# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 222 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Geng, Lei' 'Cheng, Wen-Dan' 'Zhang, Wei-Long' _publ_contact_author_name 'Wen-Dan Cheng' _publ_contact_author_address ; ; _publ_contact_author_email cwd@fjirsm.ac.cn data_a_PbBiBS4 _database_code_depnum_ccdc_archive 'CCDC 804731' #TrackingRef '- PbBiBS4.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'B Bi Pb S4' _chemical_formula_weight 555.22 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source B B 0.0013 0.0007 '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' Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting ? _symmetry_space_group_name_H-M 'P 21/m' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 5.971(10) _cell_length_b 6.273(9) _cell_length_c 9.132(15) _cell_angle_alpha 90.00 _cell_angle_beta 107.75(2) _cell_angle_gamma 90.00 _cell_volume 325.7(9) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 327 _cell_measurement_theta_min 2.3416 _cell_measurement_theta_max 27.2571 _exptl_crystal_description prism _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.13 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 5.661 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 468 _exptl_absorpt_coefficient_mu 53.929 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.0328 _exptl_absorpt_correction_T_max 0.0747 _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 'Mercury2 (2x2 bin mode)' _diffrn_measurement_method CCD_Profile_fitting _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2503 _diffrn_reflns_av_R_equivalents 0.0524 _diffrn_reflns_av_sigmaI/netI 0.0507 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.34 _diffrn_reflns_theta_max 27.35 _reflns_number_total 801 _reflns_number_gt 709 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+0.8905P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0013(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 801 _refine_ls_number_parameters 44 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0430 _refine_ls_R_factor_gt 0.0355 _refine_ls_wR_factor_ref 0.0791 _refine_ls_wR_factor_gt 0.0755 _refine_ls_goodness_of_fit_ref 1.141 _refine_ls_restrained_S_all 1.141 _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 Bi1 Bi 0.68389(11) 0.2500 0.85456(7) 0.0186(2) Uani 1 2 d S . . B1 B 0.157(3) 0.2500 0.195(2) 0.023(4) Uani 1 2 d S . . Pb1 Pb 0.74296(16) 0.19915(14) 0.44556(10) 0.0292(4) Uani 0.50 1 d P . . S1 S 0.0068(5) 0.0046(4) 0.2129(3) 0.0189(6) Uani 1 1 d . . . S2 S 0.3893(7) 0.2500 0.5796(4) 0.0199(8) Uani 1 2 d S . . S3 S 0.4340(7) 0.2500 0.1524(4) 0.0192(8) Uani 1 2 d S . . 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 Bi1 0.0171(3) 0.0197(3) 0.0204(3) 0.000 0.0078(3) 0.000 B1 0.016(9) 0.036(11) 0.016(9) 0.000 0.003(8) 0.000 Pb1 0.0219(5) 0.0397(10) 0.0254(5) -0.0018(4) 0.0064(4) -0.0036(4) S1 0.0172(14) 0.0125(12) 0.0300(16) 0.0019(12) 0.0115(12) 0.0009(11) S2 0.016(2) 0.027(2) 0.0159(18) 0.000 0.0035(16) 0.000 S3 0.014(2) 0.025(2) 0.021(2) 0.000 0.0092(17) 0.000 _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 Bi1 S2 2.590(5) . ? Bi1 S1 2.653(4) 2_656 ? Bi1 S1 2.653(4) 3_656 ? B1 S3 1.81(2) . ? B1 S1 1.814(11) . ? B1 S1 1.814(11) 4_565 ? Pb1 Pb1 0.638(2) 4_565 ? Pb1 S2 2.763(5) . ? Pb1 S3 2.768(6) . ? Pb1 S2 2.916(4) 3_656 ? S1 Bi1 2.653(4) 3_656 ? S2 Pb1 2.763(5) 4_565 ? S2 Pb1 2.916(4) 3_656 ? S2 Pb1 2.916(4) 2_656 ? S3 Pb1 2.768(6) 4_565 ? 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 Bi1 S1 95.16(14) . 2_656 ? S2 Bi1 S1 95.16(14) . 3_656 ? S1 Bi1 S1 74.04(16) 2_656 3_656 ? S3 B1 S1 121.9(5) . . ? S3 B1 S1 121.9(5) . 4_565 ? S1 B1 S1 116.1(11) . 4_565 ? Pb1 Pb1 S2 83.37(2) 4_565 . ? Pb1 Pb1 S3 83.38(2) 4_565 . ? S2 Pb1 S3 92.36(17) . . ? Pb1 Pb1 S2 165.06(9) 4_565 3_656 ? S2 Pb1 S2 85.49(8) . 3_656 ? S3 Pb1 S2 87.16(9) . 3_656 ? B1 S1 Bi1 95.2(5) . 3_656 ? Bi1 S2 Pb1 92.55(18) . 4_565 ? Bi1 S2 Pb1 92.55(18) . . ? Pb1 S2 Pb1 13.26(5) 4_565 . ? Bi1 S2 Pb1 99.44(8) . 3_656 ? Pb1 S2 Pb1 107.56(9) 4_565 3_656 ? Pb1 S2 Pb1 94.51(8) . 3_656 ? Bi1 S2 Pb1 99.44(8) . 2_656 ? Pb1 S2 Pb1 94.51(8) 4_565 2_656 ? Pb1 S2 Pb1 107.56(9) . 2_656 ? Pb1 S2 Pb1 150.11(17) 3_656 2_656 ? B1 S3 Pb1 100.2(6) . 4_565 ? B1 S3 Pb1 100.2(6) . . ? Pb1 S3 Pb1 13.24(5) 4_565 . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.35 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.640 _refine_diff_density_min -1.901 _refine_diff_density_rms 0.356 # Attachment '- PbSbBS4.txt' data_a_PbSbBS4 _database_code_depnum_ccdc_archive 'CCDC 804732' #TrackingRef '- PbSbBS4.txt' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'B Pb S4 Sb' _chemical_formula_weight 467.99 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source B B 0.0013 0.0007 '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' Sb Sb -0.5866 1.5461 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting ? _symmetry_space_group_name_H-M P21/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' _cell_length_a 5.9532(18) _cell_length_b 6.2031(13) _cell_length_c 9.250(3) _cell_angle_alpha 90.00 _cell_angle_beta 108.200(16) _cell_angle_gamma 90.00 _cell_volume 324.48(16) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 760 _cell_measurement_theta_min 2.3179 _cell_measurement_theta_max 27.4046 _exptl_crystal_description prism _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 4.790 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 404 _exptl_absorpt_coefficient_mu 31.222 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.1463 _exptl_absorpt_correction_T_max 0.3681 _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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2505 _diffrn_reflns_av_R_equivalents 0.0468 _diffrn_reflns_av_sigmaI/netI 0.0467 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.32 _diffrn_reflns_theta_max 27.39 _reflns_number_total 796 _reflns_number_gt 681 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0336P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 796 _refine_ls_number_parameters 43 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0455 _refine_ls_R_factor_gt 0.0373 _refine_ls_wR_factor_ref 0.0828 _refine_ls_wR_factor_gt 0.0778 _refine_ls_goodness_of_fit_ref 1.124 _refine_ls_restrained_S_all 1.124 _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 Sb1 Sb 0.69037(13) 0.2500 0.84074(9) 0.0191(2) Uani 1 2 d S . . B1 B 0.168(2) 0.2500 0.1965(16) 0.018(3) Uani 1 2 d S . . Pb1 Pb 0.74151(10) 0.2078(2) 0.44080(7) 0.0302(5) Uani 0.50 1 d P . . S1 S 0.0152(4) 0.0026(3) 0.2155(3) 0.0202(5) Uani 1 1 d . . . S2 S 0.3993(5) 0.2500 0.5833(3) 0.0213(7) Uani 1 2 d S . . S3 S 0.4375(5) 0.2500 0.1516(4) 0.0244(7) Uani 1 2 d S . . 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 Sb1 0.0182(4) 0.0189(5) 0.0192(4) 0.000 0.0044(3) 0.000 B1 0.024(7) 0.006(6) 0.024(7) 0.000 0.006(6) 0.000 Pb1 0.0217(3) 0.0423(13) 0.0254(4) -0.0022(4) 0.0057(2) -0.0048(3) S1 0.0196(10) 0.0135(11) 0.0286(12) 0.0010(9) 0.0089(9) -0.0001(8) S2 0.0190(14) 0.0244(16) 0.0188(15) 0.000 0.0034(12) 0.000 S3 0.0201(15) 0.0292(17) 0.0242(16) 0.000 0.0074(12) 0.000 _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 Sb1 S2 2.469(3) . ? Sb1 S1 2.523(2) 2_656 ? Sb1 S1 2.523(2) 3_656 ? B1 S3 1.777(14) . ? B1 S1 1.821(8) . ? B1 S1 1.821(8) 4_565 ? Pb1 Pb1 0.523(3) 4_565 ? Pb1 S3 2.734(3) . ? Pb1 S2 2.763(3) . ? Pb1 S2 2.9496(16) 3_656 ? S1 Sb1 2.523(2) 3_656 ? S2 Pb1 2.763(3) 4_565 ? S2 Pb1 2.9496(16) 3_656 ? S2 Pb1 2.9496(16) 2_656 ? S3 Pb1 2.734(3) 4_565 ? 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 Sb1 S1 97.16(8) . 2_656 ? S2 Sb1 S1 97.16(8) . 3_656 ? S1 Sb1 S1 76.78(9) 2_656 3_656 ? S3 B1 S1 122.5(4) . . ? S3 B1 S1 122.5(4) . 4_565 ? S1 B1 S1 114.9(7) . 4_565 ? Pb1 Pb1 S3 84.51(3) 4_565 . ? Pb1 Pb1 S2 84.57(3) 4_565 . ? S3 Pb1 S2 95.53(9) . . ? Pb1 Pb1 S2 164.32(6) 4_565 3_656 ? S3 Pb1 S2 86.14(6) . 3_656 ? S2 Pb1 S2 83.84(6) . 3_656 ? B1 S1 Sb1 95.9(4) . 3_656 ? Sb1 S2 Pb1 93.44(10) . 4_565 ? Sb1 S2 Pb1 93.44(10) . . ? Pb1 S2 Pb1 10.87(6) 4_565 . ? Sb1 S2 Pb1 99.79(6) . 3_656 ? Pb1 S2 Pb1 106.83(7) 4_565 3_656 ? Pb1 S2 Pb1 96.16(6) . 3_656 ? Sb1 S2 Pb1 99.79(6) . 2_656 ? Pb1 S2 Pb1 96.16(6) 4_565 2_656 ? Pb1 S2 Pb1 106.83(7) . 2_656 ? Pb1 S2 Pb1 148.64(11) 3_656 2_656 ? B1 S3 Pb1 98.1(5) . 4_565 ? B1 S3 Pb1 98.1(5) . . ? Pb1 S3 Pb1 10.98(6) 4_565 . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 27.39 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 1.607 _refine_diff_density_min -1.223 _refine_diff_density_rms 0.283