# Supplementary Material (ESI) 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 'Masami Sakamoto' _publ_contact_author_address ; Applied Chemistry and Biotechnology Chiba University Yayoi-cho Inage-ku Chiba 263-8522 JAPAN ; _publ_contact_author_email SAKAMOTOM@FACULTY.CHIBA-U.JP _publ_section_title ; Photochemical asymmetric synthesis of quartenary chiral carbons using chiral-memory effect on beta-hydrogen abstraction by thiocarbonyl group ; loop_ _publ_author_name 'Masami Sakamoto' 'Tsutomu Fujita' 'Yoshio Kasashima' 'Hiroya Kawanishi' 'Takashi Mino' # Attachment 'sakamoto_1a.cif.CIF' data_272_11 _database_code_depnum_ccdc_archive 'CCDC 611153' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H19 N O S' _chemical_formula_weight 345.44 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 P2(1)2(1)2(1) 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 6.126(3) _cell_length_b 9.050(4) _cell_length_c 32.991(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1829.0(13) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 3 _cell_measurement_theta_max 140 _exptl_crystal_description needle _exptl_crystal_colour yellow _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.255 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 1.627 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.5998 _exptl_absorpt_correction_T_max 0.8543 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'multiwire proportional' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2052 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0266 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 40 _diffrn_reflns_theta_min 2.68 _diffrn_reflns_theta_max 70.10 _reflns_number_total 2052 _reflns_number_gt 1732 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker FRAMBO' _computing_cell_refinement 'Bruker FRAMBO' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.1561P)^2^+0.6781P] 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 -0.02(4) _refine_ls_number_reflns 2052 _refine_ls_number_parameters 227 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0544 _refine_ls_R_factor_gt 0.0440 _refine_ls_wR_factor_ref 0.1392 _refine_ls_wR_factor_gt 0.1187 _refine_ls_goodness_of_fit_ref 0.670 _refine_ls_restrained_S_all 0.670 _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 -0.19482(15) 0.29065(11) 0.13783(3) 0.0585(3) Uani 1 1 d . . . O1 O 0.4736(4) 0.5348(3) 0.08835(7) 0.0542(6) Uani 1 1 d . . . N1 N 0.1421(4) 0.4372(3) 0.10561(7) 0.0404(6) Uani 1 1 d . . . C2 C 0.0911(5) 0.4635(4) 0.17833(8) 0.0429(7) Uani 1 1 d . . . C8 C 0.3023(5) 0.5508(3) 0.10592(7) 0.0386(6) Uani 1 1 d . . . C17 C 0.1249(5) 0.4403(3) 0.03029(8) 0.0414(7) Uani 1 1 d . . . C7 C 0.2982(6) 0.4280(5) 0.19266(9) 0.0547(9) Uani 1 1 d . . . H7 H 0.3911 0.3689 0.1774 0.066 Uiso 1 1 calc R . . C9 C 0.2441(5) 0.6937(3) 0.12536(7) 0.0384(7) Uani 1 1 d . . . C10 C 0.0372(6) 0.7562(3) 0.12074(9) 0.0465(7) Uani 1 1 d . . . H10 H -0.0715 0.7055 0.1068 0.056 Uiso 1 1 calc R . . C18 C -0.0524(6) 0.5311(4) 0.02281(9) 0.0497(8) Uani 1 1 d . . . H18 H -0.1669 0.5349 0.0413 0.060 Uiso 1 1 calc R . . C1 C 0.0166(5) 0.4031(3) 0.13874(9) 0.0398(6) Uani 1 1 d . . . C19 C -0.0608(7) 0.6166(4) -0.01206(10) 0.0568(9) Uani 1 1 d . . . H19 H -0.1795 0.6785 -0.0166 0.068 Uiso 1 1 calc R . . C15 C 0.1256(6) 0.3437(3) 0.06787(8) 0.0459(7) Uani 1 1 d . . . H15 H -0.0171 0.2948 0.0689 0.055 Uiso 1 1 calc R . . C14 C 0.4038(6) 0.7704(4) 0.14646(9) 0.0533(8) Uani 1 1 d . . . H14 H 0.5429 0.7305 0.1492 0.064 Uiso 1 1 calc R . . C3 C -0.0449(7) 0.5511(4) 0.20179(9) 0.0582(10) Uani 1 1 d . . . H3 H -0.1858 0.5714 0.1929 0.070 Uiso 1 1 calc R . . C16 C 0.2953(8) 0.2225(4) 0.06918(10) 0.0636(10) Uani 1 1 d . . . H16A H 0.4385 0.2656 0.0698 0.095 Uiso 1 1 calc R . . H16B H 0.2813 0.1613 0.0455 0.095 Uiso 1 1 calc R . . H16C H 0.2740 0.1635 0.0930 0.095 Uiso 1 1 calc R . . C20 C 0.1052(7) 0.6102(4) -0.03991(10) 0.0589(9) Uani 1 1 d . . . H20 H 0.0984 0.6670 -0.0634 0.071 Uiso 1 1 calc R . . C21 C 0.2806(7) 0.5201(4) -0.03311(10) 0.0614(10) Uani 1 1 d . . . H21 H 0.3930 0.5156 -0.0520 0.074 Uiso 1 1 calc R . . C22 C 0.2917(7) 0.4354(4) 0.00192(9) 0.0552(9) Uani 1 1 d . . . H22 H 0.4120 0.3748 0.0064 0.066 Uiso 1 1 calc R . . C12 C 0.1524(8) 0.9676(4) 0.15866(10) 0.0635(11) Uani 1 1 d . . . H12 H 0.1209 1.0589 0.1702 0.076 Uiso 1 1 calc R . . C6 C 0.3653(7) 0.4825(6) 0.23050(11) 0.0720(13) Uani 1 1 d . . . H6 H 0.5015 0.4567 0.2407 0.086 Uiso 1 1 calc R . . C13 C 0.3560(8) 0.9063(4) 0.16338(11) 0.0655(11) Uani 1 1 d . . . H13 H 0.4623 0.9566 0.1780 0.079 Uiso 1 1 calc R . . C4 C 0.0273(9) 0.6088(6) 0.23847(10) 0.0795(14) Uani 1 1 d . . . H4 H -0.0624 0.6711 0.2535 0.095 Uiso 1 1 calc R . . C11 C -0.0043(7) 0.8936(4) 0.13696(10) 0.0564(9) Uani 1 1 d . . . H11 H -0.1405 0.9369 0.1331 0.068 Uiso 1 1 calc R . . C5 C 0.2315(9) 0.5733(7) 0.25237(11) 0.0851(15) Uani 1 1 d . . . H5 H 0.2796 0.6114 0.2770 0.102 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 0.0458(4) 0.0656(5) 0.0641(5) 0.0064(4) 0.0143(4) -0.0036(4) O1 0.0471(12) 0.0645(14) 0.0511(12) -0.0037(11) 0.0172(11) 0.0003(13) N1 0.0490(14) 0.0444(13) 0.0276(10) 0.0016(9) 0.0058(10) 0.0019(12) C2 0.0444(16) 0.0531(16) 0.0313(12) 0.0111(12) 0.0077(12) 0.0095(15) C8 0.0431(15) 0.0458(15) 0.0268(11) 0.0047(11) 0.0011(12) 0.0018(15) C17 0.0500(17) 0.0420(15) 0.0324(12) -0.0030(11) 0.0002(12) -0.0001(14) C7 0.0449(17) 0.081(2) 0.0384(14) 0.0114(15) 0.0061(14) 0.016(2) C9 0.0470(16) 0.0418(14) 0.0263(11) 0.0022(10) 0.0042(11) -0.0013(13) C10 0.0514(18) 0.0479(16) 0.0402(15) 0.0044(12) -0.0044(14) 0.0007(16) C18 0.0485(18) 0.0592(18) 0.0413(14) -0.0088(14) -0.0012(14) 0.0040(17) C1 0.0369(14) 0.0442(14) 0.0382(13) 0.0098(12) 0.0083(12) 0.0111(13) C19 0.064(2) 0.0540(19) 0.0520(17) -0.0042(15) -0.0167(17) 0.0086(19) C15 0.0609(19) 0.0435(15) 0.0333(13) -0.0016(12) 0.0060(14) -0.0049(16) C14 0.0503(18) 0.066(2) 0.0440(15) -0.0031(15) -0.0061(14) -0.0033(19) C3 0.059(2) 0.078(2) 0.0378(14) 0.0070(16) 0.0136(15) 0.023(2) C16 0.099(3) 0.0462(17) 0.0452(15) 0.0016(14) 0.009(2) 0.016(2) C20 0.080(3) 