# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Cheng Ma' _publ_contact_author_email MCORG@ZJU.EDU.CN _publ_section_title ; Direct Synthesis of Functionalized Thiophenes through Copper(I)-Catalyzed Tandem Reactions of Alkylidenethiiranes with Terminal Alkynes ; loop_ _publ_author_name 'Cheng Ma' 'Ming Bian' 'Weijun Yao' 'Jianming Gu' 'Yiping Zhang' # Attachment 'ZYP.cif' data__573 _database_code_depnum_ccdc_archive 'CCDC 731411' #============================================================================== # CHEMICAL DATA _chemical_formula_sum 'C19 H17 Br O3 S2 ' _chemical_formula_moiety 'C19 H17 Br O3 S2 ' _chemical_formula_weight 437.37 _chemical_melting_point ? #============================================================================== # CRYSTAL DATA _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 1/2-X,1/2+Y,1/2-Z 3 -X,-Y,-Z 4 1/2+X,1/2-Y,1/2+Z #------------------------------------------------------------------------------ _cell_length_a 5.4744(4) _cell_length_b 24.9708(17) _cell_length_c 13.4472(11) _cell_angle_alpha 90.0000 _cell_angle_beta 91.662(2) _cell_angle_gamma 90.0000 _cell_volume ? _refine_ls_wR_factor_gt ? _cell_formula_units_Z 4 _cell_measurement_reflns_used 7066 _cell_measurement_theta_min 3.0 _cell_measurement_theta_max 27.4 _cell_measurement_temperature 296(1) #------------------------------------------------------------------------------ _exptl_crystal_description platelet _exptl_crystal_colour colorless _exptl_crystal_size_max 0.33 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.09 _exptl_crystal_density_diffrn 1.581 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 888.00 _exptl_absorpt_coefficient_mu 2.486 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; Higashi, T. (1995). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.437 _exptl_absorpt_correction_T_max 0.800 #============================================================================== # EXPERIMENTAL DATA _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71075 _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 17315 _diffrn_reflns_av_R_equivalents 0.095 _diffrn_reflns_theta_max 27.42 _diffrn_measured_fraction_theta_max 0.987 _diffrn_reflns_theta_full 27.42 _diffrn_measured_fraction_theta_full 0.987 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 #============================================================================== # REFINEMENT DATA _refine_special_details ; Refinement using reflections with F^2^ > 2.0 sigma(F^2^). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F^2^ > 2.0 sigma(F^2^) is used only for calculating R-factor (gt). ; _reflns_number_total 4132 _reflns_number_gt 2089 _reflns_threshold_expression F^2^>2.0\s(F^2^) _refine_ls_structure_factor_coef Fsqd _refine_ls_R_factor_gt 0.0607 _refine_ls_wR_factor_ref 0.0899 _refine_ls_hydrogen_treatment constr _refine_ls_number_reflns 4132 _refine_ls_number_parameters 227 _refine_ls_goodness_of_fit_ref 1.000 _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w = 1/[\s^2^(Fo^2^)+(0.0044P)^2^+2.8000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_shift/su_max 0.0010 _refine_diff_density_max 0.35 _refine_diff_density_min -0.38 _refine_ls_extinction_method none _refine_ls_extinction_coef ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.003 0.002 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; H H 0.000 0.000 ; International Tables for Crystallography (1992, Vol. C, Table 6.1.1.4) ; O O 0.011 0.006 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; S S 0.125 0.123 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; Br Br -0.290 2.459 ; International Tables for Crystallography (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4) ; #============================================================================== # ATOMIC COORDINATES AND THERMAL PARAMETERS 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 0.69397(11) 0.55909(2) 0.99621(4) 0.0822(2) Uani 1.00 1 d . . . S1 S 0.2819(2) 0.47346(5) 0.57490(9) 0.0572(3) Uani 1.00 1 d . . . S2 S 0.1061(2) 0.33165(5) 0.56798(9) 0.0582(3) Uani 1.00 1 d . . . O1 O 0.5714(5) 0.56487(11) 0.7825(2) 0.0591(8) Uani 1.00 1 d . . . O2 O 0.3572(5) 0.34476(12) 0.5468(2) 0.0753(10) Uani 1.00 1 d . . . O3 O -0.0227(5) 0.29455(12) 0.5040(2) 0.0799(10) Uani 1.00 1 d . . . C1 C 0.8475(7) 0.60126(16) 0.8999(3) 0.0525(11) Uani 1.00 1 d . . . C2 C 1.0442(8) 0.63248(19) 0.9269(3) 0.0662(13) Uani 1.00 1 d . . . C3 C 1.1581(8) 0.6631(2) 0.8565(4) 0.0734(15) Uani 1.00 1 d . . . C4 C 1.0731(8) 0.66223(18) 0.7601(4) 0.0686(14) Uani 1.00 1 d . . . C5 C 0.8745(8) 0.63031(17) 0.7317(3) 0.0587(12) Uani 1.00 1 d . . . C6 C 0.7612(7) 0.59914(17) 0.8024(3) 0.0497(11) Uani 1.00 1 d . . . C7 C 0.5014(7) 0.55692(17) 0.6813(3) 0.0567(11) Uani 1.00 1 d . . . C8 C 0.3120(7) 0.51306(16) 0.6782(3) 0.0477(10) Uani 1.00 1 d . . . C9 C 0.1552(7) 0.49791(17) 0.7485(3) 0.0503(11) Uani 1.00 1 d . . . C10 C 0.0025(7) 0.45410(16) 0.7192(3) 0.0455(10) Uani 1.00 1 d . . . C11 C 0.0500(6) 0.43712(16) 0.6257(2) 0.0435(10) Uani 1.00 1 d . . . C12 C -0.1888(7) 0.43063(17) 0.7852(3) 0.0597(12) Uani 1.00 1 d . . . C13 C -0.0650(7) 0.39278(16) 0.5667(3) 0.0535(11) Uani 1.00 1 d . . . C14 C 0.0935(7) 0.30887(16) 0.6908(3) 0.0484(11) Uani 1.00 1 d . . . C15 C 0.2748(8) 0.32267(17) 0.7595(4) 0.0613(13) Uani 1.00 1 d . . . C16 C 0.2623(9) 0.3048(2) 0.8558(4) 0.0751(15) Uani 1.00 1 d . . . C17 C 0.0696(10) 0.2737(2) 0.8839(4) 0.0760(15) Uani 1.00 1 d . . . C18 C -0.1109(9) 0.2606(2) 0.8168(4) 0.0739(15) Uani 