Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2011 # Attachment '- chem_comm.cif' data_publication_text #TrackingRef '- chem_comm.cif' _publ_requested_journal Chem.Commun. _publ_contact_author_name 'Dr Jeremy Rawson' _publ_contact_author_address ; Department of Chemistry and Biochemistry The University of Windsor 401 Sunset Avenue Windsor ON Canada N9B 3P4 ; _publ_contact_author_email jmrawson@uwindsor.ca loop_ _publ_author_name _publ_author_address Alberola ; Dep de Quimica Fisica I Analitica-Quimica Fisica Universitat Jaume I Av de Vicent Sos Bayant s/n E-12071 Castello de la Plana SPAIN ; Carter ; The School of Chemistry Cardiff University Main Building Park Place Cardiff CF10 3AT UK ; C.constantinides ; Department of Chemistry The University of Cambridge Lensfield Road Cambridge CB2 1EW UK ; D.Eisler ; Department of Chemistry The University of Cambridge Lensfield Road Cambridge CB2 1EW UK ; D.Murphy ; The School of Chemistry Cardiff University Main Building Park Place Cardiff CF10 3AT UK ; _publ_section_title ; Crystal structures, EPR and magnetic properties of 2-ClC6H4CNSSN and 2,5-Cl2C6H3CNSSN ; _publ_section_abstract ; Crystal engineering techniques have been implemented to weaken pi*-pi* dimerisation in a pair of thiazyl radicals. A combination of X-ray diffraction, EPR spectroscopy and SQUID magnetometry are used to characterise the title radicals. The EPR studies reveal that the origins of paramagnetism in the two title compounds have different microscopic origins; unpairing of the pi*-pi* dimer to generate two S = 1/2 radicals and thermal population of an excited triplet state. ; data_1 _database_code_depnum_ccdc_archive 'CCDC 796396' #TrackingRef '- chem_comm.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H4 Cl N2 S2' _chemical_formula_sum 'C7 H4 Cl N2 S2' _chemical_formula_weight 215.69 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 Pc loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, -y, z+1/2' _cell_length_a 9.5948(19) _cell_length_b 14.020(3) _cell_length_c 12.332(3) _cell_angle_alpha 90.00 _cell_angle_beta 91.24(3) _cell_angle_gamma 90.00 _cell_volume 1658.6(6) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 51311 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.48 _exptl_crystal_description needle _exptl_crystal_colour red _exptl_crystal_size_max 0.18 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.728 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 872 _exptl_absorpt_coefficient_mu 0.899 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.761 _exptl_absorpt_correction_T_max 0.941 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 12441 _diffrn_reflns_av_R_equivalents 0.0566 _diffrn_reflns_av_sigmaI/netI 0.0540 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.20 _diffrn_reflns_theta_max 24.00 _reflns_number_total 4388 _reflns_number_gt 3925 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _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^)+(0.0587P)^2^+2.5678P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.15(11) _refine_ls_number_reflns 4388 _refine_ls_number_parameters 433 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0576 _refine_ls_R_factor_gt 0.0457 _refine_ls_wR_factor_ref 0.1331 _refine_ls_wR_factor_gt 0.1099 _refine_ls_goodness_of_fit_ref 1.165 _refine_ls_restrained_S_all 1.164 _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 C10 C 0.5183(8) 0.1690(5) 0.1883(6) 0.0310(17) Uani 1 1 d . . . C11 C 0.5863(8) 0.2533(5) 0.2406(6) 0.0309(17) Uani 1 1 d . . . S11 S 0.3327(2) 0.04394(15) 0.16259(17) 0.0376(5) Uani 1 1 d . . . N11 N 0.3991(7) 0.1349(4) 0.2278(5) 0.0352(15) Uani 1 1 d . . . Cl12 