0.0562(19) 0.0402(15) 0.0040(14) -0.0068(17) -0.001(2) C21 0.069(2) 0.074(2) 0.0406(15) 0.0067(16) 0.0106(17) 0.002(2) C22 0.058(2) 0.066(2) 0.0413(15) 0.0045(15) 0.0065(16) 0.011(2) C12 0.095(3) 0.0485(18) 0.0465(17) -0.0065(15) 0.008(2) 0.007(2) C6 0.058(2) 0.114(4) 0.0439(17) 0.017(2) -0.0081(17) 0.008(3) C13 0.080(3) 0.066(2) 0.0505(18) -0.0122(17) -0.0125(19) -0.012(2) C4 0.099(3) 0.102(3) 0.0372(17) -0.004(2) 0.015(2) 0.033(3) C11 0.067(2) 0.0487(17) 0.0533(18) 0.0022(16) 0.0028(18) 0.0125(18) C5 0.102(3) 0.120(4) 0.0334(16) -0.002(2) -0.001(2) 0.012(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S1 C1 1.648(3) . ? O1 C8 1.208(4) . ? N1 C1 1.371(4) . ? N1 C8 1.422(4) . ? N1 C15 1.509(3) . ? C2 C7 1.392(5) . ? C2 C3 1.386(5) . ? C2 C1 1.487(4) . ? C8 C9 1.487(4) . ? C17 C22 1.386(5) . ? C17 C18 1.385(5) . ? C17 C15 1.517(4) . ? C7 C6 1.404(5) . ? C7 H7 0.9300 . ? C9 C10 1.396(5) . ? C9 C14 1.387(5) . ? C10 C11 1.378(4) . ? C10 H10 0.9300 . ? C18 C19 1.387(5) . ? C18 H18 0.9300 . ? C19 C20 1.371(5) . ? C19 H19 0.9300 . ? C15 C16 1.513(5) . ? C15 H15 0.9800 . ? C14 C13 1.382(5) . ? C14 H14 0.9300 . ? C3 C4 1.390(6) . ? C3 H3 0.9300 . ? C16 H16A 0.9600 . ? C16 H16B 0.9600 . ? C16 H16C 0.9600 . ? C20 C21 1.367(5) . ? C20 H20 0.9300 . ? C21 C22 1.389(5) . ? C21 H21 0.9300 . ? C22 H22 0.9300 . ? C12 C11 1.372(6) . ? C12 C13 1.374(6) . ? C12 H12 0.9300 . ? C6 C5 1.367(6) . ? C6 H6 0.9300 . ? C13 H13 0.9300 . ? C4 C5 1.371(7) . ? C4 H4 0.9300 . ? C11 H11 0.9300 . ? C5 H5 0.9300 . ? 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 C1 N1 C8 122.9(2) . . ? C1 N1 C15 119.6(3) . . ? C8 N1 C15 117.2(2) . . ? C7 C2 C3 119.4(3) . . ? C7 C2 C1 119.5(3) . . ? C3 C2 C1 121.1(3) . . ? O1 C8 N1 120.7(3) . . ? O1 C8 C9 121.3(3) . . ? N1 C8 C9 117.8(3) . . ? C22 C17 C18 118.5(3) . . ? C22 C17 C15 122.1(3) . . ? C18 C17 C15 119.3(3) . . ? C2 C7 C6 119.2(3) . . ? C2 C7 H7 120.4 . . ? C6 C7 H7 120.4 . . ? C10 C9 C14 119.5(3) . . ? C10 C9 C8 121.5(3) . . ? C14 C9 C8 118.9(3) . . ? C9 C10 C11 119.4(3) . . ? C9 C10 H10 120.3 . . ? C11 C10 H10 120.3 . . ? C19 C18 C17 120.5(3) . . ? C19 C18 H18 119.7 . . ? C17 C18 H18 119.7 . . ? N1 C1 C2 116.5(3) . . ? N1 C1 S1 124.4(2) . . ? C2 C1 S1 119.0(2) . . ? C20 C19 C18 120.3(3) . . ? C20 C19 H19 119.8 . . ? C18 C19 H19 119.8 . . ? C16 C15 N1 109.7(3) . . ? C16 C15 C17 116.3(3) . . ? N1 C15 C17 110.6(2) . . ? C16 C15 H15 106.6 . . ? N1 C15 H15 106.6 . . ? C17 C15 H15 106.6 . . ? C13 C14 C9 119.9(4) . . ? C13 C14 H14 120.0 . . ? C9 C14 H14 120.0 . . ? C4 C3 C2 120.6(4) . . ? C4 C3 H3 119.7 . . ? C2 C3 H3 119.7 . . ? C15 C16 H16A 109.5 . . ? C15 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? C15 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C19 C20 C21 119.8(3) . . ? C19 C20 H20 120.1 . . ? C21 C20 H20 120.1 . . ? C20 C21 C22 120.3(4) . . ? C20 C21 H21 119.8 . . ? C22 C21 H21 119.8 . . ? C17 C22 C21 120.5(4) . . ? C17 C22 H22 119.7 . . ? C21 C22 H22 119.7 . . ? C11 C12 C13 119.8(3) . . ? C11 C12 H12 120.1 . . ? C13 C12 H12 120.1 . . ? C5 C6 C7 120.4(4) . . ? C5 C6 H6 119.8 . . ? C7 C6 H6 119.8 . . ? C14 C13 C12 120.4(4) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C5 C4 C3 119.6(4) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? C12 C11 C10 120.9(4) . . ? C12 C11 H11 119.5 . . ? C10 C11 H11 119.5 . . ? C4 C5 C6 120.8(4) . . ? C4 C5 H5 119.6 . . ? C6 C5 H5 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 C1 N1 C8 O1 141.6(3) . . . . ? C15 N1 C8 O1 -33.4(4) . . . . ? C1 N1 C8 C9 -43.7(4) . . . . ? C15 N1 C8 C9 141.3(3) . . . . ? C3 C2 C7 C6 -0.4(5) . . . . ? C1 C2 C7 C6 -178.5(3) . . . . ? O1 C8 C9 C10 134.8(3) . . . . ? N1 C8 C9 C10 -39.9(3) . . . . ? O1 C8 C9 C14 -41.2(4) . . . . ? N1 C8 C9 C14 144.1(3) . . . . ? C14 C9 C10 C11 0.5(4) . . . . ? C8 C9 C10 C11 -175.5(3) . . . . ? C22 C17 C18 C19 -0.9(5) . . . . ? C15 C17 C18 C19 -177.7(3) . . . . ? C8 N1 C1 C2 -14.9(4) . . . . ? C15 N1 C1 C2 159.9(3) . . . . ? C8 N1 C1 S1 170.3(2) . . . . ? C15 N1 C1 S1 -14.8(4) . . . . ? C7 C2 C1 N1 -58.4(4) . . . . ? C3 C2 C1 N1 123.5(3) . . . . ? C7 C2 C1 S1 116.7(3) . . . . ? C3 C2 C1 S1 -61.4(4) . . . . ? C17 C18 C19 C20 1.1(5) . . . . ? C1 N1 C15 C16 -92.3(3) . . . . ? C8 N1 C15 C16 82.8(3) . . . . ? C1 N1 C15 C17 138.1(3) . . . . ? C8 N1 C15 C17 -46.7(4) . . . . ? C22 C17 C15 C16 -10.7(5) . . . . ? C18 C17 C15 C16 166.0(3) . . . . ? C22 C17 C15 N1 115.3(3) . . . . ? C18 C17 C15 N1 -68.0(4) . . . . ? C10 C9 C14 C13 1.3(5) . . . . ? C8 C9 C14 C13 177.4(3) . . . . ? C7 C2 C3 C4 2.9(6) . . . . ? C1 C2 C3 C4 -179.0(3) . . . . ? C18 C19 C20 C21 -0.6(6) . . . . ? C19 C20 C21 C22 -0.2(6) . . . . ? C18 C17 C22 C21 0.1(5) . . . . ? C15 C17 C22 C21 176.9(3) . . . . ? C20 C21 C22 C17 0.4(6) . . . . ? C2 C7 C6 C5 -2.1(6) . . . . ? C9 C14 C13 C12 -1.5(5) . . . . ? C11 C12 C13 C14 -0.1(6) . . . . ? C2 C3 C4 C5 -2.9(7) . . . . ? C13 C12 C11 C10 1.9(6) . . . . ? C9 C10 C11 C12 -2.1(5) . . . . ? C3 C4 C5 C6 0.4(8) . . . . ? C7 C6 C5 C4 2.2(8) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 70.10 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.178 _refine_diff_density_min -0.290 _refine_diff_density_rms 0.058 # Attachment 'sakamoto_1e.cif.cif' data_saka25c_p21 _database_code_depnum_ccdc_archive 'CCDC 611154' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H21 N O3 S' _chemical_formula_weight 355.44 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 P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 7.7525(8) _cell_length_b 12.0713(13) _cell_length_c 9.9335(10) _cell_angle_alpha 90.00 _cell_angle_beta 97.9140(10) _cell_angle_gamma 90.00 _cell_volume 920.75(17) _cell_formula_units_Z 2 _cell_measurement_temperature 173 _cell_measurement_reflns_used 3023 _cell_measurement_theta_min 2.65 _cell_measurement_theta_max 27.91 _exptl_crystal_description cubic _exptl_crystal_colour orange _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.282 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 376 _exptl_absorpt_coefficient_mu 0.194 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9441 _exptl_absorpt_correction_T_max 