# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 182/1640 data_global _publ_section_title ;Electrophilic halogenation of thioethers: 5-chloro- and 5,6-dichloro- 5,6-dihydro-1,3-dithiolo[4,5-b][1,4]dithiine-2-one and an efficient synthesis of vinylenedithio-tetrathiafulvalene (VDT-TTF) ; _publ_contact_author ; Dr Marc Fourmigu Institut des Matriaux Jean Rouxel UMR 6502 CNRS-Universit de Nantes BP 32229, 2, rue de la Houssinire 44322 Nantes cedex 03 France ; _publ_contact_author_email fourmigue@cnrs-imn.fr _publ_contact_author_fax '33 2 40 37 39 95' _publ_contact_author_phone '33 2 40 37 39 15' _publ_contact_letter ; Please find enclosed data for deposition related to two structures to be included in a paper we are submitting to Chem. Comm. Best regards ; loop_ _publ_author_address 'Dautel, Olivier, J.' ; Institut des Matriaux Jean Rouxel UMR 6502 CNRS-Universit de Nantes BP 32229, 2, rue de la Houssinire 44322 Nantes cedex 03 France ; 'Larsen, Jan' ; Institut des Matriaux Jean Rouxel UMR 6502 CNRS-Universit de Nantes BP 32229, 2, rue de la Houssinire 44322 Nantes cedex 03 France ; 'Fourmigue, Marc' ; Institut des Matriaux Jean Rouxel UMR 6502 CNRS-Universit de Nantes BP 32229, 2, rue de la Houssinire 44322 Nantes cedex 03 France ; data_dop176me _publ_requested_journal 'Chem. Commun.' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 5,6-Dichloro-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2one ; _chemical_name_common 'dichloroethylendithiolone' _chemical_melting_point 157 _chemical_formula_moiety ? _chemical_formula_sum 'C5 H2 Cl2 O S4' _chemical_formula_weight 277.21 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' 'O' 'O' 0.0106 0.0060 '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 orthorhombic _symmetry_space_group_name_H-M 'Pmmn' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z' '-x, y+1/2, -z' 'x+1/2, -y, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z' 'x, -y-1/2, z' '-x-1/2, y, z' _cell_length_a 7.0595(21) _cell_length_b 7.4252(20) _cell_length_c 9.3827(22) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 491.8(4) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1365 _cell_measurement_theta_min 2.75 _cell_measurement_theta_max 25.7 _exptl_crystal_description 'platelet' _exptl_crystal_colour white _exptl_crystal_size_max 0.308 _exptl_crystal_size_mid 0.231 _exptl_crystal_size_min 0.0192 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.875 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 276 _exptl_absorpt_coefficient_mu 1.456 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.7715 _exptl_absorpt_correction_T_max 0.9702 _exptl_absorpt_process_details 'FACEIT, STOE-IPDS' _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 'STOE-IPDS' _diffrn_measurement_method 'Oscillation, Phi incr.= 2.5' _diffrn_detector_area_resol_mean 6.66 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2833 _diffrn_reflns_av_R_equivalents 0.0337 _diffrn_reflns_av_sigmaI/netI 0.0451 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.50 _diffrn_reflns_theta_max 26.04 _reflns_number_total 558 _reflns_number_gt 323 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'EXPOSE [STOE-IPDS]' _computing_cell_refinement 'SELECT, CELL [STOE-IPDS]' _computing_data_reduction 'INTEGRATE [STOE-IPDS]' _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^)+(0.0590P)^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 558 _refine_ls_number_parameters 42 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0687 _refine_ls_R_factor_gt 0.0357 _refine_ls_wR_factor_ref 0.0970 _refine_ls_wR_factor_gt 0.0871 _refine_ls_goodness_of_fit_ref 0.816 _refine_ls_restrained_S_all 0.816 _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 -0.00186(17) 0.7500 0.74113(13) 0.0740(5) Uani 1 2 d S . . Cl1 Cl -0.2500 0.46274(17) 0.89371(16) 0.0927(6) Uani 1 2 d S . . S1 S -0.0425(2) 0.7500 0.43087(14) 0.0873(6) Uani 1 2 d S . . C2 C -0.1559(6) 0.7500 0.5963(4) 0.0542(11) Uani 1 2 d S . . 