# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Ruben Mas-Balleste' _publ_contact_author_email RUBEN.MAS@UAM.ES _publ_section_title ; Activation of the S-S bond in Metal-perthiocarboxylato compounds ; loop_ _publ_author_name 'Ruben Mas-Balleste' 'Oscar Castillo' 'Rodrigo Gonzalez-Prieto' 'Alejandro Guijarro' ; P.J.S.Miguel ; 'Felix Zamora' # Attachment 'CIFs_dalton.cif' data_compound1 _database_code_depnum_ccdc_archive 'CCDC 741333' _audit_creation_method SHELXL-97 _chemical_name_systematic ; "trans-[bis(perthioacetato-k2S,S')platinum(II)]" ; _chemical_formula_moiety 'C4 H6 Pt S6' _chemical_formula_sum 'C4 H6 Pt S6' _chemical_formula_iupac '[Pt(C2H3S3)2]' _chemical_formula_weight 441.54 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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' S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pt Pt -4.5932 6.9264 '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 5.9784(1) _cell_length_b 6.1942(1) _cell_length_c 14.9075(2) _cell_angle_alpha 90.00 _cell_angle_beta 113.389(1) _cell_angle_gamma 90.00 _cell_volume 506.69(1) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3084 _cell_measurement_theta_min 6.47 _cell_measurement_theta_max 70.65 _exptl_crystal_description prism _exptl_crystal_colour brown _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.894 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 408 _exptl_absorpt_coefficient_mu 36.940 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details '(SADABS; Sheldrick, 2005)' _exptl_absorpt_correction_T_min 0.162 _exptl_absorpt_correction_T_max 0.325 _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\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_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 3084 _diffrn_reflns_av_R_equivalents 0.0271 _diffrn_reflns_av_sigmaI/netI 0.0263 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 6.47 _diffrn_reflns_theta_max 70.65 _reflns_number_total 932 _reflns_number_gt 863 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0475P)^2^+1.6593P] 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 932 _refine_ls_number_parameters 53 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0312 _refine_ls_R_factor_gt 0.0291 _refine_ls_wR_factor_ref 0.0777 _refine_ls_wR_factor_gt 0.0763 _refine_ls_goodness_of_fit_ref 1.107 _refine_ls_restrained_S_all 1.107 _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 Pt1 Pt 0.5000 0.5000 0.5000 0.01611(17) Uani 1 2 d S . . S1 S 0.2757(3) 0.1924(2) 0.48804(10) 0.0216(3) Uani 1 1 d . . . S2 S 0.1827(3) 0.6668(2) 0.38041(10) 0.0201(3) Uani 1 1 d . . . S3 S -0.0694(3) 0.2583(3) 0.38926(10) 0.0215(3) Uani 1 1 d . . . C1 C -0.0620(13) 0.5072(8) 0.3433(5) 0.0153(14) Uani 1 1 d . . . C2 C -0.2972(12) 0.5902(12) 0.2682(5) 0.0245(14) Uani 1 1 d . . . H2A H -0.2948 0.7484 0.2683 0.037 Uiso 1 1 calc R . . H2B H -0.4330 0.5395 0.2838 0.037 Uiso 1 1 calc R . . H2C H -0.3177 0.5371 0.2035 0.037 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 Pt1 0.0189(3) 0.0209(3) 0.0080(2) -0.00044(11) 0.00484(16) 0.00212(12) S1 0.0228(8) 0.0243(8) 0.0143(7) 0.0006(6) 0.0037(6) 0.0012(6) S2 0.0208(8) 0.0235(8) 0.0130(7) 0.0022(6) 0.0036(6) 0.0021(6) S3 0.0232(8) 0.0231(8) 0.0174(7) 0.0022(6) 0.0071(6) -0.0009(6) C1 0.015(3) 0.021(3) 0.010(3) -0.0027(19) 0.004(3) 0.003(2) C2 0.020(3) 0.034(4) 0.018(3) -0.001(3) 0.006(3) 0.001(3) _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 Pt1 S2 2.2715(14) 3_666 ? Pt1 S2 2.2715(14) . ? Pt1 S1 2.2959(16) . ? Pt1 S1 2.2959(16) 3_666 ? S1 S3 2.045(2) . ? S2 C1 1.667(7) . ? S3 C1 1.695(6) . ? C1 C2 1.498(9) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag S2 Pt1 S2 180.000(1) 3_666 . ? S2 Pt1 S1 87.91(5) 3_666 . ? S2 Pt1 S1 92.09(5) . . ? S2 Pt1 S1 92.09(5) 3_666 3_666 ? S2 Pt1 S1 87.91(5) . 