# Electronic Supplementary Material (ESI) for RSC Advances # This journal is © The Royal Society of Chemistry 2014 ####################################################################### # # 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_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C4 H Cl N2 S2' _chemical_formula_sum 'C4 H Cl N2 S2' _chemical_formula_weight 176.64 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/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 7.5167(11) _cell_length_b 11.280(3) _cell_length_c 8.1382(16) _cell_angle_alpha 90.00 _cell_angle_beta 108.043(15) _cell_angle_gamma 90.00 _cell_volume 656.1(2) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2459 _cell_measurement_theta_min 3.5887 _cell_measurement_theta_max 33.4503 _exptl_crystal_description needle _exptl_crystal_colour yellow _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.788 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 352 _exptl_absorpt_coefficient_mu 1.114 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.26641 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details 'Empirical absorption correction (CrysAlis RED, Oxford Diffraction)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Sapphire3' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0288 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2781 _diffrn_reflns_av_R_equivalents 0.0291 _diffrn_reflns_av_sigmaI/netI 0.0279 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 9 _diffrn_reflns_theta_min 3.19 _diffrn_reflns_theta_max 24.99 _reflns_number_total 1102 _reflns_number_gt 905 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD' _computing_cell_refinement 'CrysAlis RED' _computing_data_reduction 'CrysAlis RED' _computing_structure_solution 'SHELXL-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; DIAMOND (Brandenburg, 2006) MERCURY (Bruno et al. 2002) ; _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^)+(0.1227P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1102 _refine_ls_number_parameters 86 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0603 _refine_ls_R_factor_gt 0.0527 _refine_ls_wR_factor_ref 0.1555 _refine_ls_wR_factor_gt 0.1521 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.045 _refine_ls_shift/su_max 0.026 _refine_ls_shift/su_mean 0.004 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 S1 S 0.12197(13) 0.23759(8) 0.89006(13) 0.0217(4) Uani 1 1 d . . . S2 S 0.21757(15) 0.06786(8) 0.97380(14) 0.0265(4) Uani 1 1 d . . . Cl1 Cl 0.61078(14) 0.26791(9) 1.32683(14) 0.0271(4) Uani 1 1 d . . . N1 N 0.3960(5) 0.1079(3) 1.1385(4) 0.0226(8) Uani 1 1 d . . . N2 N 0.0954(5) 0.5561(3) 0.8362(5) 0.0298(9) Uani 1 1 d . . . C1 C 0.4229(6) 0.2194(3) 1.1606(5) 0.0212(9) Uani 1 1 d . . . C2 C 0.3015(5) 0.3064(3) 1.0477(5) 0.0211(9) Uani 1 1 d . . . C3 C 0.3242(6) 0.4243(3) 1.0603(6) 0.0228(9) Uani 1 1 d . . . C4 C 0.1990(6) 0.4998(3) 0.9398(6) 0.0224(9) Uani 1 1 d . . . H1 H 0.418(7) 0.455(4) 1.150(7) 0.045(15) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 S1 0.0149(6) 0.0217(6) 0.0200(8) -0.0006(4) -0.0069(5) -0.0009(4) S2 0.0227(7) 0.0208(6) 0.0263(7) 0.0010(4) -0.0064(5) -0.0007(4) Cl1 0.0150(6) 0.0333(6) 0.0226(7) 0.0040(4) -0.0093(5) -0.0021(4) N1 0.0151(18) 0.0262(18) 0.021(2) 0.0047(14) -0.0022(16) 0.0025(14) N2 0.023(2) 0.0292(19) 0.029(2) 0.0032(16) -0.0034(19) 0.0006(15) C1 0.010(2) 0.025(2) 0.022(2) 0.0027(16) -0.0040(18) -0.0007(15) C2 0.012(2) 0.026(2) 0.021(2) 0.0013(16) -0.0022(18) 0.0007(16) C3 0.017(2) 0.026(2) 0.018(2) -0.0002(16) -0.007(2) 0.0010(16) C4 0.018(2) 0.0184(19) 0.026(3) -0.0046(17) -0.0005(19) -0.0045(16) _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 S1 C2 1.732(4) . ? S1 S2 2.0840(14) . ? S2 N1 1.639(4) . ? Cl1 C1 1.715(4) . ? N1 C1 1.277(5) . ? N2 C4 1.146(5) . ? C1 C2 1.456(6) . ? C2 C3 1.340(6) . ? C3 C4 1.414(6) . ? C3 H1 0.91(6) . ? 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 C2 S1 S2 93.38(14) . . ? N1 S2 S1 97.24(12) . . ? C1 N1 S2 116.1(3) . . ? N1 C1 C2 122.3(4) . . ? N1 C1 Cl1 118.8(3) . . ? C2 C1 Cl1 119.0(3) . . ? C3 C2 C1 125.5(4) . . ? C3 C2 S1 123.6(3) . . ? C1 C2 S1 110.9(3) . . ? C2 C3 C4 120.2(4) . . ? C2 C3 H1 119(3) . . ? C4 C3 H1 121(3) . . ? N2 C4 C3 176.4(4) . . ? _diffrn_measured_fraction_theta_max 0.960 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.960 _refine_diff_density_max 0.706 _refine_diff_density_min -0.803 _refine_diff_density_rms 0.150 _database_code_depnum_ccdc_archive 'CCDC 963574' ####################################################################### # # 