Cl 0.3411(2) 0.35230(14) 0.22260(18) 0.0426(5) Uani 1 1 d . . . C12 C 0.5168(8) 0.3383(5) 0.2610(6) 0.0327(18) Uani 1 1 d . . . S12 S 0.4948(2) 0.03861(14) 0.05085(16) 0.0357(5) Uani 1 1 d . . . N12 N 0.5803(7) 0.1290(4) 0.1053(5) 0.0342(15) Uani 1 1 d . . . C13 C 0.5838(9) 0.4143(6) 0.3121(7) 0.042(2) Uani 1 1 d . . . H13 H 0.5351 0.4719 0.3259 0.051 Uiso 1 1 calc R . . C14 C 0.7225(9) 0.4046(6) 0.3426(7) 0.040(2) Uani 1 1 d . . . H14 H 0.7682 0.4555 0.3796 0.048 Uiso 1 1 calc R . . C15 C 0.7947(9) 0.3243(6) 0.3209(7) 0.043(2) Uani 1 1 d . . . H15 H 0.8909 0.3197 0.3400 0.051 Uiso 1 1 calc R . . C16 C 0.7260(8) 0.2480(5) 0.2698(7) 0.0375(19) Uani 1 1 d . . . H16 H 0.7763 0.1913 0.2550 0.045 Uiso 1 1 calc R . . C20 C 0.2285(8) 0.1860(5) 0.4482(6) 0.0310(17) Uani 1 1 d . . . S21 S 0.1645(2) 0.01485(13) 0.41448(17) 0.0337(5) Uani 1 1 d . . . N21 N 0.2594(6) 0.0962(4) 0.4779(5) 0.0282(14) Uani 1 1 d . . . C21 C 0.3180(7) 0.2636(5) 0.4941(6) 0.0276(17) Uani 1 1 d . . . Cl22 Cl 0.1056(2) 0.39489(13) 0.48829(16) 0.0381(5) Uani 1 1 d . . . S22 S 0.0460(2) 0.11395(14) 0.32655(17) 0.0340(5) Uani 1 1 d . . . N22 N 0.1253(6) 0.2063(4) 0.3776(5) 0.0277(14) Uani 1 1 d . . . C22 C 0.2753(8) 0.3567(5) 0.5142(6) 0.0320(18) Uani 1 1 d . . . C23 C 0.3661(9) 0.4232(5) 0.5602(6) 0.0375(19) Uani 1 1 d . . . H23 H 0.3350 0.4861 0.5746 0.045 Uiso 1 1 calc R . . C24 C 0.5055(8) 0.3966(6) 0.5855(7) 0.041(2) Uani 1 1 d . . . H24 H 0.5677 0.4414 0.6181 0.050 Uiso 1 1 calc R . . C25 C 0.5499(8) 0.3068(6) 0.5630(6) 0.0375(19) Uani 1 1 d . . . H25 H 0.6441 0.2894 0.5779 0.045 Uiso 1 1 calc R . . C26 C 0.4578(8) 0.2407(5) 0.5183(6) 0.0292(16) Uani 1 1 d . . . H26 H 0.4902 0.1781 0.5036 0.035 Uiso 1 1 calc R . . C30 C -0.0065(8) 0.1782(5) 0.6583(6) 0.0281(17) Uani 1 1 d . . . S31 S -0.0610(2) 0.01025(13) 0.59738(17) 0.0350(5) Uani 1 1 d . . . N31 N 0.0215(6) 0.0849(4) 0.6771(5) 0.0337(15) Uani 1 1 d . . . C31 C 0.0722(8) 0.2492(5) 0.7222(6) 0.0329(18) Uani 1 1 d . . . S32 S -0.1724(2) 0.11647(13) 0.51465(17) 0.0355(5) Uani 1 1 d . . . Cl32 Cl -0.1432(2) 0.37989(15) 0.71185(17) 0.0405(5) Uani 1 1 d . . . N32 N -0.1005(6) 0.2049(4) 0.5821(5) 0.0331(15) Uani 1 1 d . . . C32 C 0.0250(8) 0.3418(5) 0.7459(6) 0.0315(17) Uani 1 1 d . . . C33 C 0.1083(9) 0.4060(6) 0.8010(7) 0.042(2) Uani 1 1 d . . . H33 H 0.0752 0.4686 0.8149 0.051 Uiso 1 1 calc R . . C34 C 0.2417(9) 0.3790(6) 0.8365(7) 0.047(2) Uani 1 1 d . . . H34 H 0.2986 0.4230 0.8758 0.056 Uiso 1 1 calc R . . C35 C 0.2920(9) 0.2877(6) 0.8144(7) 0.042(2) Uani 1 1 d . . . H35 H 0.3833 0.2694 0.8372 0.050 Uiso 1 1 calc R . . C36 C 0.2065(8) 0.2247(6) 0.7589(6) 0.039(2) Uani 1 1 d . . . H36 H 0.2400 0.1623 0.7450 0.047 Uiso 1 1 calc R . . C40 C 0.7402(8) 0.1646(5) 0.8845(6) 0.0303(17) Uani 1 1 d . . . S41 S 0.6833(2) 0.00208(14) 0.81159(16) 0.0356(5) Uani 1 1 d . . . N41 N 0.7716(6) 0.0727(4) 0.8937(5) 0.0324(15) Uani 1 1 d . . . C41 C 0.8222(8) 0.2341(5) 0.9526(6) 0.0304(17) Uani 1 1 d . . . S42 S 0.5673(2) 0.11390(14) 0.74122(16) 0.0360(5) Uani 1 1 d . . . Cl42 Cl 0.5982(2) 0.35515(15) 0.97066(18) 0.0432(5) Uani 1 1 d . . . N42 N 0.6448(7) 0.1964(4) 0.8147(5) 0.0354(16) Uani 1 1 d . . . C42 C 0.7727(8) 0.3192(5) 0.9924(6) 0.0327(18) Uani 1 1 d . . . C43 C 0.8544(9) 0.3808(6) 1.0540(7) 0.042(2) Uani 1 1 d . . . H43 H 0.8174 0.4397 1.0781 0.051 Uiso 1 1 calc R . . C44 C 0.9883(9) 0.3563(6) 1.0800(7) 0.045(2) Uani 1 1 d . . . H44 H 1.0444 0.3974 1.1239 0.055 Uiso 1 1 calc R . . C45 C 1.0433(9) 0.2701(6) 1.0417(7) 0.044(2) Uani 1 1 d . . . H45 H 1.1372 0.2534 1.0586 0.052 Uiso 1 1 calc R . . C46 C 0.9620(8) 0.2105(6) 0.9803(6) 0.0374(19) Uani 1 1 d . . . H46 H 0.9997 0.1520 0.9555 