Electronic Supplementary Material for Chemical Communications This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Varinder Aggarwal' _publ_contact_author_address ; School of Chemistry University of Bristol Cantock's Close Bristol BS8 1TS UNITED KINGDOM ; _publ_contact_author_email V.AGGARWAL@BRISTOL.AC.UK _publ_section_title ; Hemi-aminals as substrates for sulfur ylides: Direct asymmetric syntheses of functionalised pyrrolidines and piperidines ; loop_ _publ_author_name 'Varinder Aggarwal' 'Christoforos G. Kokotos' # Attachment 'hemiaminals as substrates for sulfur ylides compound 12.cif' data_ck139sad _database_code_depnum_ccdc_archive 'CCDC 298299' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H21 N O3 S' _chemical_formula_sum 'C18 H21 N O3 S' _chemical_formula_weight 331.42 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' O O 0.0492 0.0322 '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 b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' 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' '-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 8.0828(3) _cell_length_b 18.1324(5) _cell_length_c 22.0830(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3236.50(18) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 183 _cell_measurement_theta_min 4.004 _cell_measurement_theta_max 69.985 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.15 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.360 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1408 _exptl_absorpt_coefficient_mu 1.900 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.677304 _exptl_absorpt_correction_T_max 0.890000 _exptl_absorpt_process_details 'SADABS V2.10 (Sheldrick, G.M., University of G\"ottingen, 2003)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_specimen_support 'glass fibre' _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'Osmic CMF12-38Cu6 (blue) mirror optics' _diffrn_radiation_collimation 'Osmic CMF12-38Cu6 (blue) mirror optics' _diffrn_radiation_probe X-ray _diffrn_measurement_details 'frames, 0.3\% width' _diffrn_measurement_device 'three-circle diffractometer' _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector 'CCD plate' _diffrn_detector_area_resol_mean 5.602 _diffrn_detector_type 'Bruker-AXS SMART 6000' _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 14406 _diffrn_reflns_av_R_equivalents 0.0649 _diffrn_reflns_av_sigmaI/netI 0.0560 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 4.00 _diffrn_reflns_theta_max 70.00 _reflns_number_total 3033 _reflns_number_gt 2491 _reflns_threshold_expression >2sigma(I) _diffrn_source rotating-anode _diffrn_source_current 120 _diffrn_source_power 4.8 _diffrn_source_size '3 x 0.3mm' _diffrn_source_target Cu _diffrn_source_type 'MAC Science M18XCE' _diffrn_source_voltage 40 _computing_data_collection 'Bruker SMART V5.054 (Bruker, 1998)' _computing_cell_refinement 'Bruker SMART V5.054 (Bruker, 1998)' _computing_data_reduction 'Bruker SAINT V6.0 (Bruker, 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL V6.14 (Bruker AXS, 2000)' _computing_publication_material 'Bruker SHELXTL V6.14 (Bruker AXS, 2000)' _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^)+(0.0861P)^2^+1.1487P] 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_number_reflns 3033 _refine_ls_number_parameters 210 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0603 _refine_ls_R_factor_gt 0.0494 _refine_ls_wR_factor_ref 0.1426 _refine_ls_wR_factor_gt 0.1328 _refine_ls_goodness_of_fit_ref 1.043 _refine_ls_restrained_S_all 1.043 _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 1.13867(6) 0.95294(2) 0.35690(2) 0.01477(19) Uani 1 1 d . . . N1 N 0.9641(2) 0.91880(9) 0.37784(8) 0.0151(4) Uani 1 1 d . . . O1 O 1.24238(19) 0.95446(8) 0.41012(7) 0.0186(4) Uani 1 1 d . . . O2 O 1.2018(2) 0.91570(8) 0.30428(7) 0.0220(4) Uani 1 1 d . . . O3 O 0.7931(2) 0.99527(7) 0.47171(7) 0.0231(4) Uani 1 1 d . . . H3 H 0.7812 1.0049 0.5087 0.035 Uiso 1 1 calc R . . C1 C 1.0949(3) 1.04476(10) 0.33477(10) 0.0154(5) Uani 1 1 d . . . C2 C 1.0045(3) 1.08986(11) 0.37356(10) 0.0206(5) Uani 1 1 d . . . H2 H 0.9612 1.0710 0.4104 0.025 Uiso 1 1 calc R . . C3 C 0.9789(3) 1.16291(11) 0.35749(10) 0.0212(5) Uani 1 1 d . . . H3A H 0.9181 1.1942 0.3838 0.025 Uiso 1 1 calc R . . C4 C 1.0408(3) 1.19127(11) 0.30329(10) 0.0198(5) Uani 1 1 d . . . C5 C 1.1294(3) 