# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2013 # Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2012 data_publication_text _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_contact_author_name 'Richard T. Oakley' _publ_contact_author_address ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; _publ_contact_author_email oakley@uwaterloo.ca _publ_contact_author_phone 1-519-888-4582 _publ_contact_author_fax 1-519-746-0435 _publ_section_title ;Hybrid dithiazolothiadiazinyl radicals; versatile building blocks for magnetic and conductive materials ; loop_ _publ_author_name _publ_author_address 'Stephen M. Winter' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; 'Aidin R. Balo' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; 'Ryan J. Roberts' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; 'Kristina Lekin' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; 'Abdeljalil Assoud' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; 'Paul A. Dube' ;Brockhouse Institute for Materials Research, McMaster University, Hamilton, Ontario L8S 4M1, Canada ; 'Richard T. Oakley' ;Department of Chemistry, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada ; data_waterloo3 _database_code_depnum_ccdc_archive 'CCDC 912364' #TrackingRef '3c.CIF' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C11 H7 N4 S4' _chemical_formula_sum 'C11 H7 N4 S4' _chemical_formula_weight 323.45 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' 'N' 'N' 0.0311 0.0180 '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' _symmetry_cell_setting 'Orthorhombic' _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 4.82750(10) _cell_length_b 15.9086(3) _cell_length_c 16.1160(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1237.69(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'plate' _exptl_crystal_colour 'dark green' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.736 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 660 _exptl_absorpt_coefficient_mu 6.970 _exptl_absorpt_correction_type 'numerical' _exptl_absorpt_correction_T_min 0.2493 _exptl_absorpt_correction_T_max 0.8341 _exptl_absorpt_process_details 'SADABS' _exptl_special_details ; ? ; _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 ? _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 9991 _diffrn_reflns_av_R_equivalents 0.0373 _diffrn_reflns_av_sigmaI/netI 0.0344 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 3.90 _diffrn_reflns_theta_max 67.63 _reflns_number_total 2133 _reflns_number_gt 2048 _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 ; The resulting location of the 1.228 electron/Angstrom^3^maximum in the final difference map is 0.78 ang and 0.96 ang from H6C and C6, respectively. The absence of more peaks like it rules out potential disorder of the methyl group, as does the inability to refine the group in a different orientation. 