0.045 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 C10 0.030(4) 0.030(4) 0.033(5) 0.006(3) 0.004(4) -0.001(3) C11 0.030(4) 0.037(4) 0.026(4) 0.003(3) 0.001(3) 0.000(3) S11 0.0325(11) 0.0400(11) 0.0404(12) -0.0077(9) 0.0060(9) -0.0059(9) N11 0.042(4) 0.028(3) 0.036(4) -0.006(3) 0.003(3) 0.001(3) Cl12 0.0372(11) 0.0429(12) 0.0474(13) 0.0042(9) -0.0058(9) 0.0059(9) C12 0.040(5) 0.030(4) 0.028(4) 0.006(3) -0.002(3) -0.001(4) S12 0.0392(11) 0.0362(11) 0.0320(11) -0.0040(8) 0.0062(9) -0.0033(9) N12 0.038(4) 0.031(4) 0.033(4) 0.000(3) 0.004(3) -0.005(3) C13 0.051(6) 0.037(5) 0.039(5) 0.000(4) 0.007(4) 0.006(4) C14 0.052(6) 0.033(5) 0.036(5) -0.003(3) -0.006(4) -0.016(4) C15 0.037(5) 0.043(5) 0.048(5) 0.005(4) -0.007(4) -0.011(4) C16 0.039(5) 0.031(4) 0.043(5) 0.007(3) -0.005(4) 0.000(4) C20 0.027(4) 0.036(4) 0.030(4) 0.003(3) -0.006(3) 0.004(3) S21 0.0333(11) 0.0302(10) 0.0373(12) -0.0013(8) -0.0037(9) -0.0041(8) N21 0.026(3) 0.027(3) 0.032(4) -0.004(2) -0.006(3) 0.000(3) C21 0.028(4) 0.028(4) 0.027(4) 0.001(3) -0.001(3) -0.001(3) Cl22 0.0372(11) 0.0354(11) 0.0416(12) 0.0006(8) -0.0029(9) 0.0061(9) S22 0.0332(11) 0.0364(11) 0.0321(11) -0.0005(8) -0.0076(9) -0.0007(9) N22 0.029(3) 0.022(3) 0.032(4) -0.002(2) -0.005(3) 0.002(3) C22 0.037(5) 0.033(4) 0.026(4) 0.006(3) 0.003(4) 0.009(3) C23 0.053(6) 0.025(4) 0.035(5) -0.005(3) 0.003(4) -0.010(4) C24 0.037(5) 0.041(5) 0.046(5) -0.004(4) -0.015(4) -0.015(4) C25 0.036(5) 0.042(5) 0.034(5) 0.005(3) -0.010(4) 0.001(4) C26 0.029(4) 0.032(4) 0.026(4) -0.002(3) 0.001(3) 0.006(3) C30 0.030(4) 0.031(4) 0.024(4) -0.003(3) -0.001(3) 0.003(3) S31 0.0408(12) 0.0301(10) 0.0339(12) -0.0015(8) -0.0051(9) -0.0049(8) N31 0.037(4) 0.033(4) 0.030(4) -0.004(3) -0.009(3) -0.002(3) C31 0.028(4) 0.038(4) 0.032(5) -0.004(3) -0.003(3) -0.002(3) S32 0.0317(12) 0.0380(11) 0.0364(13) -0.0029(9) -0.0066(9) -0.0014(9) Cl32 0.0364(11) 0.0406(11) 0.0440(13) -0.0046(9) -0.0075(9) 0.0083(9) N32 0.033(4) 0.033(3) 0.032(4) -0.008(3) -0.006(3) 0.000(3) C32 0.029(4) 0.040(4) 0.025(4) -0.001(3) 0.003(3) 0.005(3) C33 0.048(5) 0.043(5) 0.035(5) -0.009(4) -0.001(4) -0.005(4) C34 0.042(5) 0.053(6) 0.045(5) -0.021(4) -0.009(4) -0.011(4) C35 0.032(5) 0.057(6) 0.036(5) -0.009(4) -0.004(4) 0.000(4) C36 0.042(5) 0.043(5) 0.032(5) -0.010(4) 0.000(4) 0.003(4) C40 0.037(4) 0.026(4) 0.028(4) 0.004(3) 0.003(3) 0.010(3) S41 0.0457(13) 0.0313(10) 0.0296(11) -0.0020(8) -0.0057(9) 0.0062(9) N41 0.037(4) 0.035(4) 0.025(3) -0.002(3) -0.003(3) 0.002(3) C41 0.032(4) 0.023(4) 0.037(4) 0.002(3) 0.001(3) 0.000(3) S42 0.0404(12) 0.0346(11) 0.0328(12) -0.0001(8) -0.0062(9) 0.0031(9) Cl42 0.0431(12) 0.0411(11) 0.0450(12) -0.0069(9) -0.0085(9) 0.0114(9) N42 0.038(4) 0.033(4) 0.036(4) -0.004(3) -0.005(3) 0.004(3) C42 0.034(4) 0.035(4) 0.029(4) 0.006(3) 0.001(3) 0.006(4) C43 0.047(5) 0.038(5) 0.041(5) -0.002(4) -0.008(4) -0.005(4) C44 0.048(6) 0.049(5) 0.040(5) 0.001(4) -0.011(4) -0.013(4) C45 0.031(5) 0.052(5) 0.047(6) 0.012(4) -0.009(4) -0.005(4) C46 0.034(5) 0.040(5) 0.038(5) 0.002(4) 0.000(4) -0.003(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 C10 N12 1.320(9) . ? C10 N11 1.341(9) . ? C10 C11 1.491(10) . ? C11 C16 1.382(10) . ? C11 C12 1.390(10) . ? S11 N11 1.630(6) . ? S11 S12 2.101(3) . ? Cl12 C12 1.752(8) . ? C12 C13 1.389(11) . ? S12 N12 1.645(6) . ? C13 C14 1.382(12) . ? C13 H13 0.9500 . ? C14 C15 1.352(12) . ? C14 H14 0.9500 . ? C15 C16 1.399(11) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C20 N22 1.335(9) . ? C20 N21 1.342(9) . ? C20 C21 1.491(10) . ? S21 N21 1.647(6) . ? S21 S22 2.085(3) . ? C21 C22 1.392(10) . ? C21 C26 1.405(10) . ? Cl22 C22 1.737(8) . ? S22 N22 1.622(6) . ? C22 C23 