1.14449(12) 0.26515(10) 0.0199(5) Uani 1 1 d . . . H5 H 1.1716 1.1630 0.2280 0.024 Uiso 1 1 calc R . . C6 C 1.1570(3) 1.07119(11) 0.28065(10) 0.0181(5) Uani 1 1 d . . . H6 H 1.2176 1.0397 0.2544 0.022 Uiso 1 1 calc R . . C7 C 1.0116(3) 1.27072(12) 0.28607(12) 0.0289(6) Uani 1 1 d . . . H7A H 0.9199 1.2906 0.3101 0.043 Uiso 1 1 calc R . . H7B H 0.9840 1.2737 0.2429 0.043 Uiso 1 1 calc R . . H7C H 1.1119 1.2995 0.2940 0.043 Uiso 1 1 calc R . . C8 C 0.9332(3) 0.88618(10) 0.43798(9) 0.0162(5) Uani 1 1 d . . . H8 H 1.0237 0.9030 0.4656 0.019 Uiso 1 1 calc R . . C9 C 0.7700(3) 0.91775(11) 0.46212(10) 0.0173(5) Uani 1 1 d . . . H9 H 0.7412 0.8934 0.5013 0.021 Uiso 1 1 calc R . . C10 C 0.6300(3) 0.90708(12) 0.41722(11) 0.0213(5) Uani 1 1 d . . . H10A H 0.5280 0.9300 0.4334 0.026 Uiso 1 1 calc R . . H10B H 0.6087 0.8537 0.4119 0.026 Uiso 1 1 calc R . . C11 C 0.6713(3) 0.94143(12) 0.35573(10) 0.0209(5) Uani 1 1 d . . . H11A H 0.5811 0.9309 0.3267 0.025 Uiso 1 1 calc R . . H11B H 0.6808 0.9956 0.3600 0.025 Uiso 1 1 calc R . . C12 C 0.8332(3) 0.91027(11) 0.33170(10) 0.0183(5) Uani 1 1 d . . . H12A H 0.8191 0.8574 0.3217 0.022 Uiso 1 1 calc R . . H12B H 0.8654 0.9367 0.2943 0.022 Uiso 1 1 calc R . . C13 C 0.9388(3) 0.80132(11) 0.43557(10) 0.0164(5) Uani 1 1 d . . . C14 C 1.0335(3) 0.76523(11) 0.39208(10) 0.0205(5) Uani 1 1 d . . . H14 H 1.0929 0.7933 0.3630 0.025 Uiso 1 1 calc R . . C15 C 1.0424(3) 0.68813(12) 0.39055(11) 0.0236(5) Uani 1 1 d . . . H15 H 1.1079 0.6643 0.3607 0.028 Uiso 1 1 calc R . . C16 C 0.9559(3) 0.64683(11) 0.43248(11) 0.0232(5) Uani 1 1 d . . . H16 H 0.9598 0.5945 0.4309 0.028 Uiso 1 1 calc R . . C17 C 0.8635(3) 0.68170(12) 0.47675(11) 0.0244(5) Uani 1 1 d . . . H17 H 0.8058 0.6533 0.5061 0.029 Uiso 1 1 calc R . . C18 C 0.8549(3) 0.75858(12) 0.47845(10) 0.0207(5) Uani 1 1 d . . . H18 H 0.7914 0.7821 0.5091 0.025 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 0.0163(3) 0.0134(3) 0.0146(3) 0.00127(18) 0.00258(19) 0.00169(16) N1 0.0161(10) 0.0161(8) 0.0131(9) 0.0011(7) -0.0013(7) -0.0007(6) O1 0.0136(8) 0.0231(8) 0.0190(8) 0.0035(6) 0.0008(6) 0.0004(5) O2 0.0291(10) 0.0171(7) 0.0198(8) 0.0000(6) 0.0077(7) 0.0040(6) O3 0.0338(10) 0.0156(7) 0.0200(8) -0.0021(6) 0.0054(7) 0.0018(6) C1 0.0175(12) 0.0114(9) 0.0173(11) 0.0006(8) -0.0006(9) -0.0015(7) C2 0.0225(13) 0.0180(10) 0.0214(11) 0.0002(9) 0.0052(9) 0.0007(8) C3 0.0214(13) 0.0166(10) 0.0256(12) -0.0017(9) 0.0066(10) 0.0024(8) C4 0.0175(12) 0.0158(10) 0.0259(12) 0.0020(9) -0.0017(9) -0.0009(8) C5 0.0236(13) 0.0201(11) 0.0160(11) 0.0033(9) 0.0027(9) -0.0029(8) C6 0.0208(13) 0.0154(10) 0.0182(11) -0.0005(9) 0.0030(9) 0.0007(8) C7 0.0358(16) 0.0174(11) 0.0335(14) 0.0051(10) 0.0075(11) 0.0026(9) C8 0.0185(12) 0.0150(9) 0.0150(10) 0.0023(8) 0.0002(9) -0.0014(8) C9 0.0199(13) 0.0150(10) 0.0171(11) 0.0023(8) 0.0042(9) 0.0002(8) C10 0.0157(13) 0.0222(10) 0.0259(13) 0.0038(9) 0.0024(9) 0.0013(8) C11 0.0205(13) 0.0202(10) 0.0220(12) 0.0017(9) -0.0034(10) 0.0005(9) C12 0.0209(13) 0.0183(10) 0.0155(11) 0.0001(8) -0.0049(9) -0.0014(8) C13 0.0164(12) 0.0153(9) 0.0176(11) 0.0032(8) -0.0041(9) 0.0000(7) C14 0.0238(13) 0.0170(10) 0.0207(12) 0.0027(8) 0.0005(9) 0.0000(8) C15 0.0269(14) 0.0198(11) 0.0242(12) -0.0032(9) -0.0016(10) 0.0023(9) C16 0.0254(14) 0.0159(10) 0.0284(12) 0.0025(9) -0.0087(10) -0.0013(8) C17 0.0201(13) 0.0234(11) 0.0296(13) 0.0105(10) -0.0029(10) -0.0016(8) C18 0.0194(13) 0.0215(11) 0.0211(12) 0.0040(9) 0.0023(9) 0.0022(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 S1 O2 1.4376(15) . ? S1 O1 1.4440(16) . ? S1 N1 1.6085(18) . ? S1 C1 1.7708(19) . ? N1 C8 1.475(3) . ? N1 C12 1.477(3) . ? O3 C9 1.434(2) . ? O3 H3 0.8400 . ? C1 C6 1.382(3) . ? C1 C2 1.391(3) . ? C2 C3 1.387(3) . ? C2 H2 0.9500 . ? C3 C4 1.396(3) . ? C3 H3A 0.9500 . ? C4 C5 1.393(3) . ? C4 C7 1.508(3) . ? C5 C6 1.390(3) . ? C5 H5 0.9500 . ? C6 H6 0.9500 . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 C9 1.533(3) . ? C8 C13 1.540(3) . ? C8 H8 1.0000 . ? C9 C10 1.517(3) . ? C9 H9 1.0000 . ? C10 C11 1.531(3) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 C12 1.521(3) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 C14 1.391(3) . ? C13 C18 1.399(3) . ? C14 C15 1.400(3) . ? C14 H14 0.9500 . ? C15 C16 1.381(3) . ? C15 H15 0.9500 . ? C16 C17 1.383(3) . ? C16 H16 0.9500 . ? C17 C18 1.396(3) . ? C17 H17 0.9500 . ? C18 H18 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 O2 S1 O1 117.43(9) . . ? O2 S1 N1 111.29(9) . . ? O1 S1 N1 106.41(9) . . ? O2 S1 C1 106.83(9) . . ? O1 S1 C1 108.82(9) . . ? N1 S1 C1 105.43(10) . . ? C8 N1 C12 117.23(17) . . ? C8 N1 S1 124.18(15) . . ? C12 N1 S1 118.05(14) . . ? C9 O3 H3 109.5 . . ? C6 C1 C2 121.27(18) . . ? C6 C1 S1 119.49(16) . . ? C2 C1 S1 119.18(16) . . ? C3 C2 C1 118.8(2) . . ? C3 C2 H2 120.6 . . ? C1 C2 H2 120.6 . . ? C2 C3 C4 121.2(2) . . ? C2 C3 H3A 119.4 . . ? C4 C3 H3A 119.4 . . ? C5 C4 C3 118.57(19) . . ? C5 C4 C7 120.6(2) . . ? C3 C4 C7 120.8(2) . . ? C6 C5 C4 121.0(2) . . ? C6 C5 H5 119.5 . . ? C4 C5 H5 119.5 . . ? C1 C6 C5 119.09(19) . . ? C1 C6 H6 120.5 . . ? C5 C6 H6 120.5 . . ? C4 C7 H7A 109.5 . . ? C4 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C4 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N1 C8 C9 108.00(16) . . ? N1 C8 C13 111.37(16) . . ? C9 C8 C13 114.23(17) . . ? N1 C8 H8 107.7 . . ? C9 C8 H8 107.7 . . ? C13 C8 H8 107.7 . . ? O3 C9 C10 108.58(17) . . ? O3 C9 C8 107.79(17) . . ? C10 C9 C8 111.53(18) . . ? O3 C9 H9 109.6 . . ? C10 C9 H9 109.6 . . ? C8 C9 H9 109.6 . . ? C9 C10 C11 111.40(18) . . ? C9 C10 H10A 109.3 . . ? C11 C10 H10A 109.3 . . ? C9 C10 H10B 109.3 . . ? C11 C10 H10B 109.3 . . ? H10A C10 H10B 108.0 . . ? C12 C11 C10 110.25(18) . . ? C12 C11 H11A 109.6 . . ? C10 C11 H11A 109.6 . . ? C12 C11 H11B 109.6 . . ? C10 C11 H11B 109.6 . . ? H11A C11 H11B 108.1 . . ? N1 C12 C11 109.69(17) . . ? N1 C12 H12A 109.7 . . ? C11 C12 H12A 109.7 . . ? N1 C12 H12B 109.7 . . ? C11 C12 H12B 109.7 . . ? H12A C12 H12B 108.2 . . ? C14 C13 C18 118.25(18) . . ? C14 C13 C8 120.66(18) . . ? C18 C13 C8 121.04(19) . . ? C13 C14 C15 121.0(2) . . ? C13 C14 H14 119.5 . . ? C15 C14 H14 119.5 . . ? C16 C15 C14 120.0(2) . . ? C16 C15 H15 120.0 . . ? C14 C15 H15 120.0 . . ? C15 C16 C17 119.95(19) . . ? C15 C16 H16 120.0 . . ? C17 C16 H16 120.0 . . ? C16 C17 C18 120.2(2) . . ? C16 C17 H17 119.9 . . ? C18 C17 H17 119.9 . . ? C17 C18 C13 120.7(2) . . ? C17 C18 H18 119.6 . . ? C13 C18 H18 119.6 . . ? 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 O2 S1 N1 C8 120.87(16) . . . . ? O1 S1 N1 C8 -8.19(17) . . . . ? C1 S1 N1 C8 -123.67(16) . . . . ? O2 S1 N1 C12 -50.50(16) . . . . ? O1 S1 N1 C12 -179.56(14) . . . . ? C1 S1 N1 C12 64.96(16) . . . . ? O2 S1 C1 C6 -14.3(2) . . . . ? O1 S1 C1 C6 113.45(19) . . . . ? N1 S1 C1 C6 -132.74(18) . . . . ? O2 S1 C1 C2 168.49(18) . . . . ? O1 S1 C1 C2 -63.8(2) . . . . ? N1 S1 C1 C2 50.0(2) . . . . ? C6 C1 C2 C3 -0.9(3) . . . . ? S1 C1 C2 C3 176.34(18) . . . . ? C1 C2 C3 C4 0.5(4) . . . . ? C2 C3 C4 C5 0.1(3) . . . . ? C2 C3 C4 C7 179.7(2) . . . . ? C3 C4 C5 C6 -0.4(3) . . . . ? C7 C4 C5 C6 180.0(2) . . . . ? C2 C1 C6 C5 0.6(3) . . . . ? S1 C1 C6 C5 -176.62(17) . . . . ? C4 C5 C6 C1 0.1(3) . . . . ? C12 N1 C8 C9 -55.5(2) . . . . ? S1 N1 C8 C9 133.04(16) . . . . ? C12 N1 C8 C13 70.7(2) . . . . ? S1 N1 C8 C13 -100.77(19) . . . . ? N1 C8 C9 O3 -65.4(2) . . . . ? C13 C8 C9 O3 170.07(17) . . . . ? N1 C8 C9 C10 53.7(2) . . . . ? C13 C8 C9 C10 -70.8(2) . . . . ? O3 C9 C10 C11 62.1(2) . . . . ? C8 C9 C10 C11 -56.5(2) . . . . ? C9 C10 C11 C12 55.6(2) . . . . ? C8 N1 C12 C11 56.3(2) . . . . ? S1 N1 C12 C11 -131.77(16) . . . . ? C10 C11 C12 N1 -53.2(2) . . . . ? N1 C8 C13 C14 27.3(3) . . . . ? C9 C8 C13 C14 150.0(2) . . . . ? N1 C8 C13 C18 -155.46(19) . . . . ? C9 C8 C13 C18 -32.8(3) . . . . ? C18 C13 C14 C15 1.1(3) . . . . ? C8 C13 C14 C15 178.4(2) . . . . ? C13 C14 C15 C16 0.3(3) . . . . ? C14 C15 C16 C17 -1.4(3) . . . . ? C15 C16 C17 C18 1.2(3) . . . . ? C16 C17 C18 C13 0.1(3) . . . . ? C14 C13 C18 C17 -1.3(3) . . . . ? C8 C13 C18 C17 -178.6(2) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O3 H3 O1 0.84 1.95 2.779(2) 169.8 5_776 _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 70.00 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.470 _refine_diff_density_min -0.293 _refine_diff_density_rms 0.074 # Attachment #'hemiaminals as substrates for sulfur ylides compounds 8 and 15.cif' data_ck87da _database_code_depnum_ccdc_archive 'CCDC 298300' _audit_creation_method SHELXL-97 _chemical_formula_moiety 'C17 H19 N O3 S' _chemical_formula_sum 'C17 H19 N O3 S' _chemical_formula_weight 317.39 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' 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' 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 