3_666 ? S1 Pt1 S1 180.0 . 3_666 ? S3 S1 Pt1 106.34(8) . . ? C1 S2 Pt1 109.9(2) . . ? C1 S3 S1 107.0(3) . . ? C2 C1 S2 118.9(5) . . ? C2 C1 S3 116.5(5) . . ? S2 C1 S3 124.4(4) . . ? C1 C2 H2A 109.5 . . ? C1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? 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 S2 Pt1 S1 S3 175.55(8) 3_666 . . . ? S2 Pt1 S1 S3 -4.45(8) . . . . ? S1 Pt1 S2 C1 2.9(2) . . . . ? S1 Pt1 S2 C1 -177.1(2) 3_666 . . . ? Pt1 S1 S3 C1 5.2(3) . . . . ? Pt1 S2 C1 C2 176.7(4) . . . . ? Pt1 S2 C1 S3 0.2(5) . . . . ? S1 S3 C1 C2 179.8(4) . . . . ? S1 S3 C1 S2 -3.7(5) . . . . ? _diffrn_measured_fraction_theta_max 0.953 _diffrn_reflns_theta_full 70.65 _diffrn_measured_fraction_theta_full 0.953 _refine_diff_density_max 1.674 _refine_diff_density_min -2.098 _refine_diff_density_rms 0.209 _chemical_name_common 'trans-(bis(perthioacetato-k2S,S')platinum(ii))' #===END data_compound2 _database_code_depnum_ccdc_archive 'CCDC 741334' _audit_creation_method SHELXL-97 _chemical_name_systematic ; "(dithioacetato-k2S,S')(perthioacetato-k2S,S')nickel(II)" ; _chemical_formula_moiety 'C4 H6 Ni S5' _chemical_formula_sum 'C4 H6 Ni S5' _chemical_formula_iupac '[Ni(C2H3S2)(C2H3S3)]' _chemical_formula_weight 273.10 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' 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 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 7.755(3) _cell_length_b 11.059(3) _cell_length_c 12.411(5) _cell_angle_alpha 90.00 _cell_angle_beta 113.74(5) _cell_angle_gamma 90.00 _cell_volume 974.3(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 4891 _cell_measurement_theta_min 2.57 _cell_measurement_theta_max 28.35 _exptl_crystal_description prismatic _exptl_crystal_colour 'dark blue' _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.862 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 552 _exptl_absorpt_coefficient_mu 2.989 _exptl_absorpt_correction_type numerical _exptl_absorpt_process_details 'CrysAlis RED (Oxford Diffraction, 2003)' _exptl_absorpt_correction_T_min 0.889 _exptl_absorpt_correction_T_max 0.928 _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type Xcalibur _diffrn_measurement_method \w _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 4953 _diffrn_reflns_av_R_equivalents 0.0809 _diffrn_reflns_av_sigmaI/netI 0.0869 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.57 _diffrn_reflns_theta_max 28.35 _reflns_number_total 4953 _reflns_number_gt 2506 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD (Oxford Diffraction, 2003)' _computing_cell_refinement 'CrysAlis CCD (Oxford Diffraction, 2003)' _computing_data_reduction 'CrysAlis RED (Oxford Diffraction, 2003)' _computing_structure_solution 'Sir92 (Altamore et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 (Farrugia, 1997)' _computing_publication_material 'WinGX (Farrugia, 