1.388(11) . ? C23 C24 1.416(11) . ? C23 H23 0.9500 . ? C24 C25 1.360(11) . ? C24 H24 0.9500 . ? C25 C26 1.387(11) . ? C25 H25 0.9500 . ? C26 H26 0.9500 . ? C30 N32 1.341(9) . ? C30 N31 1.354(9) . ? C30 C31 1.469(10) . ? S31 N31 1.630(6) . ? S31 S32 2.086(3) . ? C31 C36 1.400(11) . ? C31 C32 1.408(10) . ? S32 N32 1.638(6) . ? Cl32 C32 1.742(8) . ? C32 C33 1.373(11) . ? C33 C34 1.396(12) . ? C33 H33 0.9500 . ? C34 C35 1.398(12) . ? C34 H34 0.9500 . ? C35 C36 1.376(11) . ? C35 H35 0.9500 . ? C36 H36 0.9500 . ? C40 N42 1.319(9) . ? C40 N41 1.327(9) . ? C40 C41 1.499(11) . ? S41 N41 1.639(6) . ? S41 S42 2.099(3) . ? C41 C42 1.379(10) . ? C41 C46 1.416(11) . ? S42 N42 1.637(6) . ? Cl42 C42 1.763(8) . ? C42 C43 1.382(10) . ? C43 C44 1.361(12) . ? C43 H43 0.9500 . ? C44 C45 1.404(12) . ? C44 H44 0.9500 . ? C45 C46 1.363(11) . ? C45 H45 0.9500 . ? C46 H46 0.9500 . ? 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 N12 C10 N11 122.2(7) . . ? N12 C10 C11 118.2(6) . . ? N11 C10 C11 119.6(7) . . ? C16 C11 C12 117.8(7) . . ? C16 C11 C10 118.9(7) . . ? C12 C11 C10 123.4(7) . . ? N11 S11 S12 93.7(2) . . ? C10 N11 S11 115.3(5) . . ? C13 C12 C11 121.3(7) . . ? C13 C12 Cl12 118.0(6) . . ? C11 C12 Cl12 120.7(6) . . ? N12 S12 S11 94.3(2) . . ? C10 N12 S12 114.5(5) . . ? C14 C13 C12 118.8(7) . . ? C14 C13 H13 120.6 . . ? C12 C13 H13 120.6 . . ? C15 C14 C13 121.5(8) . . ? C15 C14 H14 119.2 . . ? C13 C14 H14 119.2 . . ? C14 C15 C16 119.2(8) . . ? C14 C15 H15 120.4 . . ? C16 C15 H15 120.4 . . ? C11 C16 C15 121.4(7) . . ? C11 C16 H16 119.3 . . ? C15 C16 H16 119.3 . . ? N22 C20 N21 122.3(6) . . ? N22 C20 C21 120.3(6) . . ? N21 C20 C21 117.3(6) . . ? N21 S21 S22 94.3(2) . . ? C20 N21 S21 113.8(5) . . ? C22 C21 C26 117.4(6) . . ? C22 C21 C20 125.6(6) . . ? C26 C21 C20 116.9(6) . . ? N22 S22 S21 94.8(2) . . ? C20 N22 S22 114.7(5) . . ? C23 C22 C21 121.1(7) . . ? C23 C22 Cl22 116.5(6) . . ? C21 C22 Cl22 122.3(6) . . ? C22 C23 C24 119.7(7) . . ? C22 C23 H23 120.2 . . ? C24 C23 H23 120.2 . . ? C25 C24 C23 119.8(7) . . ? C25 C24 H24 120.1 . . ? C23 C24 H24 120.1 . . ? C24 C25 C26 120.0(7) . . ? C24 C25 H25 120.0 . . ? C26 C25 H25 120.0 . . ? C25 C26 C21 121.9(7) . . ? C25 C26 H26 119.1 . . ? C21 C26 H26 119.1 . . ? N32 C30 N31 121.3(6) . . ? N32 C30 C31 121.0(6) . . ? N31 C30 C31 117.7(6) . . ? N31 S31 S32 94.2(2) . . ? C30 N31 S31 115.1(5) . . ? C36 C31 C32 117.2(7) . . ? C36 C31 C30 117.8(7) . . ? C32 C31 C30 125.0(7) . . ? N32 S32 S31 95.0(2) . . ? C30 N32 S32 114.4(5) . . ? C33 C32 C31 121.4(7) . . ? C33 C32 Cl32 116.4(6) . . ? C31 C32 Cl32 122.2(6) . . ? C32 C33 C34 119.8(8) . . ? C32 C33 H33 120.1 . . ? C34 C33 H33 120.1 . . ? C33 C34 C35 120.3(7) . . ? C33 C34 H34 119.8 . . ? C35 C34 H34 119.8 . . ? C36 C35 C34 118.7(7) . . ? C36 C35 H35 120.7 . . ? C34 C35 H35 120.7 . . ? C35 C36 C31 122.6(7) . . ? C35 C36 H36 118.7 . . ? C31 C36 H36 118.7 . . ? N42 C40 N41 122.4(7) . . ? N42 C40 C41 119.6(6) . . ? N41 C40 C41 117.9(6) . . ? N41 S41 S42 93.8(2) . . ? C40 N41 S41 114.8(5) . . ? C42 C41 C46 116.7(7) . . ? C42 C41 C40 125.6(7) . . ? C46 C41 C40 117.8(6) . . ? N42 S42 S41 93.9(2) . . ? C40 N42 S42 115.0(5) . . ? C41 C42 C43 122.7(7) . . ? C41 C42 Cl42 121.8(6) . . ? C43 C42 Cl42 115.5(6) . . ? C44 C43 C42 119.5(8) . . ? C44 C43 H43 120.2 . . ? C42 C43 H43 120.2 . . ? C43 C44 C45 119.9(8) . . ? C43 C44 H44 120.1 . . ? C45 C44 H44 120.1 . . ? C46 C45 C44 120.0(8) . . ? C46 C45 H45 120.0 . . ? C44 C45 H45 120.0 . . ? C45 C46 C41 121.2(8) . . ? C45 C46 H46 119.4 . . ? C41 C46 H46 119.4 . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 24.