10.411(2) _cell_length_b 7.7097(15) _cell_length_c 19.546(4) _cell_angle_alpha 90.00 _cell_angle_beta 94.63(3) _cell_angle_gamma 90.00 _cell_volume 1563.8(5) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3020 _cell_measurement_theta_min 2.75 _cell_measurement_theta_max 26.78 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.01 _exptl_crystal_density_diffrn 1.348 _exptl_crystal_density_method none _exptl_crystal_F_000 672 _exptl_absorpt_coefficient_mu 0.219 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.919 _exptl_absorpt_correction_T_max 1.000 _exptl_absorpt_process_details 'SADABS v2.03 (Sheldrick, 2003)' _diffrn_ambient_temperature 100(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 'Frames, each covering 0.3 \% in \w' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_decay_% 0 _diffrn_reflns_number 17082 _diffrn_reflns_av_R_equivalents 0.0442 _diffrn_reflns_av_sigmaI/netI 0.0377 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 1.96 _diffrn_reflns_theta_max 27.48 _reflns_number_total 3578 _reflns_number_gt 2953 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART v5.628 (Bruker-AXS, 2003)' _computing_cell_refinement 'SAINT v6.28A (Bruker-AXS, 2000)' _computing_data_reduction ; SAINT v6.28A and SHELXTL v6.1 (Bruker-AXS, 2000) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL v6.1 (Bruker-AXS, 2000)' _computing_publication_material 'SHELXTL v6.1 (Bruker-AXS, 2000)' _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^)+(0.0456P)^2^+0.9149P] 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_number_reflns 3578 _refine_ls_number_parameters 201 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0568 _refine_ls_R_factor_gt 0.0437 _refine_ls_wR_factor_ref 0.1054 _refine_ls_wR_factor_gt 0.0989 _refine_ls_goodness_of_fit_ref 1.065 _refine_ls_restrained_S_all 1.065 _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 C1 C 0.19509(17) 0.3536(2) 0.03672(9) 0.0152(4) Uani 1 1 d . . . H1 H 0.1018 0.3274 0.0252 0.018 Uiso 1 1 calc R . . C2 C 0.21238(18) 0.5487(2) 0.05316(9) 0.0179(4) Uani 1 1 d . . . H2 H 0.2437 0.6134 0.0134 0.021 Uiso 1 1 calc R . . C3 C 0.31182(18) 0.5516(2) 0.11462(10) 0.0204(4) Uani 1 1 d . . . H3A H 0.4000 0.5357 0.1002 0.025 Uiso 1 1 calc R . . H3B H 0.3080 0.6619 0.1403 0.025 Uiso 1 1 calc R . . C4 C 0.27233(18) 0.3996(2) 0.15730(9) 0.0195(4) Uani 1 1 d . . . H4A H 0.3441 0.3602 0.1899 0.023 Uiso 1 1 calc R . . H4B H 0.1967 0.4281 0.1828 0.023 Uiso 1 1 calc R . . C5 C 0.27271(17) 0.2976(2) -0.02214(9) 0.0154(3) Uani 1 1 d . . . C6 C 0.22414(18) 0.3358(2) -0.08904(10) 0.0202(4) Uani 1 1 d . . . H6 H 0.1429 0.3915 -0.0969 0.024 Uiso 1 1 calc R . . C7 C 0.29419(19) 0.2928(3) -0.14433(10) 0.0235(4) Uani 1 1 d . . . H7 H 0.2609 0.3203 -0.1897 0.028 Uiso 1 1 calc R . . C8 C 0.41210(19) 0.2102(2) -0.13356(10) 0.0223(4) Uani 1 1 d . . . H8 H 0.4590 0.1791 -0.1714 0.027 Uiso 1 1 calc R . . C9 C 0.46134(19) 0.1730(2) -0.06723(10) 0.0212(4) Uani 1 1 d . . . H9 H 0.5426 0.1172 -0.0596 0.025 Uiso 1 1 calc R . . C10 C 0.39210(18) 0.2172(2) -0.01161(9) 0.0179(4) Uani 1 1 d . . . H10 H 0.4268 0.1923 0.0338 0.021 Uiso 1 1 calc R . . C11 C 0.01730(17) 0.1267(2) 0.14377(9) 0.0155(4) Uani 1 1 d . . . C12 C -0.00928(18) 0.1815(2) 0.20914(9) 0.0200(4) Uani 1 1 d . . . H12 H 0.0581 0.1917 0.2447 0.024 Uiso 1 1 calc R . . C13 C -0.13517(18) 0.2210(3) 0.22154(10) 0.0225(4) Uani 1 1 d . . . H13 H -0.1535 0.2591 0.2660 0.027 Uiso 1 1 calc R . . C14 C -0.23541(18) 0.2061(2) 0.17022(10) 0.0198(4) Uani 1 1 d . . . C15 C -0.20674(18) 0.1485(2) 0.10554(10) 0.0206(4) Uani 1 1 d . . . H15 H -0.2742 0.1358 0.0702 0.025 Uiso 1 1 calc R . . C16 C -0.08133(18) 0.1095(2) 0.09204(9) 0.0186(4) Uani 1 1 d . . . H16 H -0.0630 0.0713 0.0477 0.022 Uiso 1 1 calc R . . C17 C -0.37188(19) 0.2500(3) 0.18467(11) 0.0274(4) Uani 1 1 d . . . H17A H -0.4159 0.1447 0.1983 0.041 Uiso 1 1 calc R . . H17B H -0.4177 0.2984 0.1432 0.041 Uiso 1 1 calc R . . H17C H -0.3707 0.3355 0.2218 0.041 Uiso 1 1 calc R . . N1 N 0.24004(14) 0.26874(18) 0.10294(7) 0.0149(3) Uani 1 1 d . . . O1 O 0.09156(12) 0.61448(16) 0.07111(7) 0.0232(3) Uani 1 1 d . . . H1A H 0.0963 0.7227 0.0757 0.035 Uiso 1 1 calc R . . O2 O 0.17359(13) -0.02558(16) 0.06646(6) 0.0196(3) Uani 1 1 d . . . O3 O 0.24969(13) 0.03467(16) 0.18752(7) 0.0209(3) Uani 1 1 d . . . S1 S 0.17755(4) 0.08717(5) 0.12549(2) 0.01476(12) 