C 0.2693(5) 0.2539(3) 0.0484(3) 0.0251(7) Uani 1 1 d . . . N1 N 0.3636(4) 0.3315(3) 0.02594(19) 0.0220(6) Uani 1 1 d . . . N11 N 0.3965(4) 0.6007(3) 0.11161(17) 0.0183(5) Uani 1 1 d . . . C11 C 0.3954(4) 0.5427(3) 0.1967(2) 0.0181(6) Uani 1 1 d . . . H11 H 0.4354 0.4534 0.2074 0.022 Uiso 1 1 calc R . . C10 C 0.3373(4) 0.6087(3) 0.2709(2) 0.0178(6) Uani 1 1 d . . . N10 N 0.2808(4) 0.7342(3) 0.25788(18) 0.0222(6) Uani 1 1 d . . . C13 C 0.2776(5) 0.7909(3) 0.1715(2) 0.0264(7) Uani 1 1 d . . . H13 H 0.2342 0.8794 0.1599 0.032 Uiso 1 1 calc R . . C12 C 0.3352(5) 0.7252(3) 0.0983(2) 0.0247(7) Uani 1 1 d . . . H12 H 0.3310 0.7693 0.0380 0.030 Uiso 1 1 calc R . . C14 C 0.3356(5) 0.5407(4) 0.3654(2) 0.0252(7) Uani 1 1 d . . . H14A H 0.4498 0.5641 0.4172 0.038 Uiso 1 1 calc R . . H14B H 0.3315 0.4448 0.3552 0.038 Uiso 1 1 calc R . . H14C H 0.2243 0.5687 0.3855 0.038 Uiso 1 1 calc R . . O1 O 0.7378(3) 0.4308(2) 0.10847(15) 0.0221(5) Uani 1 1 d . . . H1O1 H 0.7288 0.3633 0.1416 0.033 Uiso 1 1 d R . . C15 C 0.9190(6) 0.4869(5) 0.1419(3) 0.0454(11) Uani 1 1 d . . . H15A H 1.0073 0.4208 0.1792 0.068 Uiso 0.50 1 calc PR . . H15B H 0.9149 0.5627 0.1847 0.068 Uiso 0.50 1 calc PR . . H15C H 0.9609 0.5164 0.0849 0.068 Uiso 0.50 1 calc PR . . H15D H 0.9148 0.5791 0.1200 0.068 Uiso 0.50 1 calc PR . . H15E H 1.0071 0.4372 0.1145 0.068 Uiso 0.50 1 calc PR . . H15F H 0.9612 0.4835 0.2143 0.068 Uiso 0.50 1 calc PR . . 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 0.0174(3) 0.0148(3) 0.0121(3) 0.0005(2) 0.00632(18) -0.0036(2) S1 0.0364(6) 0.0477(8) 0.1800(18) 0.0625(10) 0.0467(9) 0.0030(5) C1 0.0201(15) 0.0184(16) 0.0379(17) 0.0060(13) 0.0095(13) 0.0032(12) N1 0.0251(13) 0.0187(13) 0.0236(12) 0.0012(10) 0.0092(11) -0.0056(10) N11 0.0231(13) 0.0189(13) 0.0140(11) -0.0005(9) 0.0069(9) -0.0020(10) C11 0.0217(14) 0.0182(14) 0.0159(13) 0.0002(10) 0.0078(11) 0.0007(11) C10 0.0159(13) 0.0227(15) 0.0149(12) -0.0039(11) 0.0044(10) -0.0036(11) N10 0.0235(13) 0.0245(14) 0.0182(12) -0.0054(10) 0.0051(10) 0.0003(11) C13 0.0372(19) 0.0184(16) 0.0239(15) -0.0016(12) 0.0091(13) 0.0050(13) C12 0.0373(18) 0.0195(16) 0.0189(14) 0.0024(11) 0.0107(13) 0.0015(13) C14 0.0305(17) 0.0319(18) 0.0154(13) 0.0005(11) 0.0101(12) -0.0013(13) O1 0.0200(11) 0.0242(12) 0.0206(10) 0.0071(8) 0.0028(8) -0.0056(9) C15 0.0243(18) 0.052(3) 0.050(2) 0.017(2) -0.0049(16) -0.0147(18) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Co1 N1 2.063(3) 3_665 ? Co1 N1 2.063(3) . ? Co1 O1 2.103(2) . ? Co1 O1 2.103(2) 3_665 ? Co1 N11 2.176(2) 3_665 ? Co1 N11 2.176(2) . ? S1 C1 1.618(3) . ? C1 N1 1.149(4) . ? N11 C11 1.334(4) . ? N11 C12 1.334(4) . ? C11 C10 1.400(4) . ? C10 N10 1.334(4) . ? C10 C14 1.497(4) . ? N10 C13 1.336(4) . ? C13 C12 1.386(4) . ? O1 C15 1.409(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Co1 N1 180.00(14) 3_665 . ? N1 Co1 O1 93.02(10) 3_665 . ? N1 Co1 O1 86.98(10) . . ? N1 Co1 O1 86.98(10) 3_665 3_665 ? N1 Co1 O1 93.02(10) . 3_665 ? O1 Co1 O1 180.0 . 3_665 ? N1 Co1 N11 88.60(10) 3_665 3_665 ? N1 Co1 N11 91.40(10) . 3_665 ? O1 Co1 N11 88.75(9) . 