1.00 1 d . . . C19 C -0.1003(8) 0.27720(18) 0.7195(3) 0.0611(13) Uani 1.00 1 d . . . H2 H 1.1010 0.6330 0.9928 0.079 Uiso 1.00 1 c R . . H3 H 1.2920 0.6843 0.8746 0.088 Uiso 1.00 1 c R . . H4 H 1.1487 0.6832 0.7128 0.082 Uiso 1.00 1 c R . . H5 H 0.8182 0.6299 0.6658 0.070 Uiso 1.00 1 c R . . H9 H 0.1475 0.5145 0.8103 0.060 Uiso 1.00 1 c R . . H16 H 0.3848 0.3139 0.9022 0.090 Uiso 1.00 1 c R . . H17 H 0.0626 0.2615 0.9491 0.091 Uiso 1.00 1 c R . . H18 H -0.2428 0.2402 0.8369 0.089 Uiso 1.00 1 c R . . H19 H -0.2219 0.2673 0.6734 0.073 Uiso 1.00 1 c R . . H45 H 0.4049 0.3440 0.7406 0.074 Uiso 1.00 1 c R . . H71 H 0.6420 0.5463 0.6436 0.068 Uiso 1.00 1 c R . . H82 H 0.4328 0.5897 0.6535 0.068 Uiso 1.00 1 c R . . H121 H -0.2330 0.4566 0.8341 0.072 Uiso 1.00 1 c R . . H122 H -0.1243 0.3993 0.8179 0.072 Uiso 1.00 1 c R . . H123 H -0.3307 0.4211 0.7455 0.072 Uiso 1.00 1 c R . . H131 H -0.0845 0.4046 0.4982 0.064 Uiso 1.00 1 c R . . H132 H -0.2242 0.3855 0.5934 0.064 Uiso 1.00 1 c 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_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Br1 0.1050(4) 0.0888(4) 0.0528(3) -0.0343(3) 0.0010(2) 0.0079(3) S1 0.0642(7) 0.0640(8) 0.0433(7) -0.0199(6) 0.0023(5) -0.0028(6) S2 0.0555(7) 0.0619(8) 0.0576(8) -0.0104(6) 0.0078(5) -0.0179(6) O1 0.073(2) 0.0561(19) 0.048(2) -0.0258(16) 0.0009(15) -0.0024(16) O2 0.0522(19) 0.083(2) 0.092(2) -0.0142(17) 0.0262(17) -0.016(2) O3 0.086(2) 0.083(2) 0.070(2) -0.0214(19) 0.0006(18) -0.036(2) C1 0.064(2) 0.041(2) 0.052(3) -0.013(2) 0.006(2) 0.001(2) C2 0.079(3) 0.066(3) 0.053(3) -0.017(2) -0.009(2) -0.004(2) C3 0.061(3) 0.068(3) 0.091(4) -0.020(2) -0.004(3) -0.005(3) C4 0.070(3) 0.048(3) 0.089(4) -0.017(2) 0.014(3) 0.006(2) C5 0.074(3) 0.049(2) 0.054(3) -0.007(2) 0.005(2) 0.000(2) C6 0.056(2) 0.042(2) 0.051(3) -0.003(2) 0.004(2) -0.004(2) C7 0.069(2) 0.049(2) 0.051(3) -0.011(2) -0.008(2) -0.000(2) C8 0.052(2) 0.043(2) 0.048(2) -0.005(2) -0.006(2) -0.000(2) C9 0.060(2) 0.050(2) 0.041(2) 0.004(2) 0.001(2) -0.004(2) C10 0.045(2) 0.046(2) 0.045(2) 0.004(2) -0.002(2) 0.002(2) C11 0.038(2) 0.047(2) 0.045(2) -0.007(2) -0.0025(19) 0.003(2) C12 0.061(2) 0.059(3) 0.060(3) -0.003(2) 0.011(2) -0.003(2) C13 0.057(2) 0.059(3) 0.045(2) -0.010(2) -0.007(2) 0.004(2) C14 0.040(2) 0.046(2) 0.059(3) 0.001(2) 0.003(2) -0.012(2) C15 0.050(2) 0.054(3) 0.079(3) 0.007(2) -0.002(2) -0.002(2) C16 0.071(3) 0.078(3) 0.075(4) 0.015(3) -0.021(3) -0.004(3) C17 0.085(4) 0.067(3) 0.076(4) 0.028(3) 0.006(3) 0.012(3) C18 0.072(3) 0.061(3) 0.090(4) 0.003(2) 0.019(3) 0.009(3) C19 0.054(2) 0.055(3) 0.075(3) -0.009(2) 0.005(2) -0.008(2) #============================================================================== _computing_data_collection PROCESS-AUTO _computing_cell_refinement