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 C1 0.0151(8) 0.0136(8) 0.0167(8) 0.0030(6) 0.0003(7) -0.0003(7) C2 0.0186(9) 0.0130(8) 0.0223(9) 0.0014(7) 0.0036(7) 0.0000(7) C3 0.0195(9) 0.0142(9) 0.0276(10) -0.0024(7) 0.0024(8) -0.0037(7) C4 0.0219(9) 0.0170(9) 0.0191(9) -0.0034(7) -0.0019(7) -0.0019(7) C5 0.0178(9) 0.0121(8) 0.0163(8) 0.0006(6) 0.0017(7) -0.0046(6) C6 0.0174(9) 0.0222(9) 0.0208(9) 0.0017(7) 0.0004(7) -0.0021(7) C7 0.0257(10) 0.0287(10) 0.0158(9) 0.0014(7) 0.0006(7) -0.0088(8) C8 0.0255(10) 0.0209(9) 0.0220(10) -0.0044(7) 0.0103(8) -0.0076(8) C9 0.0200(9) 0.0158(9) 0.0286(10) 0.0014(7) 0.0074(8) -0.0010(7) C10 0.0206(9) 0.0152(8) 0.0178(9) 0.0024(7) 0.0015(7) -0.0008(7) C11 0.0179(9) 0.0121(8) 0.0172(9) 0.0016(6) 0.0046(7) -0.0015(6) C12 0.0212(10) 0.0225(9) 0.0162(9) -0.0022(7) 0.0005(7) -0.0014(7) C13 0.0249(10) 0.0233(9) 0.0200(9) -0.0056(7) 0.0068(8) -0.0009(8) C14 0.0208(9) 0.0142(8) 0.0250(10) -0.0007(7) 0.0052(8) -0.0032(7) C15 0.0209(9) 0.0209(9) 0.0195(9) 0.0012(7) -0.0006(7) -0.0054(7) C16 0.0243(9) 0.0168(9) 0.0148(8) -0.0009(7) 0.0035(7) -0.0050(7) C17 0.0205(10) 0.0264(10) 0.0357(12) -0.0061(9) 0.0050(8) -0.0003(8) N1 0.0185(7) 0.0125(7) 0.0134(7) 0.0002(5) 0.0008(6) -0.0018(6) O1 0.0210(7) 0.0147(6) 0.0341(8) -0.0030(6) 0.0030(6) 0.0037(5) O2 0.0258(7) 0.0134(6) 0.0203(7) -0.0021(5) 0.0069(5) -0.0010(5) O3 0.0236(7) 0.0193(6) 0.0200(7) 0.0051(5) 0.0026(5) 0.0025(5) S1 0.0193(2) 0.0111(2) 0.0142(2) 0.00106(16) 0.00330(16) 0.00002(16) _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 C1 N1 1.491(2) . ? C1 C5 1.521(2) . ? C1 C2 1.546(2) . ? C1 H1 1.0000 . ? C2 O1 1.426(2) . ? C2 C3 1.521(3) . ? C2 H2 1.0000 . ? C3 C4 1.514(3) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 N1 1.484(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C10 1.389(3) . ? C5 C6 1.395(3) . ? C6 C7 1.392(3) . ? C6 H6 0.9500 . ? C7 C8 1.384(3) . ? C7 H7 0.9500 . ? C8 C9 1.385(3) . ? C8 H8 0.9500 . ? C9 C10 1.394(3) . ? C9 H9 0.9500 . ? C10 H10 0.9500 . ? C11 C16 1.388(3) . ? C11 C12 1.395(2) . ? C11 S1 1.7606(18) . ? C12 C13 1.386(3) . ? C12 H12 0.9500 . ? C13 C14 1.393(3) . ? C13 H13 0.9500 . ? C14 C15 1.395(3) . ? C14 C17 1.509(3) . ? C15 C16 1.386(3) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? N1 S1 1.6197(15) . ? O1 H1A 0.8400 . ? O2 S1 1.4426(13) . ? O3 S1 1.4321(14) . ? 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 C1 C5 112.54(14) . . ? N1 C1 C2 102.90(14) . . ? C5 C1 C2 111.93(14) . . ? N1 C1 H1 109.8 . . ? C5 C1 H1 109.8 . . ? C2 C1 H1 109.8 . . ? O1 C2 C3 110.98(15) . . ? O1 C2 C1 107.86(14) . . ? C3 C2 C1 103.80(14) . . ? O1 C2 H2 111.3 . . ? C3 C2 H2 111.3 . . ? C1 C2 H2 111.3 . . ? C4 C3 C2 103.07(14) . . ? C4 C3 H3A 111.2 . . ? C2 C3 H3A 111.2 . . ? C4 C3 H3B 111.2 . . ? C2 C3 H3B 111.2 . . ? H3A C3 H3B 109.1 . . ? N1 C4 C3 100.82(14) . . ? N1 C4 H4A 111.6 . . ? C3 C4 H4A 111.6 . . ? N1 C4 H4B 111.6 . . ? C3 C4 H4B 111.6 . . ? H4A C4 H4B 109.4 . . ? C10 C5 C6 119.05(17) . . ? C10 C5 C1 122.55(16) . . ? C6 C5 C1 118.33(16) . . ? C7 C6 C5 120.30(18) . . ? C7 C6 H6 119.9 . . ? C5 C6 H6 119.9 . . ? C8 C7 C6 120.36(18) . . ? C8 C7 H7 119.8 . . ? C6 C7 H7 119.8 . . ? C7 C8 C9 119.64(17) . . ? C7 C8 H8 120.2 . . ? C9 C8 H8 120.2 . . ? C8 C9 C10 120.24(18) . . ? C8 C9 H9 119.9 . . ? C10 C9 H9 119.9 . . ? C5 C10 C9 120.40(17) . . ? C5 C10 H10 119.8 . . ? C9 C10 H10 119.8 . . ? C16 C11 C12 120.43(17) . . ? C16 C11 S1 119.55(14) . . ? C12 C11 S1 119.97(14) . . ? C13 C12 C11 119.16(17) . . ? C13 C12 H12 120.4 . . ? C11 C12 H12 120.4 . . ? C12 C13 C14 121.34(17) . . ? C12 C13 H13 119.3 . . ? C14 C13 H13 119.3 . . ? C13 C14 C15 118.45(17) . . ? C13 C14 C17 120.58(17) . . ? C15 C14 C17 120.97(18) . . ? C16 C15 C14 121.03(17) . . ? C16 C15 H15 119.5 . . ? C14 C15 H15 119.5 . . ? C15 C16 C11 119.58(17) . . ? C15 C16 H16 120.2 . . ? C11 C16 H16 120.2 . . ? C14 C17 H17A 109.5 . . ? C14 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C14 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C4 N1 C1 111.12(13) . . ? C4 N1 S1 117.76(12) . . ? C1 N1 S1 120.68(11) . . ? C2 O1 H1A 109.5 . . ? O3 S1 O2 119.08(8) . . ? O3 S1 N1 106.25(8) . . ? O2 S1 N1 106.82(8) . . ? O3 S1 C11 108.55(8) . . ? O2 S1 C11 107.46(8) . . ? N1 S1 C11 108.29(8) . . ? 