3_665 ? O1 Co1 N11 91.25(9) 3_665 3_665 ? N1 Co1 N11 91.40(10) 3_665 . ? N1 Co1 N11 88.60(10) . . ? O1 Co1 N11 91.25(9) . . ? O1 Co1 N11 88.75(9) 3_665 . ? N11 Co1 N11 180.00(7) 3_665 . ? N1 C1 S1 178.5(3) . . ? C1 N1 Co1 167.1(3) . . ? C11 N11 C12 117.1(3) . . ? C11 N11 Co1 121.9(2) . . ? C12 N11 Co1 120.9(2) . . ? N11 C11 C10 122.4(3) . . ? N10 C10 C11 120.0(3) . . ? N10 C10 C14 118.8(3) . . ? C11 C10 C14 121.3(3) . . ? C10 N10 C13 117.5(3) . . ? N10 C13 C12 122.3(3) . . ? N11 C12 C13 120.7(3) . . ? C15 O1 Co1 129.3(2) . . ? _diffrn_measured_fraction_theta_max 0.978 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 1.667 _refine_diff_density_min -1.720 _refine_diff_density_rms 0.096 _database_code_depnum_ccdc_archive 'CCDC 936137' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_woe223 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H23 Co N10 S2, C5 H6 N2' _chemical_formula_sum 'C27 H29 Co N12 S2' _chemical_formula_weight 644.67 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' N N 0.0061 0.0033 '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' S S 0.1246 0.1234 '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' _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 8.1838(6) _cell_length_b 13.5028(11) _cell_length_c 15.2673(11) _cell_angle_alpha 101.562(9) _cell_angle_beta 99.853(9) _cell_angle_gamma 96.480(10) _cell_volume 1609.5(2) _cell_formula_units_Z 2 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 17568 _cell_measurement_theta_min 2.56 _cell_measurement_theta_max 27.00 _exptl_crystal_description block _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.330 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 668 _exptl_absorpt_coefficient_mu 0.701 _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 200(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 'STOE IPDS-1' _diffrn_measurement_method 'phi scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 17568 _diffrn_reflns_av_R_equivalents 0.0521 _diffrn_reflns_av_sigmaI/netI 0.0464 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 27.00 _reflns_number_total 6876 _reflns_number_gt 5594 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-Area (Stoe, 2008)' _computing_cell_refinement 'X-Area (Stoe, 2008)' _computing_data_reduction 'X-Area (Stoe, 2008)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; XP in SHELXTL (Sheldrick, 2008) and Diamond (Brandenburg, 2011) ; _computing_publication_material 'XCIF in SHELXTL (Sheldrick, 2008)' _refine_special_details ; The C and S atom of one of the two thiocyanato anions is disordered in two orientations and was refined using a split model, with the C atoms refined only isotropic. The methyl group of one of the coordinating ligands is also disordered in two orientation that are related by a pseudo 2-fold axis. The non-coordinating 2-methylpyrazine ligand is disordered in two separate orientations and was refined using a split model with the major component refined anisotropic and the minor component refined only isotropic. For some of these atoms larger anisotropic and isotropic displacement parameters are observed which can be traced back to the disordering, which cannot be resolved sucessfully. In this procedure several restraints (Flat and Same) were used to get a reasonable geometry. 