0.9623 _exptl_absorpt_process_details ; SADABS Sheldrick 1996 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 173 _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 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5196 _diffrn_reflns_av_R_equivalents 0.0149 _diffrn_reflns_av_sigmaI/netI 0.0272 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 28.40 _reflns_number_total 3462 _reflns_number_gt 3301 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.1000P)^2^+1.0000P] 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 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 0.03(6) _refine_ls_number_reflns 3462 _refine_ls_number_parameters 229 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0306 _refine_ls_R_factor_gt 0.0286 _refine_ls_wR_factor_ref 0.0801 _refine_ls_wR_factor_gt 0.0759 _refine_ls_goodness_of_fit_ref 0.494 _refine_ls_restrained_S_all 0.494 _refine_ls_shift/su_max 0.133 _refine_ls_shift/su_mean 0.021 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 0.8433(2) 0.85426(14) 0.81174(15) 0.0236(3) Uani 1 1 d . . . C2 C 0.99256(19) 0.88089(14) 0.91740(15) 0.0225(3) Uani 1 1 d . . . C3 C 1.0766(2) 0.79878(15) 1.00015(17) 0.0281(3) Uani 1 1 d . . . H3 H 1.0395 0.7239 0.9891 0.034 Uiso 1 1 calc R . . C4 C 1.2146(2) 0.82628(17) 1.09893(18) 0.0325(4) Uani 1 1 d . . . H4 H 1.2698 0.7704 1.1570 0.039 Uiso 1 1 calc R . . C5 C 1.2722(2) 0.93504(18) 1.11322(18) 0.0318(4) Uani 1 1 d . . . H5 H 1.3652 0.9538 1.1821 0.038 Uiso 1 1 calc R . . C6 C 1.1942(2) 1.01632(16) 1.02699(18) 0.0309(4) Uani 1 1 d . . . H6 H 1.2370 1.0901 1.0341 0.037 Uiso 1 1 calc R . . C7 C 1.0532(2) 0.98991(15) 0.93004(17) 0.0259(3) Uani 1 1 d . . . H7 H 0.9981 1.0460 0.8724 0.031 Uiso 1 1 calc R . . C8 C 0.6685(2) 0.99251(15) 0.91533(16) 0.0234(3) Uani 1 1 d . . . C9 C 0.69904(19) 0.94087(15) 1.05301(15) 0.0235(3) Uani 1 1 d . . . C10 C 0.6638(2) 0.82959(15) 1.07301(16) 0.0251(3) Uani 1 1 d . . . H10 H 0.6302 0.7827 0.9971 0.030 Uiso 1 1 calc R . . C11 C 0.6775(2) 0.78662(17) 1.20438(18) 0.0327(4) Uani 1 1 d . . . H11 H 0.6500 0.7112 1.2185 0.039 Uiso 1 1 calc R . . C12 C 0.7316(3) 0.8547(2) 1.31384(18) 0.0392(5) Uani 1 1 d . . . H12 H 0.7431 0.8254 1.4034 0.047 Uiso 1 1 calc R . . C13 C 0.7692(3) 0.9649(2) 1.29442(19) 0.0445(5) Uani 1 1 d . . . H13 H 0.8080 1.0104 1.3706 0.053 Uiso 1 1 calc R . . C14 C 0.7506(2) 1.00998(18) 1.16407(18) 0.0339(4) Uani 1 1 d . . . H14 H 0.7727 1.0864 1.1510 0.041 Uiso 1 1 calc R . . C15 C 0.6011(2) 0.95508(15) 0.66983(15) 0.0248(3) Uani 1 1 d . . . H15 H 0.6366 0.9006 0.6030 0.030 Uiso 1 1 calc R . . C16 C 0.6583(2) 1.06958(16) 0.62510(15) 0.0288(3) Uani 1 1 d . . . C17 C 0.9115(3) 1.1708(2) 0.5904(2) 0.0443(5) Uani 1 1 d . . . H17A H 0.8573 1.1899 0.4984 0.067 Uiso 1 1 calc R . . H17C H 1.0367 1.1591 0.5907 0.067 Uiso 1 1 calc R . . H17B H 0.8935 1.2314 0.6527 0.067 Uiso 1 1 calc R . . C18 C 0.4027(2) 0.94279(18) 0.66545(17) 0.0322(4) Uani 1 1 d . . . H18 H 0.3578 1.0053 0.7169 0.039 Uiso 1 1 calc R . . C19 C 0.3594(2) 0.8334(2) 0.7291(2) 0.0414(5) Uani 1 1 d . . . H19C H 0.2335 0.8205 0.7111 0.062 Uiso 1 1 calc R . . H19A H 0.3962 0.8362 0.8274 0.062 Uiso 1 1 calc R . . H19B H 0.4205 0.7730 0.6897 0.062 Uiso 1 1 calc R . . C20 C 0.3159(3) 0.9470(2) 0.5164(2) 0.0477(5) Uani 1 1 d . . . H20A H 0.3612 0.8866 0.4652 0.072 Uiso 1 1 calc R . . H20B H 0.3416 1.0182 0.4762 0.072 Uiso 1 1 calc R . . H20C H 0.1896 0.9387 0.5128 0.072 Uiso 1 1 calc R . . N1 N 0.70396(16) 0.92782(12) 0.80303(12) 0.0214(3) Uani 1 1 d . . . O1 O 0.60213(17) 1.08314(11) 0.89576(12) 0.0319(3) Uani 1 1 d . . . O2 O 0.56622(19) 1.14463(14) 0.58284(15) 0.0431(3) Uani 1 1 d . . . O3 O 0.83358(16) 1.07069(12) 0.63402(12) 0.0343(3) Uani 1 1 d . . . S1 S 0.85001(5) 0.74861(4) 0.70790(4) 0.03348(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 0.0265(7) 0.0210(8) 0.0247(7) 0.0013(6) 0.0091(6) -0.0011(6) C2 0.0212(6) 0.0235(9) 0.0243(7) -0.0013(6) 0.0082(5) 0.0008(6) C3 0.0254(7) 0.0247(9) 0.0355(8) 0.0054(7) 0.0089(6) 0.0030(7) C4 0.0283(8) 0.0355(10) 0.0344(9) 0.0081(7) 0.0062(6) 0.0073(7) C5 0.0213(7) 0.0405(11) 0.0332(8) -0.0041(8) 0.0020(6) 0.0032(7) C6 0.0285(8) 0.0270(10) 0.0376(9) -0.0044(7) 0.0065(7) -0.0031(7) C7 0.0255(7) 0.0242(9) 0.0283(7) 0.0028(6) 0.0049(6) 0.0013(6) C8 0.0226(6) 0.0221(8) 0.0262(7) -0.0025(6) 0.0055(5) -0.0028(6) C9 0.0223(7) 0.0268(9) 0.0225(7) -0.0017(6) 0.0062(5) 0.0015(6) C10 0.0234(7) 0.0248(8) 0.0276(7) 0.0004(6) 0.0056(6) 0.0006(6) C11 0.0290(8) 0.0344(10) 0.0362(9) 0.0097(7) 0.0108(6) 0.0032(7) C12 0.0430(10) 0.0530(14) 0.0228(8) 0.0050(8) 0.0091(7) 0.0102(9) C13 0.0566(12) 0.0516(15) 0.0251(8) -0.0106(9) 0.0047(8) -0.0003(10) C14 0.0415(9) 0.0315(10) 0.0296(8) -0.0071(7) 0.0076(7) -0.0032(8) C15 0.0246(7) 0.0287(9) 0.0210(7) -0.0011(6) 0.0029(5) 0.0018(6) C16 0.0373(8) 0.0297(10) 0.0196(7) 0.0012(6) 0.0041(6) 0.0010(8) C17 0.0533(11) 0.0386(12) 0.0424(10) 0.0051(9) 0.0113(9) -0.0160(10) C18 0.0241(7) 0.0400(11) 0.0317(8) -0.0081(8) 0.0013(6) 0.0014(7) C19 0.0286(8) 0.0562(15) 0.0397(10) 0.0003(9) 0.0055(7) -0.0112(9) C20 0.0410(10) 0.0575(16) 0.0398(10) 0.0014(10) -0.0111(8) -0.0004(10) N1 0.0229(6) 0.0225(7) 0.0193(6) -0.0016(5) 0.0052(4) 0.0008(5) O1 0.0413(6) 0.0228(7) 0.0313(6) -0.0022(5) 0.0048(5) 0.0065(5) O2 0.0486(8) 0.0352(8) 0.0452(8) 0.0112(6) 0.0058(6) 0.0079(6) O3 0.0340(6) 0.0363(8) 0.0327(6) 0.0082(5) 0.0053(5) -0.0064(6) S1 0.0368(2) 0.0290(2) 0.0348(2) -0.01079(19) 0.00551(15) 0.00456(19) _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 1.392(2) . ? C1 C2 1.487(2) . ? C1 S1 1.6457(17) . ? C2 C3 1.391(2) . ? C2 C7 1.397(2) . ? C3 C4 1.389(3) . ? C3 H3 0.9500 . ? C4 C5 1.388(3) . ? C4 H4 0.9500 . ? C5 C6 1.386(3) . ? C5 H5 0.9500 . ? C6 C7 1.391(2) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 O1 1.213(2) . ? C8 N1 1.419(2) . ? C8 C9 1.492(2) . ? C9 C10 1.391(2) . ? C9 C14 1.397(2) . ? C10 C11 1.395(2) . ? C10 H10 0.9500 . ? C11 C12 1.381(3) . ? C11 H11 0.9500 . ? C12 C13 1.381(3) . ? C12 H12 0.9500 . ? C13 C14 1.394(3) . ? C13 H13 0.9500 . ? C14 H14 0.9500 . ? C15 N1 1.485(2) . ? C15 C16 1.536(2) . ? C15 C18 1.539(2) . ? C15 H15 1.0000 . ? C16 O2 1.193(2) . ? C16 O3 1.349(2) . ? C17 O3 1.444(2) . ? C17 H17A 0.9800 . ? C17 H17C 0.9800 . ? C17 H17B 0.9800 . ? C18 C19 1.521(3) . ? C18 C20 1.541(3) . ? C18 H18 1.0000 . ? C19 H19C 0.9800 . ? C19 H19A 0.9800 . ? C19 H19B 0.9800 . ? C20 H20A 0.9800 . ? C20 H20B 0.9800 . ? C20 H20C 0.9800 . ? 