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.564 _refine_diff_density_min -0.583 _refine_diff_density_rms 0.168 #=== END data_2 _database_code_depnum_ccdc_archive 'CCDC 796397' #TrackingRef '- chem_comm.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H3 Cl2 N2 S2' _chemical_formula_sum 'C7 H3 Cl2 N2 S2' _chemical_formula_weight 250.13 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' Cl Cl 0.1484 0.1585 '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' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.3271(2) _cell_length_b 10.3563(3) _cell_length_c 24.6666(7) _cell_angle_alpha 88.096(2) _cell_angle_beta 81.458(2) _cell_angle_gamma 77.0090(10) _cell_volume 1803.60(9) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 34374 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 25.35 _exptl_crystal_description needle _exptl_crystal_colour black _exptl_crystal_size_max 0.16 _exptl_crystal_size_mid 0.02 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.842 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1000 _exptl_absorpt_coefficient_mu 1.127 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.902 _exptl_absorpt_correction_T_max 1.002 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 9531 _diffrn_reflns_av_R_equivalents 0.0395 _diffrn_reflns_av_sigmaI/netI 0.0589 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -29 _diffrn_reflns_limit_l_max 29 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 25.34 _reflns_number_total 5799 _reflns_number_gt 4579 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _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. A smaller higher symmetry monoclinic cell was initially identified in the P2(1)/c setting. However the thermal parameters for S and N atoms from this solution coupled with the unexpected regular pi-stack motif indicated the presence of a super-cell reported here. The structure was solved by direct methods with remaining non-H atoms identified in subsequent difference maps. H atoms were added at calculated positions and refined with a riding model. Despite an apparently satisfactory refinement, residuals remained high and the data examined using ROTAX (S. Parsons and R. Gould, Univ. Edinburgh) within CRYSTALS for possible twinning. A twin law was identified and subsequent refinement provided satisfactory R-values.(The twin matrix was 1 0 0 0 1 0 1 0 -1). ; _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^)+(0.0241P)^2^+4.0662P] 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 SHELXL _refine_ls_extinction_coef 0.0004(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 5799 _refine_ls_number_parameters 471 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0710 _refine_ls_R_factor_gt 0.0491 _refine_ls_wR_factor_ref 0.1119 _refine_ls_wR_factor_gt 0.1003 _refine_ls_goodness_of_fit_ref 1.050 _refine_ls_restrained_S_all 1.050 _refine_ls_shift/su_max 0.003 _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 C10 C 0.1092(16) 0.4968(11) 0.6136(5) 0.030(3) Uani 1 1 d . . . S11 S 0.1564(5) 0.6668(3) 0.54154(12) 0.0347(8) Uani 1 1 d . . . C11 C 0.1191(15) 0.3512(9) 0.6325(4) 0.024(3) Uani 1 1 d . . . N11 N 0.1723(13) 0.5136(9) 0.5598(4) 0.030(2) Uani 1 1 d . . . S12 S 0.0550(4) 0.7413(2) 0.62132(13) 0.0359(8) Uani 1 1 d . . . Cl12 Cl 0.1724(4) 0.4043(3) 0.73683(11) 0.0263(6) Uani 1 1 d . . . C12 C 0.1432(14) 0.3105(9) 0.6836(4) 0.016(2) Uani 1 1 d . . . N12 N 0.0568(13) 0.5940(8) 0.6484(4) 0.032(2) Uani 1 1 d . . . C13 C 0.1421(14) 0.1709(10) 0.6977(4) 0.018(2) Uani 1 1 d . . . H13 H 0.1536 0.1404 0.7341 0.022 Uiso 1 1 calc R . . C14 C 0.1249(15) 0.0861(11) 0.6592(4) 0.025(2) Uani 1 1 d . . . H14 H 0.1278 -0.0043 0.6678 0.030 Uiso 1 1 calc R . . C15 C 0.1027(14) 