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_shelxl _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C4 Br Cl N2 S2' _chemical_formula_sum 'C4 Br Cl N2 S2' _chemical_formula_weight 255.55 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' 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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P n m a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z+1/2' '-x, y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' '-x-1/2, y-1/2, z-1/2' 'x, -y-1/2, z' _cell_length_a 8.1226(8) _cell_length_b 6.7318(7) _cell_length_c 13.5987(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 743.57(12) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2247 _cell_measurement_theta_min 3.9029 _cell_measurement_theta_max 30.9085 _exptl_crystal_description needle _exptl_crystal_colour yellow _exptl_crystal_size_max 0.4 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.283 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 488 _exptl_absorpt_coefficient_mu 6.362 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.51187 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details 'Empirical absorption correction (CrysAlis RED, Oxford Diffraction)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Sapphire3' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0288 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2841 _diffrn_reflns_av_R_equivalents 0.0333 _diffrn_reflns_av_sigmaI/netI 0.0236 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.38 _diffrn_reflns_theta_max 25.00 _reflns_number_total 706 _reflns_number_gt 588 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD' _computing_cell_refinement 'CrysAlis RED' _computing_data_reduction 'CrysAlis RED' _computing_structure_solution 'SHELXL-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ; DIAMOND (Brandenburg, 2006) MERCURY (Bruno et al. 2002) ; _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^)+(0.0560P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens ? _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 706 _refine_ls_number_parameters 61 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0339 _refine_ls_R_factor_gt 0.0274 _refine_ls_wR_factor_ref 0.0715 _refine_ls_wR_factor_gt 0.0703 _refine_ls_goodness_of_fit_ref 0.950 _refine_ls_restrained_S_all 0.950 _refine_ls_shift/su_max 0.010 _refine_ls_shift/su_mean 0.001 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 Br1 Br 0.25972(6) 0.7500 0.71526(3) 0.0198(2) Uani 1 2 d S . . Cl1 Cl 0.60970(14) 0.2500 0.65226(8) 0.0190(3) Uani 1 2 d S . . S1 S -0.01566(16) 0.7500 0.55134(7) 0.0131(3) Uani 1 2 d S . . S2 S -0.10693(14) 0.7500 0.40753(8) 0.0152(3) Uani 1 2 d S . . N1 N 0.0732(4) 0.7500 0.3515(3) 0.0144(9) Uani 1 2 d S . . N2 N 0.1261(6) 0.7500 0.9469(3) 0.0242(10) Uani 1 2 d S . . C1 C 0.2022(6) 0.7500 0.4065(3) 0.0153(10) Uani 1 2 d S . . C2 C 0.1882(6) 0.7500 0.5122(3) 0.0126(9) Uani 1 2 d S . . C3 C 0.3142(6) 0.7500 0.5797(3) 0.0137(9) Uani 1 2 d S . . C4 C 0.4870(7) 0.7500 0.5604(3) 0.0159(10) 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 Br1 0.0178(3) 0.0304(3) 0.0112(3) 0.000 -0.00036(18) 0.000 Cl1 0.0152(7) 0.0276(6) 0.0141(6) 0.000 0.0048(4) 0.000 S1 0.0091(6) 0.0180(5) 0.0124(6) 0.000 0.0008(4) 0.000 S2 0.0119(7) 0.0189(5) 0.0148(6) 0.000 -0.0022(5) 0.000 N1 0.014(2) 0.0135(17) 0.016(2) 0.000 0.0002(16) 0.000 N2 0.018(3) 0.029(2) 0.025(2) 0.000 0.0077(19) 0.000 C1 0.015(3) 0.0136(19) 0.017(2) 0.000 0.0016(19) 0.000 C2 0.012(2) 0.0117(18) 0.014(2) 0.000 0.0026(18) 0.000 C3 0.012(2) 0.0178(19) 0.011(2) 0.000 0.0014(18) 0.000 C4 0.019(3) 0.016(2) 0.012(2) 0.000 -0.004(2) 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 Br1 C3 1.895(5) . ? Cl1 C1 1.723(5) 5_666 ? S1 C2 1.739(5) . ? S1 S2 2.0922(15) . ? S2 N1 1.649(4) . ? N1 C1 1.288(6) . ? N2 C4 1.135(7) 6_557 ? C1 C2 1.442(6) . ? C1 Cl1 1.723(5) 5_666 ? C2 C3 1.375(6) . ? C3 C4 1.427(8) . ? C4 N2 1.134(7) 6_657 ? 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 C2 S1 S2 93.01(16) . . ? N1 S2 S1 96.73(14) . . ? C1 N1 S2 116.9(3) . . ? N1 C1 C2 121.1(5) . . ? N1 C1 Cl1 116.9(4) . 5_666 ? C2 C1 Cl1 122.0(4) . 5_666 ? C3 C2 C1 127.4(5) . . ? C3 C2 S1 120.3(4) . . ? C1 C2 S1 112.2(4) . . ? C2 C3 C4 127.5(4) . . ? C2 C3 Br1 118.4(4) . . ? C4 C3 Br1 114.0(3) . . ? N2 C4 C3 174.4(4) 6_657 . ? _diffrn_measured_fraction_theta_max 0.986 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.986 _refine_diff_density_max 0.701 _refine_diff_density_min -0.652 _refine_diff_density_rms 0.126 _database_code_depnum_ccdc_archive 'CCDC 963573'