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 115.34(14) . . ? N1 C1 S1 123.16(12) . . ? C2 C1 S1 121.42(12) . . ? C3 C2 C7 119.58(15) . . ? C3 C2 C1 121.25(16) . . ? C7 C2 C1 119.13(15) . . ? C4 C3 C2 119.98(17) . . ? C4 C3 H3 120.0 . . ? C2 C3 H3 120.0 . . ? C5 C4 C3 120.28(17) . . ? C5 C4 H4 119.9 . . ? C3 C4 H4 119.9 . . ? C6 C5 C4 119.97(16) . . ? C6 C5 H5 120.0 . . ? C4 C5 H5 120.0 . . ? C5 C6 C7 120.04(18) . . ? C5 C6 H6 120.0 . . ? C7 C6 H6 120.0 . . ? C6 C7 C2 120.05(16) . . ? C6 C7 H7 120.0 . . ? C2 C7 H7 120.0 . . ? O1 C8 N1 119.61(15) . . ? O1 C8 C9 122.28(15) . . ? N1 C8 C9 117.85(15) . . ? C10 C9 C14 120.31(15) . . ? C10 C9 C8 121.67(14) . . ? C14 C9 C8 117.80(16) . . ? C9 C10 C11 120.11(16) . . ? C9 C10 H10 119.9 . . ? C11 C10 H10 119.9 . . ? C12 C11 C10 119.42(19) . . ? C12 C11 H11 120.3 . . ? C10 C11 H11 120.3 . . ? C11 C12 C13 120.67(17) . . ? C11 C12 H12 119.7 . . ? C13 C12 H12 119.7 . . ? C12 C13 C14 120.62(19) . . ? C12 C13 H13 119.7 . . ? C14 C13 H13 119.7 . . ? C13 C14 C9 118.82(19) . . ? C13 C14 H14 120.6 . . ? C9 C14 H14 120.6 . . ? N1 C15 C16 108.43(13) . . ? N1 C15 C18 114.57(12) . . ? C16 C15 C18 113.94(14) . . ? N1 C15 H15 106.4 . . ? C16 C15 H15 106.4 . . ? C18 C15 H15 106.4 . . ? O2 C16 O3 124.32(18) . . ? O2 C16 C15 127.03(16) . . ? O3 C16 C15 108.56(14) . . ? O3 C17 H17A 109.5 . . ? O3 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? O3 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? H17C C17 H17B 109.5 . . ? C19 C18 C15 110.42(15) . . ? C19 C18 C20 109.59(17) . . ? C15 C18 C20 109.06(15) . . ? C19 C18 H18 109.3 . . ? C15 C18 H18 109.2 . . ? C20 C18 H18 109.2 . . ? C18 C19 H19C 109.5 . . ? C18 C19 H19A 109.5 . . ? H19C C19 H19A 109.5 . . ? C18 C19 H19B 109.5 . . ? H19C C19 H19B 109.5 . . ? H19A C19 H19B 109.5 . . ? C18 C20 H20A 109.5 . . ? C18 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C18 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? C1 N1 C8 122.34(13) . . ? C1 N1 C15 120.92(12) . . ? C8 N1 C15 116.11(13) . . ? C16 O3 C17 116.59(16) . . ? 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 137.06(15) . . . . ? S1 C1 C2 C3 -46.21(19) . . . . ? N1 C1 C2 C7 -45.32(19) . . . . ? S1 C1 C2 C7 131.42(14) . . . . ? C7 C2 C3 C4 3.0(2) . . . . ? C1 C2 C3 C4 -179.36(15) . . . . ? C2 C3 C4 C5 -1.7(3) . . . . ? C3 C4 C5 C6 -1.3(3) . . . . ? C4 C5 C6 C7 2.8(2) . . . . ? C5 C6 C7 C2 -1.4(2) . . . . ? C3 C2 C7 C6 -1.5(2) . . . . ? C1 C2 C7 C6 -179.14(14) . . . . ? O1 C8 C9 C10 137.01(17) . . . . ? N1 C8 C9 C10 -37.0(2) . . . . ? O1 C8 C9 C14 -37.6(2) . . . . ? N1 C8 C9 C14 148.37(15) . . . . ? C14 C9 C10 C11 0.8(2) . . . . ? C8 C9 C10 C11 -173.68(15) . . . . ? C9 C10 C11 C12 -2.0(2) . . . . ? C10 C11 C12 C13 1.1(3) . . . . ? C11 C12 C13 C14 1.0(3) . . . . ? C12 C13 C14 C9 -2.1(3) . . . . ? C10 C9 C14 C13 1.2(3) . . . . ? C8 C9 C14 C13 175.94(17) . . . . ? N1 C15 C16 O2 -132.66(18) . . . . ? C18 C15 C16 O2 -3.8(2) . . . . ? N1 C15 C16 O3 50.72(16) . . . . ? C18 C15 C16 O3 179.58(13) . . . . ? N1 C15 C18 C19 -46.6(2) . . . . ? C16 C15 C18 C19 -172.31(14) . . . . ? N1 C15 C18 C20 -167.10(17) . . . . ? C16 C15 C18 C20 67.2(2) . . . . ? C2 C1 N1 C8 -26.0(2) . . . . ? S1 C1 N1 C8 157.35(13) . . . . ? C2 C1 N1 C15 144.57(14) . . . . ? S1 C1 N1 C15 -32.1(2) . . . . ? O1 C8 N1 C1 148.96(16) . . . . ? C9 C8 N1 C1 -36.9(2) . . . . ? O1 C8 N1 C15 -22.0(2) . . . . ? C9 C8 N1 C15 152.15(14) . . . . ? C16 C15 N1 C1 -102.57(16) . . . . ? C18 C15 N1 C1 128.92(16) . . . . ? C16 C15 N1 C8 68.53(16) . . . . ? C18 C15 N1 C8 -60.0(2) . . . . ? O2 C16 O3 C17 0.8(2) . . . . ? C15 C16 O3 C17 177.52(14) . . . . ? _diffrn_measured_fraction_theta_max 0.915 _diffrn_reflns_theta_full 28.40 _diffrn_measured_fraction_theta_full 0.915 _refine_diff_density_max 0.210 _refine_diff_density_min -0.147 _refine_diff_density_rms 0.034 # Attachment 'sakamoto_2a.cif.cif' data_saka299_11 _database_code_depnum_ccdc_archive 'CCDC 611155' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H19 N O S' _chemical_formula_weight 345.44 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 P2(1)2(1)2(1) 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 9.857(3) _cell_length_b 11.082(3) _cell_length_c 17.126(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1870.8(9) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 22 _cell_measurement_theta_min 28.17 _cell_measurement_theta_max 29.89 _exptl_crystal_description cube _exptl_crystal_colour red _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.50 _exptl_crystal_size_min 0.50 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.226 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 728 _exptl_absorpt_coefficient_mu 1.590 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.5036 _exptl_absorpt_correction_T_max 0.5036 _exptl_absorpt_process_details psiscan _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'multiwire proportional' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2034 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0059 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 4.75 _diffrn_reflns_theta_max 70.04 _reflns_number_total 2034 _reflns_number_gt 1999 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker FRAMBO' _computing_cell_refinement 'Bruker FRAMBO' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.1672P)^2^+0.4368P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.08(3) _refine_ls_number_reflns 2034 _refine_ls_number_parameters 227 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0615 _refine_ls_R_factor_gt 0.0612 _refine_ls_wR_factor_ref 0.1456 _refine_ls_wR_factor_gt 0.1447 _refine_ls_goodness_of_fit_ref 0.750 _refine_ls_restrained_S_all 0.750 _refine_ls_shift/su_max 0.005 _refine_ls_shift/su_mean 0.001 