1999)' _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^)+(0.1345P)^2^]' _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 4953 _refine_ls_number_parameters 94 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1324 _refine_ls_R_factor_gt 0.0775 _refine_ls_wR_factor_ref 0.2298 _refine_ls_wR_factor_gt 0.2117 _refine_ls_goodness_of_fit_ref 0.931 _refine_ls_restrained_S_all 0.931 _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 0.76656(12) 0.13125(7) 0.34797(7) 0.0572(3) Uani 1 1 d . . . S11 S 0.7356(3) 0.01926(15) 0.47898(14) 0.0647(5) Uani 1 1 d . . . S12 S 0.7245(3) -0.16398(16) 0.30771(18) 0.0722(6) Uani 1 1 d . . . S13 S 0.7474(3) -0.00912(16) 0.22704(15) 0.0714(6) Uani 1 1 d . . . C11 C 0.7129(9) -0.1247(5) 0.4319(6) 0.0593(17) Uani 1 1 d . . . C12 C 0.6956(11) -0.2247(6) 0.5094(6) 0.072(2) Uani 1 1 d . . . H12A H 0.5764 -0.2645 0.4707 0.108 Uiso 1 1 calc R . . H12B H 0.7039 -0.1912 0.5827 0.108 Uiso 1 1 calc R . . H12C H 0.7955 -0.2820 0.5240 0.108 Uiso 1 1 calc R . . S21 S 0.7985(3) 0.27140(15) 0.22851(15) 0.0654(5) Uani 1 1 d . . . S22 S 0.7794(3) 0.30015(16) 0.44500(16) 0.0722(6) Uani 1 1 d . . . C21 C 0.7912(10) 0.3739(6) 0.3272(6) 0.0621(18) Uani 1 1 d . . . C22 C 0.7961(10) 0.5024(5) 0.3169(6) 0.0688(19) Uani 1 1 d . . . H22A H 0.8743 0.5365 0.3918 0.103 Uiso 1 1 calc R . . H22B H 0.6708 0.5342 0.2917 0.103 Uiso 1 1 calc R . . H22C H 0.8466 0.5228 0.2601 0.103 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 Ni1 0.0601(6) 0.0608(6) 0.0559(5) -0.0054(4) 0.0286(5) -0.0029(4) S11 0.0756(15) 0.0634(10) 0.0614(10) -0.0039(8) 0.0341(11) -0.0011(10) S12 0.0941(17) 0.0594(10) 0.0770(12) -0.0019(8) 0.0489(13) -0.0005(10) S13 0.0944(16) 0.0655(11) 0.0672(11) -0.0043(8) 0.0458(12) 0.0013(10) C11 0.045(4) 0.062(4) 0.074(4) 0.000(3) 0.027(4) 0.005(3) C12 0.075(6) 0.077(5) 0.069(4) 0.019(4) 0.034(4) 0.002(4) S21 0.0793(14) 0.0640(10) 0.0607(10) 0.0022(8) 0.0364(11) -0.0032(9) S22 0.0946(16) 0.0696(11) 0.0624(11) -0.0051(9) 0.0420(12) -0.0071(10) C21 0.058(5) 0.062(4) 0.065(4) -0.003(3) 0.023(4) -0.005(3) C22 0.065(5) 0.062(4) 0.077(4) -0.001(3) 0.027(5) -0.001(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 Ni1 S13 2.1225(18) . ? Ni1 S11 2.1331(18) . ? Ni1 S22 2.2028(19) . ? Ni1 S21 2.2267(18) . ? S11 C11 1.681(6) . ? S12 C11 1.638(6) . ? S12 S13 2.027(2) . ? C11 C12 1.506(8) . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? S21 C21 1.686(6) . ? S22 C21 1.709(6) . ? C21 C22 1.429(8) . ? C22 H22A 0.9600 . ? C22 H22B 0.9600 . ? C22 H22C 0.9600 . ? 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 S13 Ni1 S11 96.73(7) . . ? S13 Ni1 S22 169.00(8) . . ? S11 Ni1 S22 94.00(7) . . ? S13 Ni1 S21 91.90(7) . . ? S11 Ni1 S21 171.35(7) . . ? S22 Ni1 S21 77.36(7) . . ? C11 S11 Ni1 108.2(2) . . ? C11 S12 S13 106.8(2) . . ? S12 S13 Ni1 105.29(9) . . ? C12 C11 S12 117.3(5) . . ? C12 C11 S11 119.8(5) . . ? S12 C11 S11 122.7(4) . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C21 S21 Ni1 86.5(2) . . ? C21 S22 Ni1 86.7(2) . . ? C22 C21 S21 126.4(5) . . ? C22 C21 S22 124.3(5) . . ? S21 C21 S22 109.3(4) . . ? C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 28.35 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 0.818 _refine_diff_density_min -0.631 _refine_diff_density_rms 0.177 _chemical_name_common '(dithioacetato-k2S,S')(perthioacetato-k2S,S')nickel(ii)'