0.1348(11) 0.6060(5) 0.024(3) Uani 1 1 d . . . Cl15 Cl 0.0735(4) 0.0312(3) 0.55628(12) 0.0284(6) Uani 1 1 d . . . C16 C 0.0917(14) 0.2704(11) 0.5935(4) 0.025(2) Uani 1 1 d . . . H16 H 0.0657 0.3044 0.5586 0.030 Uiso 1 1 calc R . . C20 C 0.5762(13) 0.4876(11) 0.6206(4) 0.022(2) Uani 1 1 d . . . S21 S 0.5819(6) 0.6651(3) 0.55085(12) 0.0366(8) Uani 1 1 d . . . C21 C 0.6030(14) 0.3407(9) 0.6380(4) 0.020(2) Uani 1 1 d . . . N21 N 0.6197(13) 0.5086(9) 0.5668(4) 0.031(2) Uani 1 1 d . . . Cl22 Cl 0.6746(4) 0.3913(3) 0.74058(12) 0.0287(6) Uani 1 1 d . . . N22 N 0.5171(14) 0.5795(8) 0.6574(4) 0.031(2) Uani 1 1 d . . . S22 S 0.4942(5) 0.7313(3) 0.63173(13) 0.0336(8) Uani 1 1 d . . . C22 C 0.6396(16) 0.2996(11) 0.6877(5) 0.025(3) Uani 1 1 d . . . C23 C 0.6485(13) 0.1573(9) 0.7013(5) 0.017(2) Uani 1 1 d . . . H23 H 0.6647 0.1268 0.7374 0.020 Uiso 1 1 calc R . . C24 C 0.6338(14) 0.0694(10) 0.6626(4) 0.019(2) Uani 1 1 d . . . H24 H 0.6461 -0.0223 0.6705 0.022 Uiso 1 1 calc R . . Cl25 Cl 0.5753(4) 0.0157(3) 0.56099(12) 0.0270(6) Uani 1 1 d . . . C25 C 0.6001(14) 0.1210(10) 0.6112(5) 0.021(2) Uani 1 1 d . . . C26 C 0.5810(13) 0.2570(11) 0.5993(4) 0.024(3) Uani 1 1 d . . . H26 H 0.5528 0.2901 0.5644 0.028 Uiso 1 1 calc R . . C30 C 0.2046(16) 0.9860(11) 0.8793(4) 0.028(2) Uani 1 1 d . . . S31 S 0.1323(6) 1.1676(3) 0.94937(12) 0.0416(10) Uani 1 1 d . . . C31 C 0.2374(13) 0.8514(10) 0.8632(4) 0.023(2) Uani 1 1 d . . . N31 N 0.1901(15) 1.0118(10) 0.9326(4) 0.035(2) Uani 1 1 d . . . Cl32 Cl 0.4124(4) 0.8962(3) 0.76024(12) 0.0291(6) Uani 1 1 d . . . S32 S 0.1210(5) 1.2340(3) 0.86818(13) 0.0377(10) Uani 1 1 d . . . C32 C 0.3234(14) 0.7928(10) 0.8105(4) 0.019(2) Uani 1 1 d . . . N32 N 0.1702(13) 1.0862(8) 0.8424(4) 0.031(2) Uani 1 1 d . . . C33 C 0.3537(17) 0.6688(12) 0.7990(5) 0.031(3) Uani 1 1 d . . . H33 H 0.4166 0.6361 0.7640 0.037 Uiso 1 1 calc R . . C34 C 0.2915(16) 0.5822(11) 0.8394(5) 0.025(2) Uani 1 1 d . . . H34 H 0.3091 0.4908 0.8313 0.030 Uiso 1 1 calc R . . Cl35 Cl 0.1345(4) 0.5193(3) 0.94003(14) 0.0319(7) Uani 1 1 d . . . C35 C 0.2068(14) 0.6296(11) 0.8896(5) 0.022(2) Uani 1 1 d . . . C36 C 0.1835(15) 0.7567(10) 0.9029(4) 0.023(2) Uani 1 1 d . . . H36 H 0.1303 0.7852 0.9392 0.028 Uiso 1 1 calc R . . C40 C 0.7319(13) 0.9910(9) 0.8852(4) 0.020(2) Uani 1 1 d . . . S41 S 0.6931(6) 1.1630(3) 0.95740(13) 0.0370(9) Uani 1 1 d . . . N41 N 0.7341(13) 1.0071(9) 0.9382(4) 0.030(2) Uani 1 1 d . . . C41 C 0.7485(13) 0.8580(10) 0.8669(4) 0.022(2) Uani 1 1 d . . . Cl42 Cl 0.9161(4) 0.9008(3) 0.76233(12) 0.0270(6) Uani 1 1 d . . . S42 S 0.6702(5) 1.2377(3) 0.87780(14) 0.0389(8) Uani 1 1 d . . . N42 N 0.6992(14) 1.0945(8) 0.8493(4) 0.032(2) Uani 1 1 d . . . C42 C 0.8257(15) 0.7988(11) 0.8124(4) 0.020(2) Uani 1 1 d . . . C43 C 0.8450(16) 0.6778(11) 0.8012(5) 0.026(2) Uani 1 1 d . . . H43 H 0.9022 0.6456 0.7657 0.031 Uiso 1 1 calc R . . C44 C 0.7822(16) 0.5905(10) 0.8410(5) 0.027(3) Uani 1 1 d . . . H44 H 0.7931 0.5003 0.8321 0.033 Uiso 1 1 calc R . . Cl45 Cl 0.6319(4) 0.5281(3) 0.94276(13) 0.0333(7) Uani 1 1 d . . . C45 C 0.7059(14) 0.6363(11) 0.8923(5) 0.025(3) Uani 1 1 d . . . C46 C 0.6917(15) 0.7629(10) 0.9064(4) 0.023(2) Uani 1 1 d . . . H46 H 0.6433 0.7905 0.9431 0.028 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 C10 0.037(6) 0.030(5) 0.026(5) 0.008(4) -0.006(4) -0.011(4) S11 0.048(2) 0.0283(13) 0.0308(16) 0.0075(9) -0.0098(11) -0.0136(13) C11 0.028(6) 0.014(4) 0.025(6) 0.003(4) 0.006(4) -0.002(4) N11 0.043(5) 0.030(4) 0.017(4) 0.003(3) -0.003(3) -0.009(4) S12 0.0437(19) 0.0232(13) 0.0373(16) 0.0019(9) 0.0019(11) -0.0056(12) Cl12 0.0307(15) 0.0290(13) 0.0197(13) -0.0033(11) -0.0023(11) -0.0083(11) C12 0.014(4) 