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 0.69399(7) 0.98431(8) 0.06013(5) 0.0646(3) Uani 1 1 d . . . O1 O 0.3052(2) 0.7995(2) -0.09982(12) 0.0597(5) Uani 1 1 d . . . N1 N 0.4913(2) 0.8778(2) -0.04048(12) 0.0457(5) Uani 1 1 d . . . C10 C 0.3160(3) 0.9741(2) 0.03992(14) 0.0449(5) Uani 1 1 d . . . C17 C 0.5115(3) 0.8076(2) -0.17252(14) 0.0447(5) Uani 1 1 d . . . C16 C 0.4252(3) 0.8286(2) -0.10151(15) 0.0450(5) Uani 1 1 d . . . C4 C 0.5190(3) 0.9443(2) 0.17741(15) 0.0474(6) Uani 1 1 d . . . C18 C 0.4793(4) 0.7107(3) -0.22068(18) 0.0617(8) Uani 1 1 d . . . H18 H 0.4018 0.6651 -0.2109 0.074 Uiso 1 1 calc R . . C2 C 0.4362(2) 0.8872(2) 0.03871(14) 0.0413(5) Uani 1 1 d . . . C3 C 0.5467(3) 0.9407(2) 0.09186(15) 0.0432(6) Uani 1 1 d . . . C21 C 0.7071(4) 0.8465(3) -0.25275(19) 0.0671(8) Uani 1 1 d . . . H21 H 0.7830 0.8931 -0.2642 0.080 Uiso 1 1 calc R . . C22 C 0.6259(4) 0.8752(3) -0.18965(17) 0.0541(6) Uani 1 1 d . . . H22 H 0.6484 0.9407 -0.1583 0.065 Uiso 1 1 calc R . . C5 C 0.4254(4) 1.0229(3) 0.2107(2) 0.0634(8) Uani 1 1 d . . . H5 H 0.3735 1.0738 0.1795 0.076 Uiso 1 1 calc R . . C1 C 0.4048(3) 0.7596(3) 0.06905(18) 0.0573(7) Uani 1 1 d . . . H1A H 0.3395 0.7218 0.0354 0.086 Uiso 1 1 calc R . . H1B H 0.3686 0.7647 0.1210 0.086 Uiso 1 1 calc R . . H1C H 0.4866 0.7126 0.0697 0.086 Uiso 1 1 calc R . . C19 C 0.5621(5) 0.6821(4) -0.2828(2) 0.0767(10) Uani 1 1 d . . . H19 H 0.5404 0.6166 -0.3144 0.092 Uiso 1 1 calc R . . C11 C 0.3323(4) 1.0887(3) 0.00890(18) 0.0631(8) Uani 1 1 d . . . H11 H 0.4129 1.1088 -0.0162 0.076 Uiso 1 1 calc R . . C20 C 0.6749(4) 0.7480(4) -0.29890(19) 0.0738(9) Uani 1 1 d . . . H20 H 0.7303 0.7270 -0.3407 0.089 Uiso 1 1 calc R . . C9 C 0.5945(4) 0.8697(3) 0.2253(2) 0.0658(8) Uani 1 1 d . . . H9 H 0.6571 0.8168 0.2035 0.079 Uiso 1 1 calc R . . C6 C 0.4111(5) 1.0239(4) 0.2915(2) 0.0824(12) Uani 1 1 d . . . H6 H 0.3483 1.0759 0.3142 0.099 Uiso 1 1 calc R . . C15 C 0.1936(3) 0.9455(4) 0.0754(2) 0.0700(9) Uani 1 1 d . . . H15 H 0.1795 0.8685 0.0954 0.084 Uiso 1 1 calc R . . C8 C 0.5774(6) 0.8734(4) 0.3053(2) 0.0874(13) Uani 1 1 d . . . H8 H 0.6283 0.8225 0.3369 0.105 Uiso 1 1 calc R . . C7 C 0.4865(6) 0.9508(4) 0.3383(2) 0.0886(14) Uani 1 1 d . . . H7 H 0.4761 0.9537 0.3922 0.106 Uiso 1 1 calc R . . C12 C 0.2294(5) 1.1739(4) 0.0149(2) 0.0871(13) Uani 1 1 d . . . H12 H 0.2410 1.2508 -0.0057 0.105 Uiso 1 1 calc R . . C14 C 0.0926(4) 1.0314(5) 0.0810(3) 0.0932(14) Uani 1 1 d . . . H14 H 0.0113 1.0117 0.1054 0.112 Uiso 1 1 calc R . . C13 C 0.1098(5) 1.1431(5) 0.0518(3) 0.0947(15) Uani 1 1 d . . . H13 H 0.0408 1.1999 0.0566 0.114 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 0.0446(4) 0.0881(5) 0.0610(4) -0.0180(4) 0.0057(3) -0.0181(3) O1 0.0433(10) 0.0796(13) 0.0562(10) -0.0030(10) -0.0054(9) -0.0090(10) N1 0.0413(11) 0.0541(11) 0.0417(10) -0.0078(9) 0.0015(9) -0.0020(9) C10 0.0400(12) 0.0533(13) 0.0416(11) 0.0015(10) 0.0008(10) 0.0021(11) C17 0.0452(12) 0.0471(11) 0.0418(11) 0.0033(10) -0.0054(10) 0.0036(11) C16 0.0408(12) 0.0471(12) 0.0471(12) 0.0006(10) -0.0041(11) 0.0023(10) C4 0.0486(14) 0.0478(11) 0.0458(12) -0.0079(10) 0.0019(12) -0.0032(11) C18 0.0615(17) 0.0680(17) 0.0555(15) -0.0100(14) -0.0031(14) -0.0059(15) C2 0.0393(12) 0.0422(11) 0.0426(11) 0.0013(9) 0.0017(10) -0.0027(10) C3 0.0431(13) 0.0392(10) 0.0474(12) -0.0049(9) -0.0003(10) 0.0018(10) C21 0.0653(19) 0.0780(19) 0.0579(16) 0.0098(15) 0.0125(15) -0.0076(17) C22 0.0619(16) 0.0509(13) 0.0496(13) 0.0050(11) 0.0021(13) -0.0066(12) C5 0.0624(17) 0.0650(16) 0.0626(16) -0.0202(14) 0.0025(14) 0.0062(15) C1 0.0686(17) 0.0436(12) 0.0596(15) 0.0057(12) -0.0067(15) -0.0097(13) C19 0.088(2) 0.083(2) 0.0589(17) -0.0207(17) 0.0043(18) -0.004(2) C11 0.074(2) 0.0557(15) 0.0595(15) 0.0131(13) 0.0096(15) 0.0122(16) C20 0.082(2) 0.091(2) 0.0487(14) -0.0041(16) 0.0109(17) 0.010(2) C9 0.074(2) 0.0631(17) 0.0599(17) -0.0028(14) -0.0064(16) 0.0086(16) C6 0.086(3) 0.091(2) 0.070(2) -0.034(2) 0.026(2) -0.008(2) C15 0.0478(16) 0.083(2) 0.079(2) 0.0050(18) 0.0132(16) -0.0019(16) C8 0.127(4) 0.081(2) 0.0543(17) 0.0071(17) -0.011(2) -0.003(3) C7 0.125(4) 0.092(2) 0.0494(15) -0.0119(18) 0.012(2) -0.035(3) C12 0.121(3) 0.074(2) 0.0660(19) 0.0101(17) -0.002(2) 0.042(2) C14 0.0514(19) 0.126(4) 0.103(3) 0.002(3) 0.019(2) 0.027(2) C13 0.089(3) 0.123(4) 0.072(2) -0.005(2) 0.000(2) 0.061(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 S1 C3 1.624(3) . ? O1 C16 1.226(3) . ? N1 C16 1.347(3) . ? N1 C2 1.465(3) . ? C10 C11 1.386(4) . ? C10 C15 1.388(4) . ? C10 C2 1.526(3) . ? C17 C22 1.386(4) . ? C17 C18 1.391(4) . ? C17 C16 1.502(4) . ? C4 C9 1.382(4) . ? C4 C5 1.391(4) . ? C4 C3 1.491(4) . ? C18 C19 1.379(5) . ? C18 H18 0.9300 . ? C2 C3 1.538(4) . ? C2 C1 1.538(3) . ? C21 C20 1.385(6) . ? C21 C22 1.382(5) . ? C21 H21 0.9300 . ? C22 H22 0.9300 . ? C5 C6 1.392(5) . ? C5 H5 0.9300 . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C19 C20 1.358(6) . ? C19 H19 0.9300 . ? C11 C12 1.389(5) . ? C11 H11 0.9300 . ? C20 H20 0.9300 . ? C9 C8 1.381(5) . ? C9 H9 0.9300 . ? C6 C7 1.360(7) . ? C6 H6 0.9300 . ? C15 C14 1.380(6) . ? C15 H15 0.9300 . ? C8 C7 1.363(7) . ? C8 H8 0.9300 . ? C7 H7 0.9300 . ? C12 C13 1.381(7) . ? C12 H12 0.9300 . ? C14 C13 1.346(8) . ? C14 H14 0.9300 . ? C13 H13 0.9300 . ? 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 C16 N1 C2 124.6(2) . . ? C11 C10 C15 118.5(3) . . ? C11 C10 C2 118.9(2) . . ? C15 C10 C2 122.5(3) . . ? C22 C17 C18 118.5(3) . . ? C22 C17 C16 123.3(2) . . ? C18 C17 C16 118.1(3) . . ? O1 C16 N1 123.7(3) . . ? O1 C16 C17 121.6(3) . . ? N1 C16 C17 114.6(2) . . ? C9 C4 C5 119.2(3) . . ? C9 C4 C3 117.9(3) . . ? C5 C4 C3 122.7(3) . . ? C19 C18 C17 120.0(3) . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 120.0 . . ? N1 C2 C3 108.2(2) . . ? N1 C2 C10 110.2(2) . . ? C3 C2 C10 107.4(2) . . ? N1 C2 C1 108.8(2) . . ? C3 C2 C1 107.3(2) . . ? C10 C2 C1 114.8(2) . . ? C4 C3 C2 117.5(2) . . ? C4 C3 S1 119.0(2) . . ? C2 C3 S1 123.35(19) . . ? C20 C21 C22 119.7(3) . . ? C20 C21 H21 120.2 . . ? C22 C21 H21 120.2 . . ? C21 C22 C17 120.8(3) . . ? C21 C22 H22 119.6 . . ? C17 C22 H22 119.6 . . ? C4 C5 C6 118.7(3) . . ? C4 C5 H5 120.7 . . ? C6 C5 H5 120.7 . . ? C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C20 C19 C18 121.2(3) . . ? C20 C19 H19 119.4 . . ? C18 C19 H19 119.4 . . ? C12 C11 C10 120.7(3) . . ? C12 C11 H11 119.7 . . ? C10 C11 H11 119.7 . . ? C21 C20 C19 119.7(3) . . ? C21 C20 H20 120.1 . . ? C19 C20 H20 120.1 . . ? C4 C9 C8 120.4(4) . . ? C4 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C7 C6 C5 121.7(4) . . ? C7 C6 H6 119.2 . . ? C5 C6 H6 119.2 . . ? C14 C15 C10 120.0(4) . . ? C14 C15 H15 120.0 . . ? C10 C15 H15 120.0 . . ? C7 C8 C9 120.7(4) . . ? C7 C8 H8 119.7 . . ? C9 C8 H8 119.7 . . ? C8 C7 C6 119.4(3) . . ? C8 C7 H7 120.3 . . ? C6 C7 H7 120.3 . . ? C11 C12 C13 119.3(4) . . ? C11 C12 H12 120.3 . . ? C13 C12 H12 120.3 . . ? C13 C14 C15 121.2(4) . . ? C13 C14 H14 119.4 . . ? C15 C14 H14 119.4 . . ? C14 C13 C12 120.3(4) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? 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 C2 N1 C16 O1 9.2(4) . . . . ? C2 N1 C16 C17 -168.8(2) . . . . ? C22 C17 C16 O1 154.9(3) . . . . ? C18 C17 C16 O1 -29.1(4) . . . . ? C22 C17 C16 N1 -27.0(4) . . . . ? C18 C17 C16 N1 148.9(3) . . . . ? C22 C17 C18 C19 1.4(5) . . . . ? C16 C17 C18 C19 -174.7(3) . . . . ? C16 N1 C2 C3 176.2(2) . . . . ? C16 N1 C2 C10 -66.7(3) . . . . ? C16 N1 C2 C1 60.0(3) . . . . ? C11 C10 C2 N1 -52.6(3) . . . . ? C15 C10 C2 N1 131.7(3) . . . . ? C11 C10 C2 C3 65.1(3) . . . . ? C15 C10 C2 C3 -110.7(3) . . . . ? C11 C10 C2 C1 -175.8(3) . . . . ? C15 C10 C2 C1 8.5(4) . . . . ? C9 C4 C3 C2 111.3(3) . . . . ? C5 C4 C3 C2 -71.6(3) . . . . ? C9 C4 C3 S1 -64.6(3) . . . . ? C5 C4 C3 S1 112.5(3) . . . . ? N1 C2 C3 C4 -172.6(2) . . . . ? C10 C2 C3 C4 68.5(3) . . . . ? C1 C2 C3 C4 -55.4(3) . . . . ? N1 C2 C3 S1 3.2(3) . . . . ? C10 C2 C3 S1 -115.8(2) . . . . ? C1 C2 C3 S1 120.4(2) . . . . ? C20 C21 C22 C17 -0.9(5) . . . . ? C18 C17 C22 C21 -0.6(4) . . . . ? C16 C17 C22 C21 175.3(3) . . . . ? C9 C4 C5 C6 0.1(5) . . . . ? C3 C4 C5 C6 -177.0(3) . . . . ? C17 C18 C19 C20 -0.8(6) . . . . ? C15 C10 C11 C12 1.5(5) . . . . ? C2 C10 C11 C12 -174.4(3) . . . . ? C22 C21 C20 C19 1.5(6) . . . . ? C18 C19 C20 C21 -0.7(6) . . . . ? C5 C4 C9 C8 -0.1(6) . . . . ? C3 C4 C9 C8 177.1(4) . . . . ? C4 C5 C6 C7 0.4(6) . . . . ? C11 C10 C15 C14 -1.7(5) . . . . ? C2 C10 C15 C14 174.1(4) . . . . ? C4 C9 C8 C7 -0.3(7) . . . . ? C9 C8 C7 C6 0.8(7) . . . . ? C5 C6 C7 C8 -0.9(7) . . . . ? C10 C11 C12 C13 -0.4(6) . . . . ? C10 C15 C14 C13 0.7(7) . . . . ? C15 C14 C13 C12 0.5(8) . . . . ? C11 C12 C13 C14 -0.7(7) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 70.04 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.386 _refine_diff_density_min -0.679 _refine_diff_density_rms 0.143 # Attachment 'sakamoto_2b.cif.cif' data_saka28b_212121 _database_code_depnum_ccdc_archive 'CCDC 611156' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C23 H21 N O S' _chemical_formula_weight 359.47 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' 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 Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' _cell_length_a 9.7025(7) _cell_length_b 9.9727(7) _cell_length_c 20.1303(15) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1947.8(2) _cell_formula_units_Z 4 _cell_measurement_temperature 173 _cell_measurement_reflns_used 4380 _cell_measurement_theta_min 2.28 _cell_measurement_theta_max 27.44 _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.226 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 760 _exptl_absorpt_coefficient_mu 0.177 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9488 _exptl_absorpt_correction_T_max 0.9825 _exptl_absorpt_process_details ; SADABS Sheldrick 1996 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 173 _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 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 11052 _diffrn_reflns_av_R_equivalents 0.0182 _diffrn_reflns_av_sigmaI/netI 0.0248 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.02 _diffrn_reflns_theta_max 28.48 _reflns_number_total 4444 _reflns_number_gt 3954 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0000P)^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 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 0.03(5) _refine_ls_number_reflns 4444 _refine_ls_number_parameters 237 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0437 _refine_ls_R_factor_gt 0.0372 _refine_ls_wR_factor_ref 0.0541 _refine_ls_wR_factor_gt 0.0534 _refine_ls_goodness_of_fit_ref 2.209 _refine_ls_restrained_S_all 2.209 _refine_ls_shift/su_max 0.580 _refine_ls_shift/su_mean 0.017 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 0.13530(19) 0.23501(13) 0.94235(7) 0.0427(4) Uani 1 1 d . . . H1A H 0.1988 0.1998 0.9760 0.064 Uiso 1 1 calc R . . H1B H 0.1772 0.2265 0.8983 0.064 Uiso 1 1 calc R . . H1C H 0.0490 0.1840 0.9436 0.064 Uiso 1 1 calc R . . C2 C 0.10532(16) 0.38374(14) 0.95679(7) 0.0301(4) Uani 1 1 d . . . C3 C 0.00069(16) 0.43012(14) 0.90448(7) 0.0308(4) Uani 1 1 d . . . C4 C 0.03805(16) 0.41287(14) 0.83323(7) 0.0312(4) Uani 1 1 d . . . C5 C 0.14742(17) 0.47863(14) 0.80320(7) 0.0406(4) Uani 1 1 d . . . H5 H 0.2062 0.5342 0.8290 0.049 Uiso 1 1 calc R . . C6 C 0.17155(19) 0.46356(15) 0.73531(7) 0.0472(5) Uani 1 1 d . . . H6 H 0.2453 0.5112 0.7151 0.057 Uiso 1 1 calc R . . C7 C 0.0904(2) 0.38084(16) 0.69710(7) 0.0474(5) Uani 1 1 d . . . C8 C -0.0148(2) 0.31233(16) 0.72761(8) 0.0542(5) Uani 1 1 d . . . H7 H -0.0700 0.2527 0.7022 0.065 Uiso 1 1 calc R . . C9 C -0.0422(2) 0.32854(15) 0.79501(8) 0.0464(5) Uani 1 1 d . . . H8 H -0.1166 0.2813 0.8148 0.056 Uiso 1 1 calc R . . C10 C 0.1173(3) 0.36696(18) 0.62292(7) 0.0743(7) Uani 1 1 d . . . H10B H 0.1288 0.4561 0.6033 0.112 Uiso 1 1 calc R . . H10C H 0.0390 0.3216 0.6019 0.112 Uiso 1 1 calc R . . H10A H 0.2012 0.3142 0.6159 0.112 Uiso 1 1 calc R . . C11 C 0.23095(15) 0.47604(16) 0.95202(6) 0.0319(4) Uani 1 1 d . . . C12 C 0.2119(2) 0.61254(16) 0.96334(7) 0.0439(5) Uani 1 1 d . . . H12 H 0.1241 0.6452 0.9766 0.053 Uiso 1 1 calc R . . C13 C 0.3208(3) 