# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Tatsuro Imakubo' _publ_contact_author_name 'Dr Tatsuro Imakubo' _publ_contact_author_address ; RIKEN 2-1, Hirosawa Wako Saitama 351-0198 JAPAN ; _publ_contact_author_email IMAKUBO@POSTMAN.RIKEN.GO.JP _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Synthesis and Properties of Hetero-halogenated TTFs ; data_compound_2 _database_code_CSD 219243 _audit_creation_method SHELXL-97 _chemical_name_systematic ; 4-Chloro[1,3]dithiole-2-thione ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C3 H Cl S3' _chemical_formula_weight 168.67 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' 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' 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 4.0483(10) _cell_length_b 10.844(3) _cell_length_c 13.748(3) _cell_angle_alpha 90.00 _cell_angle_beta 97.190(5) _cell_angle_gamma 90.00 _cell_volume 598.8(3) _cell_formula_units_Z 4 _cell_measurement_temperature 295(2) _cell_measurement_reflns_used 3548 _cell_measurement_theta_min 2.40 _cell_measurement_theta_max 28.34 _exptl_crystal_description prism _exptl_crystal_colour yellow _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.871 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 336 _exptl_absorpt_coefficient_mu 1.543 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 295(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4173 _diffrn_reflns_av_R_equivalents 0.0223 _diffrn_reflns_av_sigmaI/netI 0.0227 _diffrn_reflns_limit_h_min -4 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.40 _diffrn_reflns_theta_max 28.34 _reflns_number_total 1479 _reflns_number_gt 1364 _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^)+(0.0496P)^2^+0.5343P] 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 1479 _refine_ls_number_parameters 64 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0403 _refine_ls_R_factor_gt 0.0378 _refine_ls_wR_factor_ref 0.1112 _refine_ls_wR_factor_gt 0.1098 _refine_ls_goodness_of_fit_ref 1.170 _refine_ls_restrained_S_all 1.170 _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 S2 S 0.41125(19) 0.34827(6) 0.48469(5) 0.0405(2) Uani 1 1 d . . . Cl1 Cl 0.7817(2) 0.13671(7) 0.57984(6) 0.0544(2) Uani 1 1 d . . . S3 S 0.3927(2) 0.24700(7) 0.29005(5) 0.0482(2) Uani 1 1 d . . . S1 S 0.0781(2) 0.49129(8) 0.31562(6) 0.0513(2) Uani 1 1 d . . . C2 C 0.5985(7) 0.2056(3) 0.4736(2) 0.0397(6) Uani 1 1 d . . . C1 C 0.2828(7) 0.3682(3) 0.3606(2) 0.0379(5) Uani 1 1 d . . . C3 C 0.5910(8) 0.1588(3) 0.3840(2) 0.0455(6) Uani 1 1 d . . . H3 H 0.6869 0.0831 0.3727 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 S2 0.0517(4) 0.0347(3) 0.0347(3) -0.0025(2) 0.0044(3) 0.0005(3) Cl1 0.0661(5) 0.0485(4) 0.0478(4) 0.0120(3) 0.0045(3) 0.0074(3) S3 0.0624(5) 0.0484(4) 0.0341(4) -0.0057(3) 0.0073(3) -0.0048(3) S1 0.0535(4) 0.0477(4) 0.0505(4) 0.0101(3) -0.0021(3) 0.0025(3) C2 0.0442(13) 0.0338(12) 0.0416(14) 0.0036(11) 0.0075(11) -0.0019(10) C1 0.0377(12) 0.0379(13) 0.0377(13) 0.0010(10) 0.0029(10) -0.0080(10) C3 