0.011(4) 0.025(5) 0.001(3) 0.003(3) -0.010(3) N12 0.042(5) 0.027(4) 0.026(4) 0.005(3) 0.004(3) -0.013(4) C13 0.013(4) 0.022(5) 0.023(5) 0.009(4) -0.007(4) -0.007(4) C14 0.024(6) 0.033(6) 0.019(5) -0.001(4) 0.003(4) -0.012(4) C15 0.020(5) 0.029(6) 0.023(6) -0.006(4) 0.003(4) -0.005(4) Cl15 0.0310(15) 0.0337(14) 0.0227(13) -0.0055(11) -0.0022(11) -0.0122(12) C16 0.016(5) 0.035(6) 0.017(5) -0.002(4) 0.001(4) 0.006(4) C20 0.016(4) 0.035(5) 0.019(5) 0.005(4) 0.000(3) -0.015(4) S21 0.055(2) 0.0281(13) 0.0274(15) 0.0044(9) 0.0024(12) -0.0162(13) C21 0.027(5) 0.007(4) 0.021(5) 0.005(3) 0.009(4) -0.002(3) N21 0.042(6) 0.030(4) 0.020(4) 0.004(3) 0.000(3) -0.007(4) Cl22 0.0320(15) 0.0292(14) 0.0239(14) -0.0041(11) -0.0057(12) -0.0033(11) N22 0.050(5) 0.021(4) 0.027(4) 0.007(3) -0.006(4) -0.022(4) S22 0.0512(19) 0.0232(12) 0.0277(15) 0.0006(9) -0.0040(11) -0.0121(12) C22 0.020(5) 0.020(5) 0.035(6) -0.010(4) 0.003(4) -0.006(4) C23 0.006(4) 0.016(4) 0.028(5) 0.006(3) -0.001(3) -0.004(3) C24 0.015(5) 0.019(4) 0.021(5) 0.004(3) -0.003(4) -0.002(3) Cl25 0.0275(14) 0.0293(13) 0.0248(14) -0.0045(11) -0.0006(11) -0.0089(11) C25 0.022(5) 0.017(5) 0.021(6) -0.002(4) 0.001(4) -0.004(4) C26 0.012(4) 0.036(6) 0.019(5) 0.003(4) 0.000(4) 0.000(4) C30 0.037(6) 0.027(5) 0.017(5) 0.007(4) 0.002(4) -0.006(4) S31 0.071(3) 0.0278(14) 0.0260(16) -0.0034(9) -0.0049(12) -0.0111(15) C31 0.009(4) 0.037(6) 0.021(5) 0.008(4) -0.002(3) -0.004(4) N31 0.052(6) 0.026(4) 0.030(5) 0.000(3) -0.007(4) -0.017(4) Cl32 0.0281(14) 0.0317(13) 0.0248(14) 0.0082(12) 0.0032(11) -0.0066(11) S32 0.060(2) 0.0235(13) 0.0285(16) 0.0001(9) 0.0006(11) -0.0108(13) C32 0.016(4) 0.032(5) 0.007(4) -0.001(4) 0.002(3) -0.007(4) N32 0.040(5) 0.026(4) 0.024(4) 0.007(3) -0.007(3) 0.001(4) C33 0.038(6) 0.040(6) 0.012(5) 0.008(4) -0.001(4) -0.005(5) C34 0.026(6) 0.020(5) 0.030(6) -0.001(4) -0.007(4) -0.004(4) Cl35 0.0385(16) 0.0304(14) 0.0290(15) 0.0092(11) -0.0030(12) -0.0144(12) C35 0.019(5) 0.034(6) 0.020(6) 0.014(4) -0.011(4) -0.018(4) C36 0.032(6) 0.027(6) 0.018(5) 0.002(4) -0.006(4) -0.022(4) C40 0.013(4) 0.014(4) 0.032(6) 0.004(4) -0.001(3) 0.000(3) S41 0.053(2) 0.0280(13) 0.0282(16) -0.0073(9) 0.0044(11) -0.0119(13) N41 0.038(5) 0.021(4) 0.032(5) -0.003(3) 0.002(4) -0.015(3) C41 0.011(4) 0.032(5) 0.025(5) 0.001(4) 0.002(3) -0.010(4) Cl42 0.0242(14) 0.0286(13) 0.0269(15) 0.0081(11) 0.0014(11) -0.0076(11) S42 0.054(2) 0.0229(13) 0.0375(16) -0.0013(10) -0.0047(12) -0.0052(13) N42 0.046(5) 0.017(4) 0.030(5) 0.002(3) -0.006(4) 0.000(4) C42 0.019(5) 0.030(5) 0.010(5) 0.005(4) -0.002(3) -0.001(4) C43 0.033(6) 0.028(5) 0.016(5) 0.006(4) -0.005(4) -0.006(4) C44 0.031(6) 0.018(5) 0.031(6) -0.001(4) -0.008(4) 0.000(4) Cl45 0.0415(17) 0.0322(14) 0.0294(16) 0.0096(12) -0.0024(12) -0.0178(12) C45 0.019(5) 0.030(6) 0.029(6) 0.010(4) -0.003(4) -0.012(4) C46 0.036(6) 0.019(5) 0.018(5) -0.001(4) -0.002(4) -0.015(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 C10 N12 1.299(14) . ? C10 N11 1.357(14) . ? C10 C11 1.553(14) . ? S11 N11 1.619(9) . ? S11 S12 2.104(4) . ? C11 C12 1.339(14) . ? C11 C16 1.361(15) . ? S12 N12 1.643(8) . ? Cl12 C12 1.724(10) . ? C12 C13 1.478(13) . ? C13 C14 1.353(16) . ? C13 H13 0.9500 . ? C14 C15 1.409(16) . ? C14 H14 0.9500 . ? C15 C16 1.414(14) . ? C15 Cl15 1.723(11) . ? C16 H16 0.9500 . ? C20 N22 1.293(13) . ? C20 N21 1.340(14) . ? C20 C21 1.544(13) . ? S21 N21 1.626(10) . ? S21 S22 2.092(4) . ? C21 C22 1.332(15) . ? C21 C26 1.360(14) . ? Cl22 C22 1.720(11) . ? N22 S22 1.657(8) . ? C22 C23 1.490(14) . ? C23 C24 1.372(15) . ? C23 H23 0.9500 . ? C24 C25 1.394(15) . ? C24 H24 0.9500 . ? Cl25 C25 1.733(11) . ? C25 C26 1.409(13) . ? C26 H26 