0.7006(2) 0.95529(8) 0.0657(6) Uani 1 1 d . . . H13 H 0.3078 0.7936 0.9634 0.079 Uiso 1 1 calc R . . C14 C 0.4476(3) 0.6542(3) 0.93566(9) 0.0761(7) Uani 1 1 d . . . H14 H 0.5219 0.7149 0.9294 0.091 Uiso 1 1 calc R . . C15 C 0.46607(19) 0.5206(3) 0.92525(10) 0.0753(6) Uani 1 1 d . . . H15 H 0.5542 0.4884 0.9124 0.090 Uiso 1 1 calc R . . C16 C 0.35890(18) 0.43148(17) 0.93308(9) 0.0531(5) Uani 1 1 d . . . H16 H 0.3736 0.3386 0.9253 0.064 Uiso 1 1 calc R . . C17 C 0.10580(17) 0.36050(14) 1.08035(8) 0.0348(4) Uani 1 1 d . . . C18 C 0.01681(18) 0.37261(15) 1.14086(7) 0.0356(4) Uani 1 1 d . . . C19 C 0.0417(2) 0.28580(17) 1.19352(7) 0.0514(5) Uani 1 1 d . . . H19 H 0.1148 0.2226 1.1908 0.062 Uiso 1 1 calc R . . C20 C -0.0392(2) 0.2911(2) 1.24959(9) 0.0695(6) Uani 1 1 d . . . H20 H -0.0216 0.2311 1.2852 0.083 Uiso 1 1 calc R . . C21 C -0.1442(2) 0.3814(2) 1.25469(9) 0.0683(6) Uani 1 1 d . . . H21 H -0.1996 0.3838 1.2936 0.082 Uiso 1 1 calc R . . C22 C -0.1696(2) 0.46877(18) 1.20338(9) 0.0638(6) Uani 1 1 d . . . H22 H -0.2420 0.5325 1.2068 0.077 Uiso 1 1 calc R . . C23 C -0.08898(19) 0.46357(16) 1.14665(8) 0.0479(5) Uani 1 1 d . . . H23 H -0.1071 0.5238 1.1112 0.058 Uiso 1 1 calc R . . N1 N 0.04292(13) 0.39540(11) 1.02253(5) 0.0326(3) Uani 1 1 d . . . H2 H -0.0415 0.4273 1.0249 0.039 Uiso 1 1 calc R . . O1 O 0.22468(12) 0.32043(11) 1.08338(5) 0.0461(3) Uani 1 1 d . . . S1 S -0.15122(4) 0.48797(4) 0.92360(2) 0.04364(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 0.0545(11) 0.0335(9) 0.0402(9) 0.0020(7) 0.0001(9) 0.0054(9) C2 0.0308(9) 0.0331(9) 0.0263(8) 0.0019(6) 0.0008(7) 0.0015(8) C3 0.0301(9) 0.0282(8) 0.0341(9) 0.0037(6) 0.0010(8) -0.0054(7) C4 0.0316(9) 0.0331(9) 0.0288(8) 0.0038(7) 0.0009(8) -0.0001(8) C5 0.0428(10) 0.0453(10) 0.0336(8) -0.0002(7) 0.0023(9) -0.0058(10) C6 0.0580(12) 0.0466(10) 0.0369(9) 0.0042(8) 0.0117(10) -0.0101(10) C7 0.0744(15) 0.0359(10) 0.0319(9) 0.0020(8) 0.0063(10) 0.0007(10) C8 0.0741(15) 0.0544(11) 0.0341(10) -0.0055(8) -0.0058(11) -0.0182(11) C9 0.0466(11) 0.0524(11) 0.0403(9) 0.0013(8) 0.0011(10) -0.0158(10) C10 0.122(2) 0.0673(13) 0.0337(10) -0.0089(9) 0.0180(12) -0.0153(14) C11 0.0294(9) 0.0442(10) 0.0221(7) 0.0028(7) -0.0002(7) -0.0025(8) C12 0.0585(13) 0.0437(10) 0.0294(9) -0.0042(7) 0.0058(9) -0.0126(10) C13 0.1009(19) 0.0642(13) 0.0319(10) -0.0049(9) 0.0040(12) -0.0432(14) C14 0.0686(15) 0.119(2) 0.0409(12) 0.0079(13) -0.0078(13) -0.0615(16) C15 0.0329(11) 0.124(2) 0.0685(14) 0.0197(17) -0.0001(12) -0.0141(14) C16 0.0320(10) 0.0691(12) 0.0581(11) 0.0129(10) 0.0018(11) 0.0049(10) C17 0.0394(10) 0.0314(8) 0.0337(9) 0.0042(7) -0.0021(9) -0.0054(7) C18 0.0406(11) 0.0386(9) 0.0276(8) -0.0012(7) 0.0000(8) -0.0117(9) C19 0.0581(13) 0.0586(12) 0.0376(10) 0.0094(9) 0.0007(10) 0.0020(11) C20 0.0898(18) 0.0812(15) 0.0374(11) 0.0107(10) 0.0077(13) -0.0129(14) C21 0.0764(16) 0.0911(16) 0.0376(11) -0.0106(11) 0.0167(12) -0.0162(15) C22 0.0654(14) 0.0744(14) 0.0515(11) -0.0147(10) 0.0139(11) 0.0084(13) C23 0.0578(13) 0.0488(11) 0.0373(9) -0.0039(8) 0.0025(9) 0.0037(10) N1 0.0291(7) 0.0405(8) 0.0283(7) 0.0046(6) 0.0033(6) 0.0017(7) O1 0.0364(7) 0.0602(8) 0.0418(6) 0.0062(6) -0.0040(7) 0.0094(6) S1 0.0291(2) 0.0625(3) 0.0394(2) 0.0050(2) 0.0013(2) 0.0067(2) _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 C2 1.5392(18) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 N1 1.4599(16) . ? C2 C11 1.530(2) . ? C2 C3 1.5341(19) . ? C3 C4 1.4893(18) . ? C3 S1 1.6289(16) . ? C4 C9 1.380(2) . ? C4 C5 1.3863(19) . ? C5 C6 1.3947(19) . ? C5 H5 0.9500 . ? C6 C7 1.376(2) . ? C6 H6 0.9500 . ? C7 C8 1.373(2) . ? C7 C10 1.5222(19) . ? C8 C9 1.392(2) . ? C8 H7 0.9500 . ? C9 H8 0.9500 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C10 H10A 0.9800 . ? C11 C16 1.373(2) . ? C11 C12 1.392(2) . ? C12 C13 1.384(2) . ? C12 H12 0.9500 . ? C13 C14 1.372(3) . ? C13 H13 0.9500 . ? C14 C15 1.360(3) . ? C14 H14 0.9500 . ? C15 C16 1.377(2) . ? C15 H15 0.9500 . ? C16 H16 0.9500 . ? C17 O1 1.2223(18) . ? C17 N1 1.3594(18) . ? C17 C18 1.498(2) . ? C18 C23 1.375(2) . ? C18 C19 1.3898(19) . ? C19 C20 1.376(2) . ? C19 H19 0.9500 . ? C20 C21 1.364(3) . ? C20 H20 0.9500 . ? C21 C22 1.374(2) . ? C21 H21 0.9500 . ? C22 C23 1.385(2) . ? C22 H22 0.9500 . ? C23 H23 0.9500 . ? N1 H2 0.8800 . ? 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 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 C11 109.83(11) . . ? N1 C2 C3 108.89(12) . . ? C11 C2 C3 107.62(11) . . ? N1 C2 C1 109.04(12) . . ? C11 C2 C1 114.66(13) . . ? C3 C2 C1 106.62(12) . . ? C4 C3 C2 117.72(13) . . ? C4 C3 S1 119.25(11) . . ? C2 C3 S1 122.92(10) . . ? C9 C4 C5 118.48(14) . . ? C9 C4 C3 118.03(14) . . ? C5 C4 C3 123.48(14) . . ? C4 C5 C6 120.32(15) . . ? C4 C5 H5 119.8 . . ? C6 C5 H5 119.8 . . ? C7 C6 C5 121.09(16) . . ? C7 C6 H6 119.5 . . ? C5 C6 H6 119.5 . . ? C8 C7 C6 118.29(15) . . ? C8 C7 C10 121.39(17) . . ? C6 C7 C10 120.33(17) . . ? C7 C8 C9 121.33(16) . . ? C7 C8 H7 119.3 . . ? C9 C8 H7 119.3 . . ? C4 C9 C8 120.42(16) . . ? C4 C9 H8 119.8 . . ? C8 C9 H8 119.8 . . ? C7 C10 H10B 109.5 . . ? C7 C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C7 C10 H10A 109.5 . . ? H10B C10 H10A 109.5 . . ? H10C C10 H10A 109.5 . . ? C16 C11 C12 118.82(16) . . ? C16 C11 C2 122.89(15) . . ? C12 C11 C2 118.15(14) . . ? C13 C12 C11 119.97(19) . . ? C13 C12 H12 120.0 . . ? C11 C12 H12 120.0 . . ? C14 C13 C12 120.3(2) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C15 C14 C13 119.5(2) . . ? C15 C14 H14 120.3 . . ? C13 C14 H14 120.3 . . ? C14 C15 C16 121.0(2) . . ? C14 C15 H15 119.5 . . ? C16 C15 H15 119.5 . . ? C11 C16 C15 120.38(17) . . ? C11 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? O1 C17 N1 123.36(16) . . ? O1 C17 C18 121.98(16) . . ? N1 C17 C18 114.65(14) . . ? C23 C18 C19 118.45(16) . . ? C23 C18 C17 123.53(14) . . ? C19 C18 C17 118.02(16) . . ? C20 C19 C18 120.16(18) . . ? C20 C19 H19 119.9 . . ? C18 C19 H19 119.9 . . ? C21 C20 C19 120.91(18) . . ? C21 C20 H20 119.5 . . ? C19 C20 H20 119.5 . . ? C20 C21 C22 119.74(19) . . ? C20 C21 H21 120.1 . . ? C22 C21 H21 120.1 . . ? C21 C22 C23 119.67(19) . . ? C21 C22 H22 120.2 . . ? C23 C22 H22 120.2 . . ? C18 C23 C22 121.06(16) . . ? C18 C23 H23 119.5 . . ? C22 C23 H23 119.5 . . ? C17 N1 C2 124.72(13) . . ? C17 N1 H2 117.6 . . ? C2 N1 H2 117.6 . . ? 