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 C1 C2 O1 -95.88(16) . . . . ? C5 C1 C2 O1 143.05(15) . . . . ? N1 C1 C2 C3 21.94(17) . . . . ? C5 C1 C2 C3 -99.14(17) . . . . ? O1 C2 C3 C4 75.64(17) . . . . ? C1 C2 C3 C4 -39.99(18) . . . . ? C2 C3 C4 N1 41.38(17) . . . . ? N1 C1 C5 C10 -16.9(2) . . . . ? C2 C1 C5 C10 98.41(19) . . . . ? N1 C1 C5 C6 166.04(15) . . . . ? C2 C1 C5 C6 -78.6(2) . . . . ? C10 C5 C6 C7 0.4(3) . . . . ? C1 C5 C6 C7 177.60(16) . . . . ? C5 C6 C7 C8 0.6(3) . . . . ? C6 C7 C8 C9 -1.1(3) . . . . ? C7 C8 C9 C10 0.5(3) . . . . ? C6 C5 C10 C9 -1.0(3) . . . . ? C1 C5 C10 C9 -178.06(16) . . . . ? C8 C9 C10 C5 0.5(3) . . . . ? C16 C11 C12 C13 -0.9(3) . . . . ? S1 C11 C12 C13 176.53(14) . . . . ? C11 C12 C13 C14 0.4(3) . . . . ? C12 C13 C14 C15 0.6(3) . . . . ? C12 C13 C14 C17 -179.88(18) . . . . ? C13 C14 C15 C16 -1.0(3) . . . . ? C17 C14 C15 C16 179.45(17) . . . . ? C14 C15 C16 C11 0.5(3) . . . . ? C12 C11 C16 C15 0.5(3) . . . . ? S1 C11 C16 C15 -176.96(13) . . . . ? C3 C4 N1 C1 -28.55(18) . . . . ? C3 C4 N1 S1 -173.77(12) . . . . ? C5 C1 N1 C4 124.90(16) . . . . ? C2 C1 N1 C4 4.24(18) . . . . ? C5 C1 N1 S1 -91.04(16) . . . . ? C2 C1 N1 S1 148.31(12) . . . . ? C4 N1 S1 O3 -43.41(15) . . . . ? C1 N1 S1 O3 174.81(12) . . . . ? C4 N1 S1 O2 -171.50(13) . . . . ? C1 N1 S1 O2 46.72(15) . . . . ? C4 N1 S1 C11 73.03(15) . . . . ? C1 N1 S1 C11 -68.75(14) . . . . ? C16 C11 S1 O3 -153.72(14) . . . . ? C12 C11 S1 O3 28.84(17) . . . . ? C16 C11 S1 O2 -23.71(16) . . . . ? C12 C11 S1 O2 158.85(14) . . . . ? C16 C11 S1 N1 91.33(15) . . . . ? C12 C11 S1 N1 -86.11(15) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H1A O2 0.84 2.11 2.9070(19) 157.3 1_565 _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.417 _refine_diff_density_min -0.360 _refine_diff_density_rms 0.061 #===END data_ck91ba _database_code_depnum_ccdc_archive 'CCDC 298301' _audit_creation_method SHELXL-97 _chemical_formula_moiety 'C18 H21 N O3 S' _chemical_formula_sum 'C18 H21 N O3 S' _chemical_formula_weight 331.42 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' 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'P 21/n' _symmetry_space_group_name_Hall '-P 2yn' 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 9.4610(19) _cell_length_b 18.630(4) _cell_length_c 10.033(2) _cell_angle_alpha 90.00 _cell_angle_beta 112.92(3) _cell_angle_gamma 90.00 _cell_volume 1628.8(7) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 4307 _cell_measurement_theta_min 2.46 _cell_measurement_theta_max 27.44 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.15 _exptl_crystal_density_diffrn 1.352 _exptl_crystal_density_method none _exptl_crystal_F_000 704 _exptl_absorpt_coefficient_mu 0.213 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.866 _exptl_absorpt_correction_T_max 0.970 _exptl_absorpt_process_details 'SADABS v2.10 (Sheldrick, 2003)' _diffrn_ambient_temperature 100(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 'Frames, each covering 0.3 \% in \w' _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_decay_% 0 _diffrn_reflns_number 18207 _diffrn_reflns_av_R_equivalents 0.0334 _diffrn_reflns_av_sigmaI/netI 0.0273 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.19 _diffrn_reflns_theta_max 27.49 _reflns_number_total 3722 _reflns_number_gt 3386 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART v5.628 (Bruker-AXS, 2003)' _computing_cell_refinement 'SAINT v6.28A (Bruker-AXS, 2000)' _computing_data_reduction ; SAINT v6.28A and SHELXTL v6.1 (Bruker-AXS, 2000) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL v6.1 (Bruker-AXS, 2000)' _computing_publication_material 'SHELXTL v6.1 (Bruker-AXS, 2000)' _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^)+(0.0422P)^2^+0.9785P] 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_number_reflns 3722 _refine_ls_number_parameters 210 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0500 _refine_ls_R_factor_gt 0.0443 _refine_ls_wR_factor_ref 0.1040 _refine_ls_wR_factor_gt 0.1012 _refine_ls_goodness_of_fit_ref 1.134 _refine_ls_restrained_S_all 1.134 _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 C1 C 0.18437(18) -0.02394(8) 0.23274(17) 0.0156(3) Uani 1 1 d . . . H1A H 0.0816 -0.0035 0.2178 0.019 Uiso 1 1 calc R . . C2 C 0.2065(2) -0.02154(10) 0.08874(18) 0.0222(4) Uani 1 1 d . . . H2A H 0.1943 -0.0700 0.0450 0.027 Uiso 1 1 calc R . . H2B H 0.1312 0.0113 0.0193 0.027 Uiso 1 1 calc R . . C3 C 0.3704(2) 0.00615(11) 0.1288(2) 0.0260(4) Uani 1 1 d . . . H3A