Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name 'Lawrence Gahan' 'German Cavigliasso' 'Clint A. Sharrad' 'Robert Stranger' _publ_contact_author_name 'Dr Lawrence Gahan' _publ_contact_author_address ; Chemistry Department The University of Queensland Brisbane Queensland 4072 AUSTRALIA ; _publ_contact_author_email GAHAN@MAILBOX.UQ.EDU.AU _publ_requested_journal 'Dalton Transactions' _publ_section_title ; Synthesis, Characterization and DFT Studies of the cobalt(III) complex of a tetrapodal pentadentate N4S donor ligand ; data_cs28241 _database_code_depnum_ccdc_archive 'CCDC 228914' _audit_creation_date 2003-09-01T18:06:00-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_common '[Co(N4samp)Cl](ZnCl4)' _chemical_formula_sum 'C10 H26 Cl5 Co N4 S Zn' _chemical_formula_weight 535.96 #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 7.861(2) _cell_length_b 15.432(2) _cell_length_c 16.856(2) _cell_angle_alpha 90 _cell_angle_beta 98.64(2) _cell_angle_gamma 90 _cell_volume 2021.6(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour purple _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 1.761 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1088 #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 2.77 _exptl_absorpt_correction_type psiscans #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_measurement_device CAD4 _diffrn_measurement_method 'omega-2theta scans' _diffrn_standards_decay_% 'less than 5 %' _diffrn_reflns_av_R_equivalents 0.0488 _diffrn_reflns_av_unetI/netI 0.0425 _diffrn_reflns_number 3824 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.8 _diffrn_reflns_theta_max 24.97 _diffrn_reflns_theta_full 24.97 _diffrn_measured_fraction_theta_full 0.999 _diffrn_measured_fraction_theta_max 0.999 _reflns_number_total 3550 _reflns_number_gt 2430 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection CAD4 _computing_cell_refinement SET4 _computing_data_reduction XTAL3.2 _computing_structure_solution 'SIR-92 (Altomare et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0865P)^2^+2.2869P] 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_number_reflns 3550 _refine_ls_number_parameters 199 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0869 _refine_ls_R_factor_obs 0.051 _refine_ls_wR_factor_all 0.1518 _refine_ls_wR_factor_obs 0.1338 _refine_ls_goodness_of_fit_ref 1.078 _refine_ls_restrained_S_all 1.078 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 1.235 _refine_diff_density_min -0.432 _refine_diff_density_rms 0.134 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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' Cl