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^)+(0.0915P)^2^+5.6093P] 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 0.09(5) _refine_ls_number_reflns 2133 _refine_ls_number_parameters 177 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0729 _refine_ls_R_factor_gt 0.0703 _refine_ls_wR_factor_ref 0.1844 _refine_ls_wR_factor_gt 0.1815 _refine_ls_goodness_of_fit_ref 1.062 _refine_ls_restrained_S_all 1.062 _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 S1 S 0.9663(4) 0.68113(11) 0.39413(12) 0.0392(4) Uani 1 1 d . . . S2 S 0.9424(4) 0.80359(10) 0.44387(11) 0.0379(4) Uani 1 1 d . . . S3 S 0.2320(5) 1.02320(11) 0.28878(13) 0.0495(6) Uani 1 1 d . . . S4 S -0.2828(5) 0.84951(13) 0.05181(15) 0.0539(6) Uani 1 1 d . . . N1 N 0.7279(14) 0.6914(4) 0.3205(4) 0.0431(15) Uani 1 1 d . . . N2 N 0.4147(12) 0.7811(4) 0.2557(4) 0.0348(13) Uani 1 1 d . . . N3 N 0.0990(12) 0.8672(3) 0.1911(3) 0.0308(12) Uani 1 1 d . . . N4 N 0.0045(15) 1.0140(4) 0.2121(4) 0.0425(15) Uani 1 1 d . . . C1 C 0.6189(15) 0.7641(4) 0.3193(5) 0.0362(17) Uani 1 1 d . . . C2 C 0.6921(15) 0.8322(4) 0.3699(4) 0.0334(15) Uani 1 1 d . . . C3 C 0.5834(15) 0.9115(4) 0.3613(4) 0.0330(14) Uani 1 1 d . . . H3 H 0.6478 0.9564 0.3950 0.020(16) Uiso 1 1 calc R . . C4 C 0.3789(15) 0.9250(5) 0.3027(4) 0.0378(16) Uani 1 1 d . . . C5 C 0.2932(14) 0.8570(4) 0.2481(4) 0.0292(13) Uani 1 1 d . . . C6 C 0.3337(18) 0.7118(5) 0.2008(6) 0.048(2) Uani 1 1 d . . . H6C H 0.2096 0.7330 0.1575 0.072 Uiso 1 1 calc R . . H6B H 0.2381 0.6684 0.2331 0.072 Uiso 1 1 calc R . . H6A H 0.4995 0.6876 0.1750 0.072 Uiso 1 1 calc R . . C7 C -0.0329(16) 0.9416(4) 0.1774(4) 0.0359(15) Uani 1 1 d . . . C8 C -0.2500(16) 0.9421(5) 0.1105(4) 0.0444(18) Uani 1 1 d . . . C9 C -0.4194(16) 1.0052(5) 0.0859(4) 0.0418(17) Uani 1 1 d . . . H9 H -0.4237 1.0602 0.1089 0.022(16) Uiso 1 1 calc R . . C10 C -0.5884(18) 0.9759(5) 0.0205(5) 0.049(2) Uani 1 1 d . . . H10 H -0.7267 1.0107 -0.0035 0.059 Uiso 1 1 calc R . . C11 C -0.545(2) 0.8947(6) -0.0073(6) 0.059(2) Uani 1 1 d . . . H11 H -0.6429 0.8681 -0.0512 0.030(18) 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 S1 0.0279(9) 0.0390(9) 0.0506(9) 0.0087(7) -0.0064(7) -0.0004(7) S2 0.0310(9) 0.0347(8) 0.0480(9) 0.0065(7) -0.0035(8) -0.0023(7) S3 0.0619(13) 0.0291(9) 0.0576(11) -0.0044(8) -0.0204(10) 0.0068(9) S4 0.0491(12) 0.0474(11) 0.0652(12) 0.0052(10) -0.0120(11) 0.0001(9) N1 0.033(3) 0.046(4) 0.050(3) 0.012(3) -0.007(3) -0.001(3) N2 0.028(3) 0.030(3) 0.046(3) 0.009(2) -0.010(3) 0.001(2) N3 0.028(3) 0.026(3) 0.038(3) 0.003(2) -0.004(2) 0.004(2) N4 0.041(4) 0.034(3) 0.052(3) 0.002(3) -0.002(3) 0.005(3) C1 0.038(4) 0.027(3) 0.044(4) -0.009(3) 0.017(3) -0.011(3) C2 0.029(4) 0.034(3) 0.037(3) 0.003(3) 0.006(3) -0.007(3) C3 0.028(3) 0.032(3) 0.040(3) 0.002(3) -0.006(3) -0.006(3) C4 0.033(4) 0.046(4) 0.034(3) 0.005(3) -0.002(3) -0.007(3) C5 0.023(3) 0.025(3) 0.039(3) 0.008(3) -0.001(3) 0.000(2) C6 0.045(5) 0.033(4) 0.066(5) 0.016(4) 0.001(4) 0.008(3) C7 0.029(4) 0.034(3) 0.045(4) 0.006(3) -0.004(3) -0.002(3) C8 0.026(4) 0.074(5) 0.033(3) 0.020(3) -0.007(3) -0.012(4) C9 0.032(4) 0.053(4) 0.040(4) 0.003(3) 0.005(3) -0.010(3) C10 0.039(4) 0.051(5) 0.058(5) 0.020(4) -0.016(4) 0.006(4) C11 0.053(5) 0.062(5) 0.062(5) 0.012(4) -0.016(5) -0.005(5) _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 N1 1.661(6) . ? S1 S2 2.110(3) . ? S2 C2 1.757(7) . ? S3 N4 1.660(7) . ? S3 C4 1.730(8) . ? S4 C11 1.741(10) . ? S4 C8 1.758(9) . ? N1 C1 1.270(10) . ? N2 C5 1.347(9) . ? N2 