H 0.4464 -0.0330 0.1669 0.031 Uiso 1 1 calc R . . H3B H 0.3829 0.0283 0.0444 0.031 Uiso 1 1 calc R . . C4 C 0.3870(2) 0.06152(10) 0.24492(19) 0.0229(4) Uani 1 1 d . . . H4A H 0.4962 0.0708 0.3061 0.028 Uiso 1 1 calc R . . H4B H 0.3363 0.1073 0.2022 0.028 Uiso 1 1 calc R . . C5 C 0.19818(19) -0.09951(8) 0.29876(18) 0.0180(3) Uani 1 1 d . . . H5 H 0.2189 -0.0948 0.4040 0.022 Uiso 1 1 calc R . . C6 C 0.04863(19) -0.13991(8) 0.22480(17) 0.0176(3) Uani 1 1 d . . . C7 C -0.0838(2) -0.11756(9) 0.24313(19) 0.0221(4) Uani 1 1 d . . . H7 H -0.0784 -0.0777 0.3039 0.026 Uiso 1 1 calc R . . C8 C -0.2224(2) -0.15244(9) 0.1745(2) 0.0246(4) Uani 1 1 d . . . H8 H -0.3111 -0.1364 0.1881 0.030 Uiso 1 1 calc R . . C9 C -0.2319(2) -0.21111(9) 0.08541(19) 0.0231(4) Uani 1 1 d . . . H9 H -0.3269 -0.2351 0.0377 0.028 Uiso 1 1 calc R . . C10 C -0.1017(2) -0.23401(9) 0.0672(2) 0.0241(4) Uani 1 1 d . . . H10 H -0.1073 -0.2742 0.0069 0.029 Uiso 1 1 calc R . . C11 C 0.03779(19) -0.19871(9) 0.13636(19) 0.0212(4) Uani 1 1 d . . . H11 H 0.1264 -0.2151 0.1229 0.025 Uiso 1 1 calc R . . C12 C 0.09072(18) 0.11575(8) 0.35311(17) 0.0146(3) Uani 1 1 d . . . C13 C 0.08296(19) 0.17859(8) 0.27476(18) 0.0182(3) Uani 1 1 d . . . H13 H 0.1741 0.2014 0.2779 0.022 Uiso 1 1 calc R . . C14 C -0.0595(2) 0.20724(9) 0.19239(18) 0.0195(3) Uani 1 1 d . . . H14 H -0.0651 0.2509 0.1415 0.023 Uiso 1 1 calc R . . C15 C -0.19483(19) 0.17366(9) 0.18227(18) 0.0186(3) Uani 1 1 d . . . C16 C -0.18439(19) 0.11204(9) 0.26418(18) 0.0190(3) Uani 1 1 d . . . H16 H -0.2755 0.0894 0.2612 0.023 Uiso 1 1 calc R . . C17 C -0.04318(18) 0.08331(8) 0.34980(18) 0.0167(3) Uani 1 1 d . . . H17 H -0.0376 0.0416 0.4061 0.020 Uiso 1 1 calc R . . C18 C -0.3495(2) 0.20174(10) 0.0830(2) 0.0270(4) Uani 1 1 d . . . H18A H -0.3783 0.1801 -0.0130 0.041 Uiso 1 1 calc R . . H18B H -0.3445 0.2540 0.0752 0.041 Uiso 1 1 calc R . . H18C H -0.4263 0.1893 0.1224 0.041 Uiso 1 1 calc R . . N1 N 0.30719(15) 0.02550(7) 0.32839(14) 0.0155(3) Uani 1 1 d . . . O1 O 0.31962(14) -0.13904(6) 0.28396(14) 0.0241(3) Uani 1 1 d . . . H1 H 0.4038 -0.1255 0.3470 0.036 Uiso 1 1 calc R . . O2 O 0.24613(13) 0.02336(6) 0.54667(12) 0.0180(2) Uani 1 1 d . . . O3 O 0.38638(13) 0.12644(6) 0.49996(13) 0.0207(3) Uani 1 1 d . . . S1 S 0.26800(4) 0.07262(2) 0.44655(4) 0.01399(11) 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 C1 0.0127(7) 0.0182(8) 0.0138(7) -0.0013(6) 0.0030(6) 0.0013(6) C2 0.0229(9) 0.0287(9) 0.0148(8) 0.0012(7) 0.0071(7) 0.0039(7) C3 0.0228(9) 0.0371(10) 0.0225(9) 0.0038(7) 0.0137(7) 0.0046(7) C4 0.0187(8) 0.0291(9) 0.0254(9) 0.0035(7) 0.0135(7) -0.0021(7) C5 0.0180(8) 0.0172(8) 0.0156(8) -0.0006(6) 0.0030(6) 0.0017(6) C6 0.0205(8) 0.0159(7) 0.0152(8) 0.0022(6) 0.0056(6) 0.0013(6) C7 0.0281(9) 0.0172(8) 0.0251(9) -0.0025(6) 0.0150(7) -0.0006(7) C8 0.0232(9) 0.0224(8) 0.0338(10) 0.0022(7) 0.0172(8) 0.0018(7) C9 0.0192(8) 0.0223(8) 0.0257(9) 0.0028(7) 0.0064(7) -0.0016(6) C10 0.0234(9) 0.0223(9) 0.0244(9) -0.0061(7) 0.0068(7) -0.0009(7) C11 0.0174(8) 0.0217(8) 0.0229(9) -0.0034(7) 0.0060(7) 0.0033(6) C12 0.0133(7) 0.0150(7) 0.0142(7) -0.0013(6) 0.0039(6) 0.0016(6) C13 0.0176(8) 0.0154(7) 0.0212(8) -0.0007(6) 0.0073(7) -0.0025(6) C14 0.0245(9) 0.0145(7) 0.0190(8) 0.0024(6) 0.0078(7) 0.0016(6) C15 0.0177(8) 0.0199(8) 0.0167(8) -0.0012(6) 0.0049(7) 0.0042(6) C16 0.0143(8) 0.0214(8) 0.0221(8) -0.0007(6) 0.0080(7) -0.0003(6) C17 0.0174(8) 0.0151(7) 0.0190(8) 0.0005(6) 0.0085(6) 0.0005(6) C18 0.0198(9) 0.0294(9) 0.0274(10) 0.0048(7) 0.0043(7) 0.0062(7) N1 0.0131(6) 0.0181(7) 0.0170(7) -0.0001(5) 0.0078(5) -0.0007(5) O1 0.0146(6) 0.0204(6) 0.0293(7) -0.0045(5) -0.0001(5) 0.0040(5) O2 0.0181(6) 0.0196(6) 0.0163(6) 0.0022(4) 0.0068(5) 0.0024(4) O3 0.0145(6) 0.0190(6) 0.0237(6) -0.0012(5) 0.0023(5) -0.0026(4) S1 0.01162(19) 0.01437(19) 0.0147(2) -0.00013(14) 0.00370(14) -0.00032(13) _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 C1 N1 1.500(2) . ? C1 C2 1.539(2) . ? C1 C5 1.540(2) . ? C1 H1A 1.0000 . ? C2 C3 1.532(3) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? C3 C4 1.518(3) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 N1 1.488(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 O1 1.420(2) . ? C5 C6 1.517(2) . ? C5 H5 1.0000 . ? C6 C11 1.388(2) . ? C6 C7 1.398(2) . ? C7 C8 1.383(3) . ? C7 H7 0.9500 . ? C8 C9 1.392(3) . ? C8 H8 0.9500 . ? C9 C10 1.382(2) . ? C9 H9 0.9500 . ? C10 C11 1.394(2) . ? C10 H10 0.9500 . ? C11 H11 0.9500 . ? C12 C17 1.392(2) . ? C12 C13 1.396(2) . ? C12 S1 1.7644(16) . ? C13 C14 1.385(2) . ? C13 H13 0.9500 . ? C14 C15 1.392(2) . ? C14 H14 0.9500 . ? C15 C16 1.393(2) . ? C15 C18 1.507(2) . ? C16 C17 1.384(2) . ? C16 H16 0.9500 . ? C17 H17 0.9500 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? C18 H18C 0.9800 . ? N1 S1 1.6298(14) . ? O1 H1 0.8400 . ? O2 S1 1.4338(12) . ? O3 S1 1.4419(12) . ? 