PROCESS-AUTO _computing_data_reduction CrystalStructure _computing_structure_solution SIR97 _computing_structure_refinement SHELXL _computing_publication_material 'CrystalStructure 3.7.0' _computing_molecular_graphics ? #============================================================================== # MOLECULAR GEOMETRY _geom_special_details ; ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_publ_flag _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 Br1 C1 1.886(4) ? . . S1 C8 1.709(4) ? . . S1 C11 1.718(3) ? . . S2 O2 1.449(3) ? . . S2 O3 1.436(3) ? . . S2 C13 1.791(4) ? . . S2 C14 1.750(4) ? . . O1 C6 1.367(5) ? . . O1 C7 1.417(5) ? . . C1 C2 1.370(6) ? . . C1 C6 1.382(6) ? . . C2 C3 1.381(7) ? . . C3 C4 1.364(8) ? . . C4 C5 1.393(6) ? . . C5 C6 1.389(6) ? . . C7 C8 1.508(5) ? . . C8 C9 1.350(5) ? . . C9 C10 1.425(5) ? . . C10 C11 1.359(5) ? . . C10 C12 1.511(5) ? . . C11 C13 1.490(5) ? . . C14 C15 1.379(6) ? . . C14 C19 1.387(6) ? . . C15 C16 1.373(7) ? . . C16 C17 1.373(7) ? . . C17 C18 1.358(8) ? . . C18 C19 1.376(8) ? . . C2 H2 0.930 ? . . C3 H3 0.930 ? . . C4 H4 0.930 ? . . C5 H5 0.930 ? . . C7 H71 0.970 ? . . C7 H82 0.970 ? . . C9 H9 0.930 ? . . C12 H121 0.960 ? . . C12 H122 0.960 ? . . C12 H123 0.960 ? . . C13 H131 0.970 ? . . C13 H132 0.970 ? . . C15 H45 0.930 ? . . C16 H16 0.930 ? . . C17 H17 0.930 ? . . C18 H18 0.930 ? . . C19 H19 0.930 ? . . loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_publ_flag _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 C8 S1 C11 92.2(2) ? . . . O2 S2 O3 118.69(19) ? . . . O2 S2 C13 107.72(19) ? . . . O2 S2 C14 108.82(19) ? . . . O3 S2 C13 107.25(19) ? . . . O3 S2 C14 108.90(19) ? . . . C13 S2 C14 104.6(2) ? . . . C6 O1 C7 117.3(3) ? . . . Br1 C1 C2 119.9(3) ? . . . Br1 C1 C6 118.9(3) ? . . . C2 C1 C6 121.2(4) ? . . . C1 C2 C3 120.1(4) ? . . . C2 C3 C4 119.6(4) ? . . . C3 C4 C5 120.8(4) ? . . . C4 C5 C6 119.6(4) ? . . . O1 C6 C1 116.6(3) ? . . . O1 C6 C5 124.7(3) ? . . . C1 C6 C5 118.8(3) ? . . . O1 C7 C8 107.2(3) ? . . . S1 C8 C7 119.5(3) ? . . . S1 C8 C9 111.1(3) ? . . . C7 C8 C9 129.4(3) ? . . . C8 C9 C10 113.6(3) ? . . . C9 C10 C11 111.7(3) ? . . . C9 C10 C12 123.1(3) ? . . . C11 C10 C12 125.2(3) ? . . . S1 C11 C10 111.5(2) ? . . . S1 C11 C13 119.1(3) ? . . . C10 C11 C13 129.4(3) ? . . . S2 C13 C11 114.6(2) ? . . . S2 C14 C15 120.2(3) ? . . . S2 C14 C19 120.0(3) ? . . . C15 C14 C19 119.8(4) ? . . . C14 C15 C16 119.7(4) ? . . . C15 C16 C17 120.2(4) ? . . . C16 C17 C18 120.3(5) ? . . . C17 C18 C19 120.6(4) ? . . . C14 C19 C18 119.4(4) ? . . . C1 C2 H2 120.0 ? . . . C3 C2 H2 120.0 ? . . . C2 C3 H3 120.2 ? . . . C4 C3 H3 120.2 ? . . . C3 C4 H4 119.6 ? . . . C5 C4 H4 119.6 ? . . . C4 C5 H5 120.2 ? . . . C6 C5 H5 120.2 ? . . . O1 C7 H71 