Cl 0.1484 0.1585 '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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Zn1 Zn 0.32441(10) 0.24040(5) 0.31534(4) 0.0448(2) Uani 1 1 d . . . Co1 Co 0.75616(10) 0.09714(5) 0.08911(5) 0.0348(2) Uani 1 1 d . . . Cl5 Cl 0.5758(2) 0.31620(11) 0.33602(9) 0.0464(4) Uani 1 1 d . . . Cl1 Cl 0.7616(2) 0.00467(11) -0.01935(9) 0.0457(4) Uani 1 1 d . . . S1 S 0.6987(2) 0.17810(10) 0.18697(9) 0.0366(4) Uani 1 1 d . . . Cl4 Cl 0.1407(3) 0.31077(12) 0.38495(12) 0.0586(5) Uani 1 1 d . . . Cl2 Cl 0.2144(2) 0.24202(17) 0.18173(11) 0.0707(6) Uani 1 1 d . . . Cl3 Cl 0.3643(3) 0.10342(13) 0.35460(14) 0.0721(6) Uani 1 1 d . . . N3 N 0.5517(6) 0.1536(3) 0.0282(3) 0.0392(12) Uani 1 1 d . . . H3A H 0.5566 0.1466 -0.0244 0.047 Uiso 1 1 calc R . . H3B H 0.4579 0.125 0.0388 0.047 Uiso 1 1 calc R . . N1 N 0.6386(7) 0.0052(3) 0.1415(3) 0.0426(13) Uani 1 1 d . . . H1A H 0.525 0.0102 0.1243 0.051 Uiso 1 1 calc R . . H1B H 0.6722 -0.0461 0.1238 0.051 Uiso 1 1 calc R . . N2 N 0.9721(7) 0.0491(4) 0.1474(3) 0.0493(14) Uani 1 1 d . . . H2A H 1.0108 0.0101 0.1146 0.059 Uiso 1 1 calc R . . H2B H 1.0491 0.0927 0.1535 0.059 Uiso 1 1 calc R . . N4 N 0.8943(7) 0.1836(4) 0.0396(3) 0.0471(14) Uani 1 1 d . . . H4A H 0.9952 0.1892 0.0723 0.057 Uiso 1 1 calc R . . H4B H 0.9181 0.1604 -0.0065 0.057 Uiso 1 1 calc R . . C8 C 0.8273(9) 0.2716(4) 0.0208(4) 0.0467(16) Uani 1 1 d . . . H8A H 0.779 0.2743 -0.0356 0.056 Uiso 1 1 calc R . . H8B H 0.922 0.3125 0.0299 0.056 Uiso 1 1 calc R . . C5 C 0.8360(9) 0.1385(4) 0.2753(4) 0.0440(15) Uani 1 1 d . . . H5A H 0.9521 0.1603 0.2766 0.053 Uiso 1 1 calc R . . H5B H 0.7932 0.1578 0.3234 0.053 Uiso 1 1 calc R . . C2 C 0.8355(9) 0.0387(4) 0.2714(4) 0.0449(16) Uani 1 1 d . . . C9 C 0.6912(9) 0.2984(4) 0.0704(4) 0.0441(15) Uani 1 1 d . . . C6 C 0.7581(9) 0.2859(4) 0.1607(4) 0.0459(16) Uani 1 1 d . . . H6A H 0.7068 0.3284 0.1922 0.055 Uiso 1 1 calc R . . H6B H 0.8821 0.2927 0.171 0.055 Uiso 1 1 calc R . . C7 C 0.5248(8) 0.2487(4) 0.0428(4) 0.0437(15) Uani 1 1 d . . . H7A H 0.4497 0.2547 0.0832 0.052 Uiso 1 1 calc R . . H7B H 0.4669 0.2747 -0.0063 0.052 Uiso 1 1 calc R . . C4 C 0.9794(9) 0.0070(4) 0.2266(4) 0.0479(17) Uani 1 1 d . . . H4C H 1.0899 0.0191 0.2587 0.058 Uiso 1 1 calc R . . H4D H 0.9699 -0.0553 0.2193 0.058 Uiso 1 1 calc R . . C1 C 0.8700(11) 0.0050(5) 0.3574(4) 0.063(2) Uani 1 1 d . . . H1C H 0.9775 0.0277 0.3837 0.095 Uiso 1 1 calc R . . H1D H 0.8751 -0.0571 0.3569 0.095 Uiso 1 1 calc R . . H1E H 0.779 0.0233 0.3857 0.095 Uiso 1 1 calc R . . C10 C 0.6516(11) 0.3961(4) 0.0572(5) 0.063(2) Uani 1 1 d . . . H10A H 0.5659 0.4134 0.0891 0.094 