01 O -0.2500 0.7500 0.1988(5) 0.118(2) Uani 1 4 d S . . C1 C -0.2500 0.7500 0.3266(7) 0.080(2) Uani 1 4 d S . . C3 C -0.1594(8) 0.6951(6) 0.8844(5) 0.0486(15) Uani 0.50 1 d P . . 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 0.0469(6) 0.1244(12) 0.0506(7) 0.000 -0.0003(6) 0.000 Cl1 0.1445(14) 0.0451(6) 0.0884(11) 0.0031(7) 0.000 0.000 S1 0.0979(11) 0.1222(12) 0.0417(7) 0.000 0.0244(7) 0.000 C2 0.064(3) 0.065(2) 0.033(2) 0.000 0.0072(19) 0.000 01 0.191(6) 0.135(5) 0.027(3) 0.000 0.000 0.000 C1 0.138(7) 0.075(5) 0.028(4) 0.000 0.000 0.000 C3 0.067(3) 0.044(3) 0.035(3) 0.004(2) -0.003(2) 0.004(3) _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 C2 1.738(4) . ? S2 C3 1.789(5) . ? S2 C3 1.789(5) 7_575 ? Cl1 C3 1.844(5) 8 ? Cl1 C3 1.844(5) . ? S1 C2 1.744(4) . ? S1 C1 1.758(4) . ? C2 C2 1.327(9) 2_465 ? 01 C1 1.198(8) . ? C1 S1 1.758(4) 2_465 ? C3 C3 0.816(9) 7_575 ? C3 C3 1.277(11) 8 ? C3 C3 1.516(10) 2_465 ? 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 S2 C3 101.4(2) . . ? C2 S2 C3 101.4(2) . 7_575 ? C3 S2 C3 26.4(3) . 7_575 ? C3 Cl1 C3 40.5(3) 8 . ? C2 S1 C1 96.5(2) . . ? C2 C2 S2 128.66(14) 2_465 . ? C2 C2 S1 117.26(15) 2_465 . ? S2 C2 S1 114.1(2) . . ? 01 C1 S1 123.74(18) . 2_465 ? 01 C1 S1 123.74(18) . . ? S1 C1 S1 112.5(4) 2_465 . ? C3 C3 C3 89.999(4) 7_575 8 ? C3 C3 C3 57.4(4) 7_575 2_465 ? C3 C3 C3 32.6(4) 8 2_465 ? C3 C3 S2 76.82(15) 7_575 . ? C3 C3 S2 128.35(16) 8 . ? C3 C3 S2 113.6(3) 2_465 . ? C3 C3 Cl1 159.54(16) 7_575 . ? C3 C3 Cl1 69.74(16) 8 . ? C3 C3 Cl1 102.3(4) 2_465 . ? S2 C3 Cl1 117.6(3) . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 26.04 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.433 _refine_diff_density_min -0.228 _refine_diff_density_rms 0.060 #===END data_dop205bmer _publ_requested_journal 'test' _audit_creation_method SHELXL-97 _chemical_name_systematic ; 2-[1,3]dithiol-2-ylidene-[1,3]dithiolo[4,5-b][1,4]dithiine ; _chemical_name_common 'VDT-TTF' _chemical_melting_point 185 _chemical_formula_moiety ? _chemical_formula_sum 'C8 H4 S6' _chemical_formula_weight 292.47 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P21/n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.4203(13) _cell_length_b 14.905(3) _cell_length_c 11.648(2) _cell_angle_alpha 90.00 _cell_angle_beta 93.58(3) _cell_angle_gamma 90.00 _cell_volume 1112.4(4) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 7040 _cell_measurement_theta_min 2.2 _cell_measurement_theta_max 25.85 _exptl_crystal_description 'platelet' _exptl_crystal_colour red _exptl_crystal_size_max 0.5006 _exptl_crystal_size_mid 0.3466 _exptl_crystal_size_min 0.1156 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.746 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 592 _exptl_absorpt_coefficient_mu 1.182 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.6433 _exptl_absorpt_correction_T_max 0.8721 _exptl_absorpt_process_details 'FACEIT, STOE-IPDS' _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 'STOE-IPDS' _diffrn_measurement_method 'Oscillation, Phi incr.