0.0567(16) 0.0354(13) 0.0462(15) -0.0028(11) 0.0141(13) 0.0007(12) _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 S2 C1 1.733(3) . ? S2 C2 1.738(3) . ? Cl1 C2 1.724(3) . ? S3 C3 1.723(3) . ? S3 C1 1.725(3) . ? S1 C1 1.650(3) . ? C2 C3 1.329(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 C1 S2 C2 96.02(14) . . ? C3 S3 C1 97.46(14) . . ? C3 C2 Cl1 125.3(2) . . ? C3 C2 S2 117.5(2) . . ? Cl1 C2 S2 117.21(17) . . ? S1 C1 S3 123.92(17) . . ? S1 C1 S2 123.00(17) . . ? S3 C1 S2 113.08(16) . . ? C2 C3 S3 116.0(2) . . ? _diffrn_measured_fraction_theta_max 0.985 _diffrn_reflns_theta_full 28.34 _diffrn_measured_fraction_theta_full 0.985 _refine_diff_density_max 0.371 _refine_diff_density_min -0.366 _refine_diff_density_rms 0.107 data_ClIPS _database_code_CSD 219244 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C8 H2 Cl I N2 S2 Se2' _chemical_formula_weight 510.51 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' Se Se -0.0929 2.2259 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M Pn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y, z+1/2' _cell_length_a 6.7584(15) _cell_length_b 4.0939(9) _cell_length_c 22.946(5) _cell_angle_alpha 90.00 _cell_angle_beta 97.097(4) _cell_angle_gamma 90.00 _cell_volume 630.0(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1559 _cell_measurement_theta_min 3.06 _cell_measurement_theta_max 28.25 _exptl_crystal_description needle _exptl_crystal_colour red _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 2.691 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 468 _exptl_absorpt_coefficient_mu 8.833 _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 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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2464 _diffrn_reflns_av_R_equivalents 0.0264 _diffrn_reflns_av_sigmaI/netI 0.0484 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 3 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 4 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.79 _diffrn_reflns_theta_max 28.26 _reflns_number_total 1391 _reflns_number_gt 1314 _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^)+(0.1207P)^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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.0(2) _refine_ls_number_reflns 1391 _refine_ls_number_parameters 146 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0628 _refine_ls_R_factor_gt 0.0602 _refine_ls_wR_factor_ref 0.1595 _refine_ls_wR_factor_gt 0.1572 _refine_ls_goodness_of_fit_ref 1.119 _refine_ls_restrained_S_all 1.118 _refine_ls_shift/su_max 0.003 _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 C7 C 0.659(3) 1.036(4) 0.1715(6) 0.030(3) Uani 1 1 d . . . I1 I 0.72096(12) 0.1290(2) -0.14820(4) 0.0343(3) Uani 1 1 d . . . Se3 Se 0.5803(3) 0.8526(5) 0.09683(8) 0.0347(5) Uani 1 1 d . . . Se2 Se 1.0492(3) 0.8208(4) 0.14980(9) 0.0338(4) Uani 1 1 d . . . Cl1 Cl 1.2300(7) 0.1186(12) -0.0860(2) 0.0398(11) Uani 1 1 d . . . N1 N 0.932(3) 1.137(4) 0.2475(6) 0.037(4) Uani 1 1 d . . . C1 C 0.845(3) 0.724(5) 