Uiso 1 1 calc R . . H10B H 0.6097 0.4065 0.0016 0.094 Uiso 1 1 calc R . . H10C H 0.7547 0.4291 0.0729 0.094 Uiso 1 1 calc R . . C3 C 0.6636(9) 0.0018(4) 0.2309(4) 0.0462(16) Uani 1 1 d . . . H3C H 0.6551 -0.0581 0.2475 0.055 Uiso 1 1 calc R . . H3D H 0.5711 0.0337 0.2497 0.055 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 Zn1 0.0480(5) 0.0449(5) 0.0397(4) -0.0064(3) 0.0002(3) 0.0013(3) Co1 0.0355(5) 0.0388(5) 0.0288(4) -0.0061(3) 0.0003(3) -0.0025(3) Cl5 0.0480(9) 0.0516(10) 0.0386(8) -0.0053(7) 0.0032(7) 0.0015(7) Cl1 0.0483(9) 0.0505(9) 0.0365(8) -0.0112(7) 0.0012(7) -0.0021(7) S1 0.0420(8) 0.0383(9) 0.0289(7) -0.0033(6) 0.0036(6) 0.0017(7) Cl4 0.0632(11) 0.0542(11) 0.0631(11) -0.0030(9) 0.0245(9) 0.0023(9) Cl2 0.0491(10) 0.1200(19) 0.0398(10) -0.0063(10) -0.0031(8) -0.0162(11) Cl3 0.0868(15) 0.0422(10) 0.0816(14) -0.0027(10) -0.0061(11) 0.0026(10) N3 0.041(3) 0.039(3) 0.036(3) -0.002(2) -0.001(2) -0.010(2) N1 0.044(3) 0.043(3) 0.037(3) -0.001(2) -0.002(2) -0.004(3) N2 0.038(3) 0.061(4) 0.047(3) -0.013(3) -0.001(2) 0.011(3) N4 0.047(3) 0.054(4) 0.042(3) -0.004(3) 0.013(3) -0.009(3) C8 0.051(4) 0.050(4) 0.040(4) -0.001(3) 0.009(3) -0.015(3) C5 0.050(4) 0.049(4) 0.031(3) -0.004(3) -0.003(3) 0.005(3) C2 0.055(4) 0.042(4) 0.035(3) -0.002(3) -0.002(3) 0.002(3) C9 0.053(4) 0.036(3) 0.041(4) -0.003(3) 0.000(3) -0.006(3) C6 0.062(4) 0.038(3) 0.039(4) -0.014(3) 0.012(3) -0.006(3) C7 0.044(4) 0.044(4) 0.042(4) 0.001(3) 0.002(3) 0.003(3) C4 0.051(4) 0.046(4) 0.042(4) -0.002(3) -0.010(3) 0.009(3) C1 0.082(6) 0.057(5) 0.045(4) 0.003(4) -0.005(4) 0.005(4) C10 0.087(6) 0.038(4) 0.064(5) 0.000(4) 0.014(4) -0.003(4) C3 0.063(4) 0.038(4) 0.038(4) 0.006(3) 0.006(3) -0.002(3) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 Zn1 Cl3 2.223(2) . ? Zn1 Cl4 2.270(2) . ? Zn1 Cl5 2.2780(19) . ? Zn1 Cl2 2.288(2) . ? Co1 N1 1.973(5) . ? Co1 N2 1.974(5) . ? Co1 N3 1.975(5) . ? Co1 N4 1.982(5) . ? Co1 S1 2.1701(17) . ? Co1 Cl1 2.3247(17) . ? S1 C6 1.800(7) . ? S1 C5 1.809(6) . ? N3 C7 1.508(8) . ? N1 C3 1.491(8) . ? N2 C4 1.478(9) . ? N4 C8 1.474(9) . ? C8 C9 1.511(9) . ? C5 C2 1.542(9) . ? C2 C1 1.526(9) . ? C2 C3 1.529(10) . ? C2 C4 1.531(10) . ? C9 C7 1.527(9) . ? C9 C6 1.547(9) . ? C9 C10 1.549(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag Cl3 Zn1 Cl4 111.92(9) . . ? Cl3 Zn1 Cl5 111.25(8) . . ? Cl4 Zn1 Cl5 106.26(7) . . ? Cl3 Zn1 Cl2 108.60(9) . . ? Cl4 Zn1 Cl2 109.13(8) . . ? Cl5 Zn1 Cl2 109.63(7) . . ? N1 Co1 N2 86.2(2) . . ? N1 Co1 N3 98.7(2) . . ? N2 Co1 N3 175.1(2) . . ? N1 Co1 N4 174.7(2) . . ? N2 Co1 N4 88.7(2) . . ? N3 Co1 N4 86.5(2) . . ? N1 Co1 S1 84.76(16) . . ? N2 Co1 S1 