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^)+(0.0796P)^2^+1.8183P] 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 0.022(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 6876 _refine_ls_number_parameters 418 _refine_ls_number_restraints 54 _refine_ls_R_factor_all 0.0660 _refine_ls_R_factor_gt 0.0537 _refine_ls_wR_factor_ref 0.1558 _refine_ls_wR_factor_gt 0.1480 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.036 _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 Co1 Co 0.30240(4) 0.67671(3) 0.28494(2) 0.02434(15) Uani 1 1 d . A . N1 N 0.1277(3) 0.6776(2) 0.36772(18) 0.0340(5) Uani 1 1 d . . . C1 C 0.0412(10) 0.7038(7) 0.4166(5) 0.027(3) Uiso 0.75 1 d PD A 1 S1 S -0.0832(3) 0.7383(2) 0.4857(2) 0.0452(5) Uani 0.75 1 d PD A 1 C1' C 0.051(3) 0.712(2) 0.4253(16) 0.032(9) Uiso 0.25 1 d PD A 2 S1' S -0.0398(11) 0.7670(7) 0.5034(6) 0.0528(18) Uani 0.25 1 d PD A 2 N2 N 0.4779(3) 0.67739(19) 0.20248(17) 0.0316(5) Uani 1 1 d . . . C2 C 0.5725(4) 0.7117(2) 0.1639(2) 0.0310(6) Uani 1 1 d . A . S2 S 0.70649(16) 0.76094(9) 0.11240(10) 0.0705(4) Uani 1 1 d . . . N11 N -0.0729(3) 0.3953(2) 0.05135(19) 0.0387(6) Uani 1 1 d D A . N12 N 0.1349(3) 0.55627(17) 0.17962(15) 0.0258(5) Uani 1 1 d D . . C11 C -0.1372(4) 0.4668(2) 0.1028(2) 0.0317(6) Uani 1 1 d D . . C12 C -0.0319(3) 0.5479(2) 0.16667(19) 0.0285(6) Uani 1 1 d D A . H12 H -0.0808 0.5984 0.2018 0.034 Uiso 1 1 calc R . . C13 C 0.1982(4) 0.4841(2) 0.1274(2) 0.0333(6) Uani 1 1 d D A . H13 H 0.3164 0.4875 0.1342 0.040 Uiso 1 1 calc R . . C14 C 0.0944(4) 0.4052(2) 0.0640(2) 0.0392(7) Uani 1 1 d D . . H14 H 0.1437 0.3558 0.0278 0.047 Uiso 1 1 calc R A . C15 C -0.3238(4) 0.4584(3) 0.0897(3) 0.0479(9) Uani 1 1 d D A . H15C H -0.3588 0.5210 0.0744 0.072 Uiso 1 1 calc R . . H15B H -0.3591 0.4493 0.1462 0.072 Uiso 1 1 calc R . . H15A H -0.3759 0.3996 0.0400 0.072 Uiso 1 1 calc R . . N21 N 0.5311(4) 0.3923(2) 0.4042(2) 0.0427(7) Uani 1 1 d . A . N22 N 0.4059(3) 0.55432(18) 0.34087(16) 0.0274(5) Uani 1 1 d . . . C21 C 0.6306(4) 0.4623(2) 0.3792(2) 0.0349(6) Uani 1 1 d . . . C22 C 0.5671(3) 0.5430(2) 0.3481(2) 0.0299(6) Uani 1 1 d . A . H22 H 0.6415 0.5920 0.3314 0.036 Uiso 1 1 calc R . . C23 C 0.3065(4) 0.4835(2) 0.3658(2) 0.0365(7) Uani 1 1 d . A . H23 H 0.1906 0.4881 0.3619 0.044 Uiso 1 1 calc R . . C24 C 0.3698(4) 0.4045(3) 0.3970(3) 0.0444(8) Uani 1 1 d . . . H24 H 0.2955 0.3561 0.4143 0.053 Uiso 1 1 calc R A . C25 C 0.8122(4) 0.4512(3) 0.3861(3) 0.0545(10) Uani 1 1 d . A . H25C H 0.8328 0.3899 0.4087 0.082 Uiso 1 1 calc R . . H25B H 0.8814 0.5116 0.4283 0.082 Uiso 1 1 calc R . . H25A H 0.8412 0.4451 0.3258 0.082 Uiso 1 1 calc R . . N31 N 0.6868(4) 0.9462(2) 0.52746(19) 0.0412(6) Uani 1 1 d . A . N32 N 0.4731(3) 0.79398(18) 0.39097(16) 0.0293(5) Uani 1 1 d . . . C31 C 0.6816(4) 0.9430(2) 0.4396(2) 0.0382(7) Uani 1 1 d . . . C32 C 0.5745(4) 0.8678(2) 0.3715(2) 0.0330(6) Uani 1 1 d . A . H32 H 0.5735 0.8690 0.3094 0.040 Uiso 1 1 calc R . . C33 C 0.4812(4) 0.7959(2) 0.4798(2) 0.0322(6) Uani 1 1 d . A . H33 H 0.4138 0.7439 0.4971 0.039 Uiso 1 1 calc R . . C34 C 0.5859(4) 0.8722(3) 0.5470(2) 0.0383(7) Uani 1 1 d . . . C35 C 0.7970(7) 1.0180(4) 0.4152(4) 0.0652(16) Uani 0.75 1 d P A 1 H35A H 0.7707 1.0866 0.4367 0.098 Uiso 0.75 1 calc PR A 1 H35B H 0.7858 1.0035 0.3487 0.098 Uiso 0.75 1 calc PR A 1 H35C H 0.9123 1.0143 0.4437 0.098 Uiso 0.75 1 calc PR A 1 C35' C 0.5920(11) 0.8719(6) 0.6392(4) 0.029(2) Uani 0.25 1 d PR A 2 H35D H 0.7082 0.8712 0.6685 0.043 Uiso 0.25 1 d PR A 2 H35E H 0.5204 0.8109 0.6442 0.043 Uiso 0.25 1 d PR A 2 H35F H 0.5529 0.9329 0.6694 0.043 Uiso 0.25 1 d PR A 2 N41 N 0.0776(4) 0.9567(2) 0.1604(2) 0.0495(7) Uani 1 1 d . A . N42 N 0.1962(3) 0.79620(18) 0.22904(16) 0.0290(5) Uani 1 1 d . . . C41 C 0.1234(5) 0.8779(3) 0.1063(2) 0.0430(8) Uani 1 1 d . . . C42 C 0.1827(4) 0.7987(2) 0.1413(2) 0.0336(6) Uani 1 1 d . A . H42 H 0.2149 0.7442 0.1013 0.040 Uiso 1 1 calc R . . C43 C 0.1488(5) 0.8741(2) 0.2825(2) 0.0401(7) Uani 1 1 d . A . H43 H 0.1548 0.8751 0.3454 0.048 Uiso 1 1 calc R . . C44 C 0.0910(5) 0.9534(3) 0.2476(3) 0.0505(9) Uani 1 1 d . . . H44 H 0.0595 1.0079 0.2879 0.061 Uiso 1 1 calc R A . C45 C 0.1127(9) 0.8798(4) 0.0093(3) 0.0825(18) Uani 1 1 d . A . H45A H 0.0664 0.9407 -0.0027 0.124 Uiso 1 1 calc R . . H45B H 0.0395 0.8184 -0.0288 0.124 Uiso 1 1 calc R . . H45C H 0.2250 0.8816 -0.0052 0.124 Uiso 1 1 calc R . . N51 N 0.3511(8) 0.7475(4) 0.8045(4) 0.0771(16) Uani 0.75 1 d PD B 1 N52 N 0.5108(10) 0.9522(6) 0.8549(8) 0.133(4) Uani 0.75 1 d PD B 1 C51 C 0.2626(8) 0.8236(5) 0.7990(4) 0.0585(14) Uani 0.75 1 d PD B 1 C52 C 0.3444(11) 0.9261(6) 0.8268(7) 0.101(3) Uani 0.75 1 d PD B 1 H52 H 0.2778 0.9792 0.8255 0.122 Uiso 0.75 1 calc PR B 1 C53 C 0.5928(11) 0.8712(8) 0.8565(9) 0.125(4) Uani 0.75 1 d PD B 1 H53 H 0.7114 0.8838 0.8755 0.150 Uiso 0.75 1 calc PR B 1 C54 C 0.5167(10) 0.7745(6) 0.8329(7) 0.096(3) Uani 0.75 1 d PD B 1 H54 H 0.5839 0.7220 0.8364 0.115 Uiso 0.75 1 calc PR B 1 C55 C 0.0758(8) 0.7968(6) 0.7672(5) 0.0682(17) Uani 0.75 1 d PD B 1 H55A H 0.0468 0.7938 0.7016 0.102 Uiso 0.75 1 calc PR B 1 H55B H 0.0208 0.8490 0.8002 0.102 Uiso 0.75 1 calc PR B 1 H55C H 0.0380 0.7301 0.7789 0.102 Uiso 0.75 1 calc PR B 1 N51' N 0.330(6) 0.781(3) 0.865(3) 0.236(12) Uiso 0.25 1 d PD C 2 N52' N 0.497(6) 0.881(3) 0.756(3) 0.236(12) Uiso 0.25 1 d PD C 2 C51' C 0.245(5) 0.803(3) 0.791(3) 0.236(12) Uiso 0.25 1 d PD C 2 C52' C 0.331(6) 0.854(3) 0.737(3) 0.236(12) Uiso 0.25 1 d PD C 2 H52' H 0.2682 0.8705 0.6845 0.283 Uiso 0.25 1 calc PR C 2 C53' C 0.579(5) 0.855(4) 0.830(4) 0.236(12) Uiso 0.25 1 d PD C 2 H53' H 0.6983 0.8702 0.8453 0.283 Uiso 0.25 1 calc PR C 2 C54' C 0.497(6) 0.809(4) 0.884(3) 0.236(12) Uiso 0.25 1 d PD C 2 H54' H 0.5605 0.7959 0.9381 0.283 Uiso 0.25 1 calc PR C 2 C55' C 0.057(5) 0.773(4) 0.768(5) 0.236(12) Uiso 0.25 1 d PD C 2 H55D H 0.0282 0.7066 0.7246 0.354 Uiso 0.25 1 calc PR C 2 H55E H 0.0059 0.8247 0.7399 0.354 Uiso 0.25 1 calc PR C 2 H55F H 0.0148 0.7689 0.8233 0.354 Uiso 0.25 1 calc PR C 2 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Co1 0.0233(2) 0.0276(2) 0.0214(2) 0.00360(13) 0.00411(13) 0.00482(13) N1 0.0312(12) 