0.9500 . ? C30 N31 1.334(15) . ? C30 N32 1.363(13) . ? C30 C31 1.421(15) . ? S31 N31 1.624(10) . ? S31 S32 2.103(4) . ? C31 C36 1.438(13) . ? C31 C32 1.448(14) . ? Cl32 C32 1.758(10) . ? S32 N32 1.620(9) . ? C32 C33 1.287(15) . ? C33 C34 1.412(16) . ? C33 H33 0.9500 . ? C34 C35 1.355(16) . ? C34 H34 0.9500 . ? Cl35 C35 1.765(10) . ? C35 C36 1.334(14) . ? C36 H36 0.9500 . ? C40 N41 1.325(15) . ? C40 N42 1.370(12) . ? C40 C41 1.437(14) . ? S41 N41 1.648(9) . ? S41 S42 2.102(4) . ? C41 C46 1.446(13) . ? C41 C42 1.475(14) . ? Cl42 C42 1.752(10) . ? S42 N42 1.620(9) . ? C42 C43 1.264(14) . ? C43 C44 1.411(16) . ? C43 H43 0.9500 . ? C44 C45 1.360(16) . ? C44 H44 0.9500 . ? Cl45 C45 1.754(11) . ? C45 C46 1.345(14) . ? C46 H46 0.9500 . ? 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 N12 C10 N11 122.9(10) . . ? N12 C10 C11 121.2(9) . . ? N11 C10 C11 115.8(10) . . ? N11 S11 S12 94.1(3) . . ? C12 C11 C16 123.1(9) . . ? C12 C11 C10 122.8(10) . . ? C16 C11 C10 114.1(9) . . ? C10 N11 S11 114.2(8) . . ? N12 S12 S11 93.9(3) . . ? C11 C12 C13 118.0(9) . . ? C11 C12 Cl12 127.3(8) . . ? C13 C12 Cl12 114.7(8) . . ? C10 N12 S12 114.7(7) . . ? C14 C13 C12 120.4(10) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C13 C14 C15 118.6(10) . . ? C13 C14 H14 120.7 . . ? C15 C14 H14 120.7 . . ? C14 C15 C16 120.8(10) . . ? C14 C15 Cl15 120.1(9) . . ? C16 C15 Cl15 119.0(9) . . ? C11 C16 C15 118.8(10) . . ? C11 C16 H16 120.6 . . ? C15 C16 H16 120.6 . . ? N22 C20 N21 125.1(10) . . ? N22 C20 C21 119.6(9) . . ? N21 C20 C21 115.3(10) . . ? N21 S21 S22 94.8(4) . . ? C22 C21 C26 122.4(9) . . ? C22 C21 C20 122.4(9) . . ? C26 C21 C20 115.2(9) . . ? C20 N21 S21 112.9(8) . . ? C20 N22 S22 113.4(7) . . ? N22 S22 S21 93.8(3) . . ? C21 C22 C23 117.7(10) . . ? C21 C22 Cl22 128.2(9) . . ? C23 C22 Cl22 114.1(9) . . ? C24 C23 C22 121.1(9) . . ? C24 C23 H23 119.4 . . ? C22 C23 H23 119.4 . . ? C23 C24 C25 116.9(9) . . ? C23 C24 H24 121.5 . . ? C25 C24 H24 121.5 . . ? C24 C25 C26 121.8(10) . . ? C24 C25 Cl25 119.1(8) . . ? C26 C25 Cl25 119.0(8) . . ? C21 C26 C25 119.8(10) . . ? C21 C26 H26 120.1 . . ? C25 C26 H26 120.1 . . ? N31 C30 N32 120.8(10) . . ? N31 C30 C31 117.8(10) . . ? N32 C30 C31 121.1(10) . . ? N31 S31 S32 94.1(4) . . ? C30 C31 C36 118.7(9) . . ? C30 C31 C32 128.1(9) . . ? C36 C31 C32 113.2(9) . . ? C30 N31 S31 115.7(8) . . ? N32 S32 S31 94.4(3) . . ? C33 C32 C31 125.0(9) . . ? C33 C32 Cl32 117.3(8) . . ? C31 C32 Cl32 117.4(8) . . ? C30 N32 S32 115.0(7) . . ? C32 C33 C34 118.7(10) . . ? C32 C33 H33 120.7 . . ? C34 C33 H33 120.7 . . ? C35 C34 C33 120.0(10) . . ? C35 C34 H34 120.0 . . ? C33 C34 H34 120.0 . . ? C36 C35 C34 121.8(10) . . ? C36 C35 Cl35 118.8(9) . . ? C34 C35 Cl35 119.3(9) . . ? C35 C36 C31 121.2(10) . . ? C35 C36 H36 119.4 . . ? C31 C36 H36 119.4 . . ? N41 C40 N42 123.2(9) . . ? N41 C40 C41 116.7(9) . . ? N42 C40 C41 119.8(9) . . ? N41 S41 S42 93.9(4) . . ? C40 N41 S41 114.2(8) . . ? C40 C41 C46 118.3(9) . . ? C40 C41 C42 129.1(9) . . ? C46 C41 C42 112.6(9) . . ? N42 S42 S41 95.5(4) . . ? C40 N42 S42 113.1(7) . . ? C43 C42 C41 124.4(10) . . ? C43 C42 Cl42 118.3(9) . . ? C41 C42 Cl42 117.0(8) . . ? C42 C43 C44 120.4(11) . . ? C42 C43 H43 119.8 . . ? C44 C43 H43 119.8 . . ? C45 C44 C43 119.6(10) . . ? C45 C44 H44 120.2 . . ? C43 C44 H44 120.2 . . ? C46 C45 C44 121.5(10) . . ? C46 C45 Cl45 118.4(9) . . ? C44 C45 Cl45 120.1(9) . . ? C45 C46 C41 121.5(10) . . ? C45 C46 H46 119.3 . . ? C41 C46 H46 119.3 . . ? _diffrn_measured_fraction_theta_max 0.877 _diffrn_reflns_theta_full 25.34 _diffrn_measured_fraction_theta_full 0.877 _refine_diff_density_max 0.410 _refine_diff_density_min -0.466 _refine_diff_density_rms 0.094