95.71(17) . . ? N3 Co1 S1 83.98(16) . . ? N4 Co1 S1 97.04(17) . . ? N1 Co1 Cl1 88.63(16) . . ? N2 Co1 Cl1 92.57(17) . . ? N3 Co1 Cl1 88.38(16) . . ? N4 Co1 Cl1 90.33(17) . . ? S1 Co1 Cl1 169.02(7) . . ? C6 S1 C5 111.7(3) . . ? C6 S1 Co1 104.7(2) . . ? C5 S1 Co1 105.3(2) . . ? C7 N3 Co1 117.9(4) . . ? C3 N1 Co1 118.6(4) . . ? C4 N2 Co1 121.9(4) . . ? C8 N4 Co1 120.7(4) . . ? N4 C8 C9 113.2(5) . . ? C2 C5 S1 107.8(4) . . ? C1 C2 C3 108.4(6) . . ? C1 C2 C4 108.7(6) . . ? C3 C2 C4 109.3(5) . . ? C1 C2 C5 107.5(5) . . ? C3 C2 C5 112.8(5) . . ? C4 C2 C5 110.0(6) . . ? C8 C9 C7 109.9(5) . . ? C8 C9 C6 110.2(6) . . ? C7 C9 C6 112.7(5) . . ? C8 C9 C10 109.3(6) . . ? C7 C9 C10 107.5(6) . . ? C6 C9 C10 107.1(5) . . ? C9 C6 S1 107.2(4) . . ? N3 C7 C9 113.8(5) . . ? N2 C4 C2 111.9(5) . . ? N1 C3 C2 114.2(5) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag N1 Co1 S1 C6 -171.9(3) . . . . ? N2 Co1 S1 C6 102.5(3) . . . . ? N3 Co1 S1 C6 -72.6(3) . . . . ? N4 Co1 S1 C6 13.1(3) . . . . ? Cl1 Co1 S1 C6 -118.7(4) . . . . ? N1 Co1 S1 C5 70.2(3) . . . . ? N2 Co1 S1 C5 -15.4(3) . . . . ? N3 Co1 S1 C5 169.5(3) . . . . ? N4 Co1 S1 C5 -104.8(3) . . . . ? Cl1 Co1 S1 C5 123.3(4) . . . . ? N1 Co1 N3 C7 122.5(4) . . . . ? N2 Co1 N3 C7 -48(3) . . . . ? N4 Co1 N3 C7 -58.7(4) . . . . ? S1 Co1 N3 C7 38.7(4) . . . . ? Cl1 Co1 N3 C7 -149.2(4) . . . . ? N2 Co1 N1 C3 58.5(5) . . . . ? N3 Co1 N1 C3 -120.6(5) . . . . ? N4 Co1 N1 C3 73(3) . . . . ? S1 Co1 N1 C3 -37.6(4) . . . . ? Cl1 Co1 N1 C3 151.2(5) . . . . ? N1 Co1 N2 C4 -30.8(5) . . . . ? N3 Co1 N2 C4 140(2) . . . . ? N4 Co1 N2 C4 150.5(5) . . . . ? S1 Co1 N2 C4 53.6(5) . . . . ? Cl1 Co1 N2 C4 -119.2(5) . . . . ? N1 Co1 N4 C8 -161(2) . . . . ? N2 Co1 N4 C8 -146.5(5) . . . . ? N3 Co1 N4 C8 32.6(5) . . . . ? S1 Co1 N4 C8 -50.9(5) . . . . ? Cl1 Co1 N4 C8 121.0(5) . . . . ? Co1 N4 C8 C9 23.0(7) . . . . ? C6 S1 C5 C2 -154.5(5) . . . . ? Co1 S1 C5 C2 -41.4(5) . . . . ? S1 C5 C2 C1 -152.3(5) . . . . ? S1 C5 C2 C3 -32.9(7) . . . . ? S1 C5 C2 C4 89.5(6) . . . . ? N4 C8 C9 C7 -71.8(7) . . . . ? N4 C8 C9 C6 52.9(7) . . . . ? N4 C8 C9 C10 170.4(6) . . . . ? C8 C9 C6 S1 -90.8(6) . . . . ? C7 C9 C6 S1 32.3(7) . . . . ? C10 C9 C6 S1 150.4(5) . . . . ? C5 S1 C6 C9 156.8(5) . . . . ? Co1 S1 C6 C9 43.3(5) . . . . ? Co1 N3 C7 C9 27.4(7) . . . . ? C8 C9 C7 N3 43.7(7) . . . . ? C6 C9 C7 N3 -79.6(7) . . . . ? C10 C9 C7 N3 162.6(6) . . . . ? Co1 N2 C4 C2 -24.6(7) . . . . ? C1 C2 C4 N2 -170.1(6) . . . . ? C3 C2 C4 N2 71.8(7) . . . . ? C5 C2 C4 N2 -52.7(7) . . . . ? Co1 N1 C3 C2 -28.0(7) . . . . ? C1 C2 C3 N1 -161.5(6) . . . . ? C4 C2 C3 N1 -43.2(7) . . . . ? C5 C2 C3 N1 79.5(7) . . . . ?