0.0393(14) 0.0307(13) 0.0042(10) 0.0091(10) 0.0045(10) S1 0.0360(10) 0.0498(13) 0.0506(13) 0.0002(9) 0.0240(9) 0.0069(7) S1' 0.059(5) 0.060(5) 0.046(4) 0.006(3) 0.027(4) 0.021(3) N2 0.0303(12) 0.0362(13) 0.0299(13) 0.0067(10) 0.0102(10) 0.0073(10) C2 0.0301(14) 0.0314(14) 0.0311(15) 0.0026(11) 0.0077(11) 0.0082(11) S2 0.0727(7) 0.0618(7) 0.0906(9) 0.0190(6) 0.0566(7) 0.0020(5) N11 0.0386(14) 0.0333(13) 0.0369(14) -0.0036(11) 0.0021(11) 0.0045(11) N12 0.0237(11) 0.0273(11) 0.0240(11) 0.0023(9) 0.0016(9) 0.0046(9) C11 0.0291(14) 0.0305(14) 0.0321(15) 0.0048(11) -0.0001(11) 0.0036(11) C12 0.0264(13) 0.0300(14) 0.0268(13) 0.0021(11) 0.0024(10) 0.0066(10) C13 0.0305(14) 0.0338(15) 0.0343(16) 0.0018(12) 0.0071(12) 0.0090(11) C14 0.0419(17) 0.0362(16) 0.0366(17) -0.0039(12) 0.0108(13) 0.0107(13) C15 0.0290(16) 0.0450(19) 0.061(2) 0.0005(16) -0.0004(15) 0.0021(13) N21 0.0434(15) 0.0390(15) 0.0513(17) 0.0223(13) 0.0088(13) 0.0083(12) N22 0.0248(11) 0.0319(12) 0.0259(12) 0.0081(9) 0.0041(9) 0.0045(9) C21 0.0325(15) 0.0336(15) 0.0371(16) 0.0095(12) 0.0006(12) 0.0061(12) C22 0.0267(13) 0.0308(14) 0.0321(14) 0.0105(11) 0.0026(11) 0.0029(11) C23 0.0308(15) 0.0400(16) 0.0424(17) 0.0156(13) 0.0120(13) 0.0026(12) C24 0.0443(18) 0.0433(18) 0.054(2) 0.0245(16) 0.0174(16) 0.0053(14) C25 0.0339(17) 0.050(2) 0.083(3) 0.026(2) 0.0025(18) 0.0124(15) N31 0.0389(14) 0.0397(15) 0.0366(15) -0.0053(11) 0.0032(11) 0.0031(11) N32 0.0296(12) 0.0293(12) 0.0261(12) 0.0025(9) 0.0017(9) 0.0048(9) C31 0.0343(15) 0.0356(16) 0.0391(17) -0.0002(13) 0.0053(13) 0.0002(12) C32 0.0352(15) 0.0321(15) 0.0296(15) 0.0032(11) 0.0059(12) 0.0037(12) C33 0.0340(15) 0.0345(15) 0.0253(14) 0.0053(11) 0.0011(11) 0.0038(12) C34 0.0395(16) 0.0406(17) 0.0296(15) -0.0001(12) 0.0002(13) 0.0093(13) C35 0.060(3) 0.050(3) 0.074(4) -0.001(3) 0.012(3) -0.013(3) C35' 0.028(5) 0.023(5) 0.026(5) -0.003(4) -0.002(4) -0.006(4) N41 0.063(2) 0.0383(15) 0.0516(18) 0.0161(13) 0.0093(15) 0.0191(14) N42 0.0312(12) 0.0272(11) 0.0265(12) 0.0036(9) 0.0012(9) 0.0074(9) C41 0.055(2) 0.0355(16) 0.0367(17) 0.0110(13) 0.0000(15) 0.0089(14) C42 0.0417(16) 0.0300(14) 0.0271(14) 0.0043(11) 0.0018(12) 0.0087(12) C43 0.055(2) 0.0348(16) 0.0340(16) 0.0064(13) 0.0115(14) 0.0189(14) C44 0.070(2) 0.0393(18) 0.051(2) 0.0127(15) 0.0205(18) 0.0267(17) C45 0.154(6) 0.057(3) 0.040(2) 0.0190(19) 0.009(3) 0.030(3) N51 0.081(4) 0.069(3) 0.084(4) 0.031(3) 0.001(3) 0.020(3) N52 0.084(5) 0.088(5) 0.231(12) 0.056(6) 0.030(6) 0.003(4) C51 0.077(4) 0.070(4) 0.042(3) 0.026(3) 0.024(3) 0.026(3) C52 0.109(7) 0.080(5) 0.140(8) 0.052(5) 0.051(6) 0.030(5) C53 0.068(5) 0.101(7) 0.221(14) 0.071(8) 0.030(7) 0.013(5) C54 0.076(5) 0.088(6) 0.136(8) 0.055(6) 0.014(5) 0.025(4) C55 0.084(4) 0.079(4) 0.048(3) 0.019(3) 0.014(3) 0.034(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 Co1 N1 2.063(3) . ? Co1 N2 2.066(2) . ? Co1 N42 2.168(2) . ? Co1 N32 2.186(2) . ? Co1 N12 2.191(2) . ? Co1 N22 2.193(2) . ? N1 C1 1.147(7) . ? N1 C1' 1.214(16) . ? C1 S1 1.626(6) . ? C1' S1' 1.612(15) . ? N2 C2 1.160(4) . ? C2 S2 1.613(3) . ? N11 C11 1.334(4) . ? N11 C14 1.338(4) . ? N12 C12 1.334(3) . ? N12 C13 