110.0 ? . . . O1 C7 H82 110.0 ? . . . C8 C7 H71 110.0 ? . . . C8 C7 H82 110.0 ? . . . H71 C7 H82 109.5 ? . . . C8 C9 H9 123.2 ? . . . C10 C9 H9 123.2 ? . . . C10 C12 H121 109.5 ? . . . C10 C12 H122 109.5 ? . . . C10 C12 H123 109.5 ? . . . H121 C12 H122 109.5 ? . . . H121 C12 H123 109.5 ? . . . H122 C12 H123 109.5 ? . . . S2 C13 H131 108.2 ? . . . S2 C13 H132 108.2 ? . . . C11 C13 H131 108.2 ? . . . C11 C13 H132 108.2 ? . . . H131 C13 H132 109.5 ? . . . C14 C15 H45 120.1 ? . . . C16 C15 H45 120.1 ? . . . C15 C16 H16 119.9 ? . . . C17 C16 H16 119.9 ? . . . C16 C17 H17 119.9 ? . . . C18 C17 H17 119.9 ? . . . C17 C18 H18 119.7 ? . . . C19 C18 H18 119.7 ? . . . C14 C19 H19 120.3 ? . . . C18 C19 H19 120.3 ? . . . 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_publ_flag _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 C8 S1 C11 C10 -1.4(3) ? . . . . C8 S1 C11 C13 179.7(3) ? . . . . C11 S1 C8 C7 -180.0(3) ? . . . . C11 S1 C8 C9 1.5(3) ? . . . . O2 S2 C13 C11 -48.2(3) ? . . . . O2 S2 C14 C15 22.6(4) ? . . . . O2 S2 C14 C19 -157.9(3) ? . . . . O3 S2 C13 C11 -177.0(2) ? . . . . O3 S2 C14 C15 153.4(3) ? . . . . O3 S2 C14 C19 -27.2(4) ? . . . . C13 S2 C14 C15 -92.2(3) ? . . . . C13 S2 C14 C19 87.2(3) ? . . . . C14 S2 C13 C11 67.5(3) ? . . . . C6 O1 C7 C8 173.3(3) ? . . . . C7 O1 C6 C1 -172.0(3) ? . . . . C7 O1 C6 C5 6.3(5) ? . . . . Br1 C1 C2 C3 179.6(3) ? . . . . Br1 C1 C6 O1 -1.7(5) ? . . . . Br1 C1 C6 C5 179.9(2) ? . . . . C2 C1 C6 O1 177.0(3) ? . . . . C2 C1 C6 C5 -1.4(6) ? . . . . C6 C1 C2 C3 0.9(6) ? . . . . C1 C2 C3 C4 0.2(5) ? . . . . C2 C3 C4 C5 -0.7(7) ? . . . . C3 C4 C5 C6 0.2(5) ? . . . . C4 C5 C6 O1 -177.4(3) ? . . . . C4 C5 C6 C1 0.8(6) ? . . . . O1 C7 C8 S1 -151.9(2) ? . . . . O1 C7 C8 C9 26.4(5) ? . . . . S1 C8 C9 C10 -1.2(4) ? . . . . C7 C8 C9 C10 -179.5(3) ? . . . . C8 C9 C10 C11 0.1(3) ? . . . . C8 C9 C10 C12 -179.3(3) ? . . . . C9 C10 C11 S1 1.0(4) ? . . . . C9 C10 C11 C13 179.7(3) ? . . . . C12 C10 C11 S1 -179.6(3) ? . . . . C12 C10 C11 C13 -0.9(6) ? . . . . S1 C11 C13 S2 79.8(3) ? . . . . C10 C11 C13 S2 -98.8(4) ? . . . . S2 C14 C15 C16 179.6(3) ? . . . . S2 C14 C19 C18 -178.5(3) ? . . . . C15 C14 C19 C18 1.0(6) ? . . . . C19 C14 C15 C16 0.1(5) ? . . . . C14 C15 C16 C17 -0.4(7) ? . . . . C15 C16 C17 C18 -0.4(8) ? . . . . C16 C17 C18 C19 1.6(8) ? . . . . C17 C18 C19 C14 -1.8(7) ? . . . . #============================================================================== # Additional structures and associated data_? identifiers # should be added at this point if there is more than one # structure analysis in the CIF. #============================================================================== # End of CIF #==============================================================================