C1 1.447(10) . ? N2 C6 1.468(10) . ? N3 C5 1.323(9) . ? N3 C7 1.362(9) . ? N4 C7 1.293(9) . ? C1 C2 1.403(9) . ? C2 C3 1.373(10) . ? C3 C4 1.383(10) . ? C3 H3 0.9500 . ? C4 C5 1.454(10) . ? C6 H6C 0.9800 . ? C6 H6B 0.9800 . ? C6 H6A 0.9800 . ? C7 C8 1.504(10) . ? C8 C9 1.354(12) . ? C9 C10 1.412(12) . ? C9 H9 0.9500 . ? C10 C11 1.383(13) . ? C10 H10 0.9500 . ? C11 H11 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 N1 S1 S2 98.2(2) . . ? C2 S2 S1 91.1(2) . . ? N4 S3 C4 106.7(3) . . ? C11 S4 C8 90.8(4) . . ? C1 N1 S1 112.8(6) . . ? C5 N2 C1 122.0(6) . . ? C5 N2 C6 120.1(6) . . ? C1 N2 C6 117.9(6) . . ? C5 N3 C7 123.4(6) . . ? C7 N4 S3 119.5(5) . . ? N1 C1 C2 126.1(8) . . ? N1 C1 N2 117.7(6) . . ? C2 C1 N2 116.0(6) . . ? C3 C2 C1 123.7(7) . . ? C3 C2 S2 124.7(5) . . ? C1 C2 S2 111.6(5) . . ? C2 C3 C4 119.0(6) . . ? C2 C3 H3 120.5 . . ? C4 C3 H3 120.5 . . ? C3 C4 C5 120.0(7) . . ? C3 C4 S3 121.4(6) . . ? C5 C4 S3 118.5(5) . . ? N3 C5 N2 118.9(6) . . ? N3 C5 C4 122.0(6) . . ? N2 C5 C4 119.2(6) . . ? N2 C6 H6C 109.5 . . ? N2 C6 H6B 109.5 . . ? H6C C6 H6B 109.5 . . ? N2 C6 H6A 109.5 . . ? H6C C6 H6A 109.5 . . ? H6B C6 H6A 109.5 . . ? N4 C7 N3 129.7(7) . . ? N4 C7 C8 113.7(7) . . ? N3 C7 C8 116.5(6) . . ? C9 C8 C7 129.4(8) . . ? C9 C8 S4 114.2(5) . . ? C7 C8 S4 116.4(6) . . ? C8 C9 C10 108.8(7) . . ? C8 C9 H9 125.6 . . ? C10 C9 H9 125.6 . . ? C11 C10 C9 117.6(8) . . ? C11 C10 H10 121.2 . . ? C9 C10 H10 121.2 . . ? C10 C11 S4 108.5(7) . . ? C10 C11 H11 125.7 . . ? S4 C11 H11 125.7 . . ? 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 N1 S1 S2 C2 -1.7(3) . . . . ? S2 S1 N1 C1 -0.2(6) . . . . ? C4 S3 N4 C7 1.2(7) . . . . ? S1 N1 C1 C2 3.1(10) . . . . ? S1 N1 C1 N2 178.0(5) . . . . ? C5 N2 C1 N1 -178.2(7) . . . . ? C6 N2 C1 N1 4.1(10) . . . . ? C5 N2 C1 C2 -2.8(9) . . . . ? C6 N2 C1 C2 179.5(6) . . . . ? N1 C1 C2 C3 174.3(7) . . . . ? N2 C1 C2 C3 -0.6(10) . . . . ? N1 C1 C2 S2 -4.7(9) . . . . ? N2 C1 C2 S2 -179.6(5) . . . . ? S1 S2 C2 C3 -175.8(6) . . . . ? S1 S2 C2 C1 3.2(5) . . . . ? C1 C2 C3 C4 3.8(11) . . . . ? S2 C2 C3 C4 -177.4(5) . . . . ? C2 C3 C4 C5 -3.6(11) . . . . ? C2 C3 C4 S3 179.7(5) . . . . ? N4 S3 C4 C3 178.5(6) . . . . ? N4 S3 C4 C5 1.7(7) . . . . ? C7 N3 C5 N2 -178.8(6) . . . . ? C7 N3 C5 C4 1.3(10) . . . . ? C1 N2 C5 N3 -176.9(6) . . . . ? C6 N2 C5 N3 0.7(10) . . . . ? C1 N2 C5 C4 3.0(10) . . . . ? C6 N2 C5 C4 -179.4(6) . . . . ? C3 C4 C5 N3 -179.8(7) . . . . ? S3 C4 C5 N3 -3.0(9) . . . . ? C3 C4 C5 N2 0.3(10) . . . . ? S3 C4 C5 N2 177.1(5) . . . . ? S3 N4 C7 N3 -3.5(11) . . . . ? S3 N4 C7 C8 178.5(5) . . . . ? C5 N3 C7 N4 2.4(12) . . . . ? C5 N3 C7 C8 -179.6(6) . . . . ? N4 C7 C8 C9 -4.5(11) . . . . ? N3 C7 C8 C9 177.2(7) . . . . ? N4 C7 C8 S4 172.4(5) . . . . ? N3 C7 C8 S4 -5.9(9) . . . . ? C11 S4 C8 C9 -2.1(7) . . . . ? C11 S4 C8 C7 -179.5(6) . . . . ? C7 C8 C9 C10 179.9(7) . . . . ? S4 C8 C9 C10 2.9(8) . . . . ? C8 C9 C10 C11 -2.6(11) . . . . ? C9 C10 C11 S4 1.1(11) . . . . ? C8 S4 C11 C10 0.5(7) . . . . ? _diffrn_measured_fraction_theta_max 0.959 _diffrn_reflns_theta_full 67.63 _diffrn_measured_fraction_theta_full 0.958 _refine_diff_density_max 1.228 _refine_diff_density_min -0.422 _refine_diff_density_rms 0.117