1.340(4) . ? C11 C12 1.401(4) . ? C11 C15 1.495(4) . ? C13 C14 1.376(4) . ? N21 C21 1.334(4) . ? N21 C24 1.337(5) . ? N22 C22 1.334(4) . ? N22 C23 1.341(4) . ? C21 C22 1.390(4) . ? C21 C25 1.498(5) . ? C23 C24 1.369(5) . ? N31 C31 1.327(5) . ? N31 C34 1.337(5) . ? N32 C32 1.336(4) . ? N32 C33 1.341(4) . ? C31 C32 1.395(4) . ? C31 C35 1.452(6) . ? C33 C34 1.387(4) . ? C34 C35' 1.401(7) . ? N41 C44 1.329(5) . ? N41 C41 1.341(5) . ? N42 C42 1.332(4) . ? N42 C43 1.335(4) . ? C41 C42 1.387(4) . ? C41 C45 1.474(5) . ? C43 C44 1.382(5) . ? N51 C51 1.330(7) . ? N51 C54 1.335(9) . ? N52 C52 1.339(10) . ? N52 C53 1.348(11) . ? C51 C52 1.414(10) . ? C51 C55 1.502(8) . ? C53 C54 1.331(11) . ? N51' C51' 1.331(16) . ? N51' C54' 1.343(17) . ? N52' C52' 1.335(17) . ? N52' C53' 1.343(17) . ? C51' C52' 1.405(16) . ? C51' C55' 1.508(16) . ? C53' C54' 1.348(17) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Co1 N2 179.43(10) . . ? N1 Co1 N42 89.79(10) . . ? N2 Co1 N42 89.85(10) . . ? N1 Co1 N32 89.88(10) . . ? N2 Co1 N32 89.68(10) . . ? N42 Co1 N32 89.37(9) . . ? N1 Co1 N12 90.43(9) . . ? N2 Co1 N12 90.02(9) . . ? N42 Co1 N12 92.03(9) . . ? N32 Co1 N12 178.57(9) . . ? N1 Co1 N22 89.69(10) . . ? N2 Co1 N22 90.67(10) . . ? N42 Co1 N22 179.08(9) . . ? N32 Co1 N22 91.38(9) . . ? N12 Co1 N22 87.22(9) . . ? C1 N1 C1' 6.9(16) . . ? C1 N1 Co1 162.9(5) . . ? C1' N1 Co1 157.9(14) . . ? N1 C1 S1 178.7(8) . . ? N1 C1' S1' 175(2) . . ? C2 N2 Co1 157.4(2) . . ? N2 C2 S2 178.7(3) . . ? C11 N11 C14 116.8(3) . . ? C12 N12 C13 116.9(2) . . ? C12 N12 Co1 122.76(18) . . ? C13 N12 Co1 120.32(18) . . ? N11 C11 C12 120.6(3) . . ? N11 C11 C15 118.1(3) . . ? C12 C11 C15 121.2(3) . . ? N12 C12 C11 122.0(3) . . ? N12 C13 C14 121.0(3) . . ? N11 C14 C13 122.7(3) . . ? C21 N21 C24 116.2(3) . . ? C22 N22 C23 116.3(3) . . ? C22 N22 Co1 122.69(19) . . ? C23 N22 Co1 120.9(2) . . ? N21 C21 C22 120.8(3) . . ? N21 C21 C25 117.9(3) . . ? C22 C21 C25 121.3(3) . . ? N22 C22 C21 122.6(3) . . ? N22 C23 C24 120.9(3) . . ? N21 C24 C23 123.2(3) . . ? C31 N31 C34 116.2(3) . . ? C32 N32 C33 116.2(2) . . ? C32 N32 Co1 122.3(2) . . ? C33 N32 Co1 121.5(2) . . ? N31 C31 C32 121.8(3) . . ? N31 C31 C35 118.1(3) . . ? C32 C31 C35 120.0(4) . . ? N32 C32 C31 122.0(3) . . ? N32 C33 C34 121.4(3) . . ? N31 C34 C33 122.4(3) . . ? N31 C34 C35' 117.5(3) . . ? C33 C34 C35' 120.0(3) . . ? C44 N41 C41 116.3(3) . . ? C42 N42 C43 116.7(3) . . ? C42 N42 Co1 122.2(2) . . ? C43 N42 Co1 121.0(2) . . ? N41 C41 C42 120.8(3) . . ? N41 C41 C45 117.8(3) . . ? C42 C41 C45 121.4(4) . . ? N42 C42 C41 122.4(3) . . ? N42 C43 C44 120.8(3) . . ? N41 C44 C43 123.0(3) . . ? C51 N51 C54 116.0(6) . . ? C52 N52 C53 113.4(8) . . ? N51 C51 C52 119.8(6) . . ? N51 C51 C55 117.9(6) . . ? C52 C51 C55 122.2(6) . . ? N52 C52 C51 123.5(7) . . ? C54 C53 N52 123.7(8) . . ? C53 C54 N51 123.5(7) . . ? C51' N51' C54' 117(2) . . ? C52' N52' C53' 116(2) . . ? N51' C51' C52' 120(2) . . ? N51' C51' C55' 119(2) . . ? C52' C51' C55' 121(2) . . ? N52' C52' C51' 122(2) . . ? N52' C53' C54' 122(2) . . ? N51' C54' C53' 122(2) . . ? _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 1.251 _refine_diff_density_min -0.600 _refine_diff_density_rms 0.078 _database_code_depnum_ccdc_archive 'CCDC 936138' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_woe699 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H6 Cd N4 S2' _chemical_formula_sum 'C7 H6 Cd N4 S2' _chemical_formula_weight 322.68 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' Cd Cd -0.8075 1.2024 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/n' _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 8.4262(3) _cell_length_b 9.6325(3) _cell_length_c 13.0926(5) _cell_angle_alpha 90.00 _cell_angle_beta 94.251(3) _cell_angle_gamma 90.00 _cell_volume 1059.74(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 19854 _cell_measurement_theta_min 2.63 _cell_measurement_theta_max 29.18 _exptl_crystal_description block _exptl_crystal_colour white _exptl_crystal_size_max 0.1761 _exptl_crystal_size_mid 0.1140 _exptl_crystal_size_min 0.0501 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.022 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 2.418 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.4838 _exptl_absorpt_correction_T_max 0.8164 _exptl_absorpt_process_details 'X-Shape and X-Red32 (Stoe, 2008)' _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 'STOE IPDS-2' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 19854 _diffrn_reflns_av_R_equivalents 0.0332 _diffrn_reflns_av_sigmaI/netI 0.0160 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 29.18 _reflns_number_total 2859 _reflns_number_gt 2609 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'X-Area (Stoe, 2008)' _computing_cell_refinement 'X-Area (Stoe, 2008)' _computing_data_reduction 'X-Area (Stoe, 2008)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; XP in SHELXTL (Sheldrick, 2008) and Diamond (Brandenburg, 2011) ; _computing_publication_material 'XCIF in SHELXTL (Sheldrick, 2008)' _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^)+(0.0246P)^2^+0.7547P] 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 2859 _refine_ls_number_parameters 128 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0258 _refine_ls_R_factor_gt 0.0216 _refine_ls_wR_factor_ref 0.0516 _refine_ls_wR_factor_gt 0.0503 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.068 _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 Cd1 Cd 0.146492(18) 0.789715(15) 0.374334(10) 0.02695(5) Uani 1 1 d . . . N1 N 0.1635(2) 1.0115(2) 0.43395(16) 0.0385(4) Uani 1 1 d . . . C1 C 0.1435(2) 1.1148(2) 0.47595(16) 0.0302(4) Uani 1 1 d . . . S1 S 0.12101(7) 1.26319(6) 0.53445(5) 0.03797(13) Uani 1 1 d . . . N2 N 0.1424(3) 0.5543(2) 0.33689(17) 0.0432(5) Uani 1 1 d . . . C2 C 0.1226(2) 0.4532(2) 0.29023(16) 0.0302(4) Uani 1 1 d . . . S2 S 0.08691(7) 0.30918(6) 0.22497(5) 0.03599(12) Uani 1 1 d . . . N11 N 0.4929(2) 0.6775(2) 0.70906(13) 0.0308(4) Uani 1 1 d . . . N12 N 0.3105(2) 0.7254(2) 0.52713(15) 0.0350(4) Uani 1 1 d . . . C12 C 0.2687(3) 0.6314(2) 0.59453(17) 0.0342(5) Uani 1 1 d . . . H10 H 0.1754 0.5814 0.5800 0.041 Uiso 1 1 calc R . . C11 C 0.3592(2) 0.6045(2) 0.68629(16) 0.0292(4) Uani 1 1 d . . . C14 C 0.5364(3) 0.7692(3) 