0.0863(6) 0.030(4) Uani 1 1 d . . . C4 C 0.590(4) 1.295(5) 0.2527(9) 0.053(6) Uani 1 1 d . . . H4 H 0.4994 1.4029 0.2733 0.064 Uiso 1 1 calc R . . C5 C 0.887(2) 0.572(4) 0.0369(6) 0.024(3) Uani 1 1 d . . . C3 C 0.786(4) 1.277(5) 0.2777(9) 0.051(6) Uani 1 1 d . . . H3 H 0.8211 1.3585 0.3154 0.061 Uiso 1 1 calc R . . C6 C 0.852(3) 0.295(4) -0.0663(7) 0.026(3) Uani 1 1 d . . . N2 N 0.522(3) 1.166(4) 0.1999(8) 0.045(4) Uani 1 1 d . . . C2 C 0.866(2) 1.016(4) 0.1948(6) 0.024(3) Uani 1 1 d . . . S1 S 1.1243(8) 0.4370(13) 0.0244(2) 0.0369(10) Uani 1 1 d . . . S2 S 0.6925(6) 0.4735(13) -0.01998(18) 0.0342(10) Uani 1 1 d . . . C8 C 1.048(3) 0.294(4) -0.0463(7) 0.034(4) Uani 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 C7 0.033(9) 0.034(8) 0.024(7) 0.001(6) 0.013(7) -0.013(7) I1 0.0438(7) 0.0351(5) 0.0252(5) -0.0043(4) 0.0090(4) -0.0022(5) Se3 0.0291(10) 0.0472(11) 0.0279(8) -0.0084(6) 0.0035(7) 0.0010(8) Se2 0.0297(9) 0.0437(9) 0.0278(8) -0.0107(6) 0.0034(7) -0.0004(8) Cl1 0.030(2) 0.055(3) 0.037(2) -0.0082(17) 0.015(2) 0.005(2) N1 0.046(10) 0.045(10) 0.021(6) -0.006(5) 0.010(7) -0.003(7) C1 0.027(9) 0.050(10) 0.014(6) -0.002(6) 0.004(6) 0.000(8) C4 0.082(18) 0.045(11) 0.043(10) -0.006(8) 0.050(12) -0.004(11) C5 0.020(7) 0.031(8) 0.020(6) -0.005(5) 0.003(6) -0.006(6) C3 0.09(2) 0.028(9) 0.038(9) -0.006(7) 0.022(11) 0.002(11) C6 0.030(9) 0.028(8) 0.023(6) -0.004(5) 0.011(7) 0.006(7) N2 0.060(12) 0.037(9) 0.043(8) 0.001(6) 0.024(9) 0.010(8) C2 0.032(9) 0.027(8) 0.015(6) 0.001(5) 0.007(6) -0.007(7) S1 0.028(2) 0.053(3) 0.0301(19) -0.0130(17) 0.0028(17) -0.001(2) S2 0.025(2) 0.053(3) 0.0237(17) -0.0098(16) 0.0027(17) 0.001(2) C8 0.044(11) 0.037(9) 0.024(7) -0.001(6) 0.021(8) 0.002(8) _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 C7 N2 1.31(2) . ? C7 C2 1.43(2) . ? C7 Se3 1.886(16) . ? I1 C6 2.090(16) . ? Se3 C1 1.911(18) . ? Se2 C2 1.886(15) . ? Se2 C1 1.919(17) . ? Cl1 C8 1.773(16) . ? N1 C2 1.33(2) . ? N1 C3 1.40(3) . ? C1 C5 1.353(19) . ? C4 N2 1.35(3) . ? C4 C3 1.38(4) . ? C5 S1 1.752(16) . ? C5 S2 1.782(16) . ? C6 C8 1.34(3) . ? C6 S2 1.765(14) . ? S1 C8 1.741(18) . ? 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 N2 C7 C2 123.6(16) . . ? N2 C7 Se3 118.4(16) . . ? C2 C7 Se3 118.0(11) . . ? C7 Se3 C1 93.4(7) . . ? C2 Se2 C1 92.6(7) . . ? C2 N1 C3 115.0(18) . . ? C5 C1 Se3 121.9(13) . . ? C5 C1 Se2 121.7(13) . . ? Se3 C1 Se2 116.3(8) . . ? N2 C4 C3 123.7(17) . . ? C1 C5 S1 124.9(13) . . ? C1 C5 S2 120.4(13) . . ? S1 C5 S2 114.6(8) . . ? C4 C3 N1 121.1(18) . . ? C8 C6 S2 116.4(12) . . ? C8 C6 I1 126.7(10) . . ? S2 C6 I1 116.9(9) . . ? C7 N2 C4 115(2) . . ? N1 C2 C7 121.4(13) . . ? N1 C2 Se2 118.9(12) . . ? C7 C2 Se2 119.6(10) . . ? C8 S1 C5 94.9(8) . . ? C6 S2 C5 94.8(8) . . ? C6 C8 S1 119.0(11) . . ? C6 C8 Cl1 122.8(12) . . ? S1 C8 Cl1 117.9(12) . . ? _diffrn_measured_fraction_theta_max 0.814 _diffrn_reflns_theta_full 28.26 _diffrn_measured_fraction_theta_full 0.814 _refine_diff_density_max 2.025 _refine_diff_density_min -1.372 _refine_diff_density_rms 0.352