= 1.6' _diffrn_detector_area_resol_mean 6.66 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8649 _diffrn_reflns_av_R_equivalents 0.0515 _diffrn_reflns_av_sigmaI/netI 0.0451 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.22 _diffrn_reflns_theta_max 25.85 _reflns_number_total 2142 _reflns_number_gt 1587 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'EXPOSE [STOE-IPDS]' _computing_cell_refinement 'SELECT, CELL [STOE-IPDS]' _computing_data_reduction 'INTEGRATE [STOE-IPDS]' _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^)+(0.0236P)^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 refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2142 _refine_ls_number_parameters 143 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0412 _refine_ls_R_factor_gt 0.0268 _refine_ls_wR_factor_ref 0.0590 _refine_ls_wR_factor_gt 0.0565 _refine_ls_goodness_of_fit_ref 0.886 _refine_ls_restrained_S_all 0.886 _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 S1 S 0.17209(8) 0.61244(4) 0.90147(5) 0.03553(14) Uani 1 1 d . . . S2 S 0.01320(9) 0.47814(5) 0.69429(5) 0.05142(18) Uani 1 1 d . . . S3 S -0.40194(9) 0.46942(5) 0.78755(6) 0.04997(18) Uani 1 1 d . . . S4 S -0.24521(8) 0.60585(4) 0.99468(5) 0.03515(14) Uani 1 1 d . . . S5 S -0.16563(9) 0.77237(5) 1.13772(6) 0.04887(18) Uani 1 1 d . . . S6 S 0.29069(10) 0.78186(5) 1.02967(6) 0.05193(18) Uani 1 1 d . . . C1 C -0.0830(3) 0.56895(14) 0.88723(18) 0.0311(5) Uani 1 1 d . . . C2 C -0.1478(3) 0.51271(15) 0.80280(18) 0.0342(5) Uani 1 1 d . . . C3 C -0.1941(5) 0.4396(2) 0.6038(2) 0.0580(8) Uani 1 1 d . . . C4 C -0.3785(5) 0.4359(2) 0.6456(2) 0.0584(8) Uani 1 1 d . . . C5 C -0.0881(3) 0.69917(14) 1.03069(19) 0.0347(5) Uani 1 1 d . . . C6 C 0.0720(4) 0.7798(2) 1.2219(3) 0.0572(7) Uani 1 1 d . . . C7 C 0.2563(4) 0.7827(2) 1.1784(2) 0.0581(8) Uani 1 1 d . . . C8 C 0.1001(3) 0.70255(14) 0.98735(19) 0.0354(5) Uani 1 1 d . . . H1 H -0.167(4) 0.4247(19) 0.538(2) 0.061(9) Uiso 1 1 d . . . H2 H -0.503(5) 0.4149(19) 0.607(2) 0.071(9) Uiso 1 1 d . . . H3 H 0.053(4) 0.7737(19) 1.303(2) 0.061(8) Uiso 1 1 d . . . H4 H 0.382(4) 0.7815(18) 1.229(2) 0.063(8) 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 0.0268(3) 0.0404(3) 0.0399(3) -0.0045(3) 0.0056(2) -0.0020(2) S2 0.0419(3) 0.0670(4) 0.0463(4) -0.0186(3) 0.0103(3) -0.0013(3) S3 0.0350(3) 0.0596(4) 0.0556(4) -0.0171(3) 0.0051(3) -0.0110(3) S4 0.0281(3) 0.0408(3) 0.0370(3) -0.0043(3) 0.0058(2) -0.0023(2) S5 0.0370(3) 0.0547(4) 0.0544(4) -0.0207(3) -0.0014(3) 0.0102(3) S6 0.0400(3) 0.0449(4) 0.0707(5) -0.0104(3) 0.0022(3) -0.0119(3) C1 0.0268(10) 0.0326(11) 0.0340(12) 0.0009(10) 0.0036(8) 0.0007(9) C2 0.0306(11) 0.0372(12) 0.0347(12) -0.0016(10) 0.0022(9) 0.0006(9) C3 0.0642(18) 0.0668(19) 0.0427(16) -0.0200(15) 0.0012(14) -0.0037(15) C4 0.0524(16) 0.0676(19) 0.0535(17) -0.0205(15) -0.0096(13) -0.0076(14) C5 0.0331(11) 0.0344(12) 0.0360(12) -0.0042(10) -0.0026(9) 0.0037(9) C6 0.0505(16) 0.0668(19) 0.0530(17) -0.0281(15) -0.0076(13) 0.0069(13) C7 0.0405(15) 0.0652(18) 0.0666(18) -0.0316(15) -0.0117(13) 0.0027(13) C8 0.0322(11) 0.0333(12) 0.0400(12) -0.0022(10) -0.0015(9) -0.0025(9) _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 C8 1.754(2) . ? S1 C1 1.760(2) . ? S2 C3 1.743(3) . ? S2 C2 1.759(2) . ? S3 C4 1.743(3) . ? S3 C2 1.753(2) . ? S4 C5 1.754(2) . ? S4 C1 1.765(2) . ? S5 C5 1.752(2) . ? S5 C6 1.765(3) . ? S6 C8 1.750(2) . ? S6 C7 1.760(3) . ? C1 C2 1.339(3) . ? C3 C4 1.309(4) . ? C5 C8 1.339(3) . ? C6 C7 1.317(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 C8 S1 C1 93.39(10) . . ? C3 S2 C2 94.04(13) . . ? C4 S3 C2 93.83(12) . . ? C5 S4 C1 93.48(10) . . ? C5 S5 C6 99.21(12) . . ? C8 S6 C7 98.85(13) . . ? C2 C1 S1 123.00(16) . . ? C2 C1 S4 123.10(16) . . ? S1 C1 S4 113.91(12) . . ? C1 C2 S3 123.33(16) . . ? C1 C2 S2 122.80(16) . . ? S3 C2 S2 113.84(12) . . ? C4 C3 S2 117.6(2) . . ? C3 C4 S3 118.3(2) . . ? C8 C5 S5 123.22(17) . . ? C8 C5 S4 117.31(17) . . ? S5 C5 S4 118.64(13) . . ? C7 C6 S5 123.7(2) . . ? C6 C7 S6 123.3(2) . . ? C5 C8 S6 123.41(17) . . ? C5 C8 S1 117.53(17) . . ? S6 C8 S1 118.27(12) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.85 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.296 _refine_diff_density_min -0.177 _refine_diff_density_rms 0.058 #===END