0.63966(17) 0.0365(5) Uani 1 1 d . . . H12 H 0.6306 0.8184 0.6530 0.044 Uiso 1 1 calc R . . C13 C 0.4468(3) 0.7932(3) 0.54939(18) 0.0383(5) Uani 1 1 d . . . H13 H 0.4817 0.8576 0.5031 0.046 Uiso 1 1 calc R . . C15 C 0.3092(3) 0.4973(2) 0.75924(18) 0.0388(5) Uani 1 1 d . . . H14A H 0.4017 0.4547 0.7931 0.058 Uiso 1 1 calc R . . H14B H 0.2463 0.4279 0.7225 0.058 Uiso 1 1 calc R . . H14C H 0.2472 0.5402 0.8092 0.058 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 Cd1 0.03143(8) 0.02680(8) 0.02214(8) -0.00176(5) -0.00125(5) -0.00003(5) N1 0.0430(11) 0.0318(9) 0.0423(11) -0.0074(8) 0.0137(8) -0.0058(8) C1 0.0304(10) 0.0309(10) 0.0297(10) 0.0023(8) 0.0053(8) -0.0056(8) S1 0.0437(3) 0.0290(3) 0.0426(3) -0.0085(2) 0.0128(2) -0.0070(2) N2 0.0561(13) 0.0327(10) 0.0410(11) -0.0048(8) 0.0058(9) -0.0013(9) C2 0.0330(10) 0.0295(9) 0.0284(10) 0.0016(8) 0.0045(8) 0.0019(8) S2 0.0349(3) 0.0356(3) 0.0382(3) -0.0104(2) 0.0073(2) -0.0077(2) N11 0.0286(8) 0.0393(9) 0.0241(8) 0.0004(7) -0.0003(6) -0.0029(7) N12 0.0384(10) 0.0375(10) 0.0279(9) 0.0020(7) -0.0051(7) -0.0064(8) C12 0.0337(10) 0.0339(11) 0.0336(11) 0.0035(8) -0.0059(8) -0.0059(9) C11 0.0305(10) 0.0294(9) 0.0273(9) -0.0003(8) -0.0009(7) -0.0007(8) C14 0.0333(11) 0.0490(13) 0.0268(10) 0.0019(9) -0.0003(8) -0.0130(10) C13 0.0422(12) 0.0459(13) 0.0262(10) 0.0054(9) -0.0009(9) -0.0118(10) C15 0.0414(12) 0.0368(11) 0.0370(11) 0.0087(9) -0.0049(9) -0.0076(10) _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 Cd1 N1 2.2751(19) . ? Cd1 N2 2.320(2) . ? Cd1 N12 2.4260(18) . ? Cd1 N11 2.4582(17) 4_575 ? Cd1 S1 2.6769(6) 3_576 ? Cd1 S2 2.6842(6) 2 ? N1 C1 1.155(3) . ? C1 S1 1.639(2) . ? S1 Cd1 2.6769(6) 3_576 ? N2 C2 1.155(3) . ? C2 S2 1.645(2) . ? S2 Cd1 2.6842(6) 2_545 ? N11 C14 1.338(3) . ? N11 C11 1.342(3) . ? N11 Cd1 2.4582(17) 4_676 ? N12 C12 1.330(3) . ? N12 C13 1.334(3) . ? C12 C11 1.399(3) . ? C11 C15 1.488(3) . ? C14 C13 1.374(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Cd1 N2 171.84(8) . . ? N1 Cd1 N12 86.51(7) . . ? N2 Cd1 N12 85.60(7) . . ? N1 Cd1 N11 101.36(7) . 4_575 ? N2 Cd1 N11 86.62(7) . 4_575 ? N12 Cd1 N11 171.62(6) . 4_575 ? N1 Cd1 S1 93.41(5) . 3_576 ? N2 Cd1 S1 84.75(6) . 3_576 ? N12 Cd1 S1 91.75(5) . 3_576 ? N11 Cd1 S1 90.64(5) 4_575 3_576 ? N1 Cd1 S2 93.83(5) . 2 ? N2 Cd1 S2 88.03(6) . 2 ? N12 Cd1 S2 88.35(5) . 2 ? N11 Cd1 S2 88.26(5) 4_575 2 ? S1 Cd1 S2 172.753(18) 3_576 2 ? C1 N1 Cd1 164.63(18) . . ? N1 C1 S1 178.1(2) . . ? C1 S1 Cd1 99.95(8) . 3_576 ? C2 N2 Cd1 159.25(19) . . ? N2 C2 S2 177.7(2) . . ? C2 S2 Cd1 100.57(8) . 2_545 ? C14 N11 C11 117.57(18) . . ? C14 N11 Cd1 111.10(14) . 4_676 ? C11 N11 Cd1 129.88(14) . 4_676 ? C12 N12 C13 117.00(19) . . ? C12 N12 Cd1 123.94(14) . . ? C13 N12 Cd1 118.94(15) . . ? N12 C12 C11 122.8(2) . . ? N11 C11 C12 119.25(19) . . ? N11 C11 C15 119.59(18) . . ? C12 C11 C15 121.16(19) . . ? N11 C14 C13 122.3(2) . . ? N12 C13 C14 121.0(2) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 29.18 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.336 _refine_diff_density_min -0.457 _refine_diff_density_rms 0.073 _database_code_depnum_ccdc_archive 'CCDC 936139'