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 C1 C2 103.18(13) . . ? N1 C1 C5 111.80(12) . . ? C2 C1 C5 114.24(13) . . ? N1 C1 H1A 109.1 . . ? C2 C1 H1A 109.1 . . ? C5 C1 H1A 109.1 . . ? C3 C2 C1 104.91(14) . . ? C3 C2 H2A 110.8 . . ? C1 C2 H2A 110.8 . . ? C3 C2 H2B 110.8 . . ? C1 C2 H2B 110.8 . . ? H2A C2 H2B 108.8 . . ? C4 C3 C2 102.80(14) . . ? C4 C3 H3A 111.2 . . ? C2 C3 H3A 111.2 . . ? C4 C3 H3B 111.2 . . ? C2 C3 H3B 111.2 . . ? H3A C3 H3B 109.1 . . ? N1 C4 C3 101.66(14) . . ? N1 C4 H4A 111.4 . . ? C3 C4 H4A 111.4 . . ? N1 C4 H4B 111.4 . . ? C3 C4 H4B 111.4 . . ? H4A C4 H4B 109.3 . . ? O1 C5 C6 109.26(13) . . ? O1 C5 C1 111.45(13) . . ? C6 C5 C1 109.67(13) . . ? O1 C5 H5 108.8 . . ? C6 C5 H5 108.8 . . ? C1 C5 H5 108.8 . . ? C11 C6 C7 118.17(15) . . ? C11 C6 C5 121.79(15) . . ? C7 C6 C5 120.03(15) . . ? C8 C7 C6 121.25(16) . . ? C8 C7 H7 119.4 . . ? C6 C7 H7 119.4 . . ? C7 C8 C9 120.01(16) . . ? C7 C8 H8 120.0 . . ? C9 C8 H8 120.0 . . ? C10 C9 C8 119.30(16) . . ? C10 C9 H9 120.3 . . ? C8 C9 H9 120.3 . . ? C9 C10 C11 120.56(16) . . ? C9 C10 H10 119.7 . . ? C11 C10 H10 119.7 . . ? C6 C11 C10 120.71(16) . . ? C6 C11 H11 119.6 . . ? C10 C11 H11 119.6 . . ? C17 C12 C13 120.19(14) . . ? C17 C12 S1 118.87(12) . . ? C13 C12 S1 120.78(12) . . ? C14 C13 C12 118.99(15) . . ? C14 C13 H13 120.5 . . ? C12 C13 H13 120.5 . . ? C13 C14 C15 121.60(15) . . ? C13 C14 H14 119.2 . . ? C15 C14 H14 119.2 . . ? C14 C15 C16 118.38(15) . . ? C14 C15 C18 121.38(15) . . ? C16 C15 C18 120.22(15) . . ? C17 C16 C15 120.96(15) . . ? C17 C16 H16 119.5 . . ? C15 C16 H16 119.5 . . ? C16 C17 C12 119.76(15) . . ? C16 C17 H17 120.1 . . ? C12 C17 H17 120.1 . . ? C15 C18 H18A 109.5 . . ? C15 C18 H18B 109.5 . . ? H18A C18 H18B 109.5 . . ? C15 C18 H18C 109.5 . . ? H18A C18 H18C 109.5 . . ? H18B C18 H18C 109.5 . . ? C4 N1 C1 110.68(13) . . ? C4 N1 S1 118.39(11) . . ? C1 N1 S1 117.20(10) . . ? C5 O1 H1 109.5 . . ? O2 S1 O3 119.20(7) . . ? O2 S1 N1 107.49(7) . . ? O3 S1 N1 106.32(7) . . ? O2 S1 C12 107.28(7) . . ? O3 S1 C12 108.72(7) . . ? N1 S1 C12 107.30(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 C1 C2 C3 19.68(16) . . . . ? C5 C1 C2 C3 -101.90(16) . . . . ? C1 C2 C3 C4 -37.59(17) . . . . ? C2 C3 C4 N1 39.91(16) . . . . ? N1 C1 C5 O1 -76.13(16) . . . . ? C2 C1 C5 O1 40.57(18) . . . . ? N1 C1 C5 C6 162.75(13) . . . . ? C2 C1 C5 C6 -80.55(17) . . . . ? O1 C5 C6 C11 -10.7(2) . . . . ? C1 C5 C6 C11 111.74(17) . . . . ? O1 C5 C6 C7 170.25(15) . . . . ? C1 C5 C6 C7 -67.31(19) . . . . ? C11 C6 C7 C8 -0.5(3) . . . . ? C5 C6 C7 C8 178.58(16) . . . . ? C6 C7 C8 C9 0.2(3) . . . . ? C7 C8 C9 C10 0.3(3) . . . . ? C8 C9 C10 C11 -0.3(3) . . . . ? C7 C6 C11 C10 0.4(3) . . . . ? C5 C6 C11 C10 -178.63(16) . . . . ? C9 C10 C11 C6 0.0(3) . . . . ? C17 C12 C13 C14 -1.0(2) . . . . ? S1 C12 C13 C14 174.25(12) . . . . ? C12 C13 C14 C15 -2.1(2) . . . . ? C13 C14 C15 C16 3.7(2) . . . . ? C13 C14 C15 C18 -174.95(16) . . . . ? C14 C15 C16 C17 -2.2(2) . . . . ? C18 C15 C16 C17 176.45(16) . . . . ? C15 C16 C17 C12 -0.8(2) . . . . ? C13 C12 C17 C16 2.5(2) . . . . ? S1 C12 C17 C16 -172.90(12) . . . . ? C3 C4 N1 C1 -28.88(17) . . . . ? C3 C4 N1 S1 -168.29(11) . . . . ? C2 C1 N1 C4 5.79(16) . . . . ? C5 C1 N1 C4 129.01(14) . . . . ? C2 C1 N1 S1 145.73(11) . . . . ? C5 C1 N1 S1 -91.05(14) . . . . ? C4 N1 S1 O2 -159.00(12) . . . . ? C1 N1 S1 O2 64.19(12) . . . . ? C4 N1 S1 O3 -30.30(14) . . . . ? C1 N1 S1 O3 -167.11(11) . . . . ? C4 N1 S1 C12 85.89(13) . . . . ? C1 N1 S1 C12 -50.91(13) . . . . ? C17 C12 S1 O2 -20.59(15) . . . . ? C13 C12 S1 O2 164.08(13) . . . . ? C17 C12 S1 O3 -150.74(13) . . . . ? C13 C12 S1 O3 33.93(15) . . . . ? C17 C12 S1 N1 94.66(14) . . . . ? C13 C12 S1 N1 -80.67(14) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H1 O3 0.84 1.98 2.792(2) 161.9 3_656 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.525 _refine_diff_density_min -0.344 _refine_diff_density_rms 0.058