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 N1 C2 C3 C4 -173.69(11) . . . . ? C11 C2 C3 C4 67.31(15) . . . . ? C1 C2 C3 C4 -56.17(17) . . . . ? N1 C2 C3 S1 2.43(17) . . . . ? C11 C2 C3 S1 -116.58(12) . . . . ? C1 C2 C3 S1 119.94(12) . . . . ? C2 C3 C4 C9 116.91(16) . . . . ? S1 C3 C4 C9 -59.35(17) . . . . ? C2 C3 C4 C5 -64.22(19) . . . . ? S1 C3 C4 C5 119.52(15) . . . . ? C9 C4 C5 C6 2.6(2) . . . . ? C3 C4 C5 C6 -176.29(15) . . . . ? C4 C5 C6 C7 -1.8(3) . . . . ? C5 C6 C7 C8 -0.5(3) . . . . ? C5 C6 C7 C10 179.27(17) . . . . ? C6 C7 C8 C9 2.0(3) . . . . ? C10 C7 C8 C9 -177.81(18) . . . . ? C5 C4 C9 C8 -1.1(2) . . . . ? C3 C4 C9 C8 177.78(16) . . . . ? C7 C8 C9 C4 -1.1(3) . . . . ? N1 C2 C11 C16 126.37(15) . . . . ? C3 C2 C11 C16 -115.23(16) . . . . ? C1 C2 C11 C16 3.2(2) . . . . ? N1 C2 C11 C12 -57.86(17) . . . . ? C3 C2 C11 C12 60.54(16) . . . . ? C1 C2 C11 C12 178.96(12) . . . . ? C16 C11 C12 C13 0.1(2) . . . . ? C2 C11 C12 C13 -175.81(13) . . . . ? C11 C12 C13 C14 0.5(3) . . . . ? C12 C13 C14 C15 -1.1(3) . . . . ? C13 C14 C15 C16 1.0(3) . . . . ? C12 C11 C16 C15 -0.2(3) . . . . ? C2 C11 C16 C15 175.52(15) . . . . ? C14 C15 C16 C11 -0.4(3) . . . . ? O1 C17 C18 C23 151.86(16) . . . . ? N1 C17 C18 C23 -29.1(2) . . . . ? O1 C17 C18 C19 -29.0(2) . . . . ? N1 C17 C18 C19 149.98(15) . . . . ? C23 C18 C19 C20 0.6(3) . . . . ? C17 C18 C19 C20 -178.60(15) . . . . ? C18 C19 C20 C21 -0.3(3) . . . . ? C19 C20 C21 C22 -0.3(3) . . . . ? C20 C21 C22 C23 0.6(3) . . . . ? C19 C18 C23 C22 -0.2(3) . . . . ? C17 C18 C23 C22 178.86(15) . . . . ? C21 C22 C23 C18 -0.3(3) . . . . ? O1 C17 N1 C2 3.2(2) . . . . ? C18 C17 N1 C2 -175.83(12) . . . . ? C11 C2 N1 C17 -63.66(17) . . . . ? C3 C2 N1 C17 178.72(12) . . . . ? C1 C2 N1 C17 62.75(18) . . . . ? _diffrn_measured_fraction_theta_max 0.938 _diffrn_reflns_theta_full 28.48 _diffrn_measured_fraction_theta_full 0.938 _refine_diff_density_max 0.357 _refine_diff_density_min -0.277 _refine_diff_density_rms 0.034 # Attachment 'sakamoto_2d.cif.cif' data_saka26p212121 _database_code_depnum_ccdc_archive 'CCDC 611157' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H18 Cl N O S' _chemical_formula_weight 379.88 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' Cl Cl 0.1484 0.1585 '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 Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' '-x+1/2, -y, z+1/2' _cell_length_a 9.6375(5) _cell_length_b 10.0167(5) _cell_length_c 20.0523(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1935.77(17) _cell_formula_units_Z 4 _cell_measurement_temperature 173 _cell_measurement_reflns_used 7027 _cell_measurement_theta_min 2.27 _cell_measurement_theta_max 28.23 _exptl_crystal_description cubic _exptl_crystal_colour red _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.35 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.303 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 0.315 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.8842 _exptl_absorpt_correction_T_max 0.8976 _exptl_absorpt_process_details ; SADABS Sheldrick 1996 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 173 _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 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10893 _diffrn_reflns_av_R_equivalents 0.0217 _diffrn_reflns_av_sigmaI/netI 0.0271 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 25 _diffrn_reflns_theta_min 2.03 _diffrn_reflns_theta_max 28.39 _reflns_number_total 4458 _reflns_number_gt 4211 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0000P)^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 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 -0.05(5) _refine_ls_number_reflns 4458 _refine_ls_number_parameters 236 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0369 _refine_ls_R_factor_gt 0.0346 _refine_ls_wR_factor_ref 0.0752 _refine_ls_wR_factor_gt 0.0746 _refine_ls_goodness_of_fit_ref 2.206 _refine_ls_restrained_S_all 2.206 _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 C1 C 0.35289(19) 0.76532(14) 0.94246(8) 0.0439(4) Uani 1 1 d . . . H1A H 0.2894 0.7984 0.9769 0.066 Uiso 1 1 calc R . . H1B H 0.3087 0.7730 0.8986 0.066 Uiso 1 1 calc R . . H1C H 0.4384 0.8183 0.9431 0.066 Uiso 1 1 calc R . . C2 C 0.38778(13) 0.61791(13) 0.95640(6) 0.0288(3) Uani 1 1 d . . . C3 C 0.49294(14) 0.57437(13) 0.90308(7) 0.0298(3) Uani 1 1 d . . . C4 C 0.45401(15) 0.59546(14) 0.83182(7) 0.0308(3) Uani 1 1 d . . . C5 C 0.34453(16) 0.52867(15) 0.80128(7) 0.0392(3) Uani 1 1 d . . . H5 H 0.2873 0.4709 0.8269 0.047 Uiso 1 1 calc R . . C6 C 0.31801(19) 0.54562(17) 0.73373(8) 0.0472(4) Uani 1 1 d . . . H6 H 0.2448 0.4979 0.7127 0.057 Uiso 1 1 calc R . . C7 C 0.3988(2) 0.63200(17) 0.69784(8) 0.0499(4) Uani 1 1 d . . . C8 C 0.5051(2) 0.70168(18) 0.72689(8) 0.0561(5) Uani 1 1 d . . . H8 H 0.5587 0.7627 0.7013 0.067 Uiso 1 1 calc R . . C9 C 0.53373(18) 0.68239(17) 0.79391(8) 0.0455(4) Uani 1 1 d . . . H9 H 0.6086 0.7291 0.8141 0.055 Uiso 1 1 calc R . . C10 C 0.26391(13) 0.52237(15) 0.95139(7) 0.0320(3) Uani 1 1 d . . . C11 C 0.28826(18) 0.38599(17) 0.95964(7) 0.0422(4) Uani 1 1 d . . . H11 H 0.3786 0.3552 0.9708 0.051 Uiso 1 1 calc R . . C12 C 0.1810(2) 0.2955(2) 0.95157(8) 0.0658(6) Uani 1 1 d . . . H12 H 0.1982 0.2028 0.9573 0.079 Uiso 1 1 calc R . . C13 C 0.0505(2) 0.3386(3) 0.93546(10) 0.0785(8) Uani 1 1 d . . . H13 H -0.0225 0.2760 0.9295 0.094 Uiso 1 1 calc R . . C14 C 0.02617(19) 0.4714(3) 0.92806(12) 0.0805(8) Uani 1 1 d . . . H14 H -0.0649 0.5009 0.9175 0.097 Uiso 1 1 calc R . . C15 C 0.13200(16) 0.5652(2) 0.93566(9) 0.0561(5) Uani 1 1 d . . . H15 H 0.1133 0.6576 0.9300 0.067 Uiso 1 1 calc R . . C16 C 0.39045(14) 0.63930(13) 1.08038(7) 0.0324(3) Uani 1 1 d . . . C17 C 0.48023(15) 0.62550(14) 1.14088(7) 0.0337(3) Uani 1 1 d . . . C18 C 0.4575(2) 0.71197(18) 1.19431(8) 0.0485(4) Uani 1 1 d . . . H18 H 0.3857 0.7767 1.1919 0.058 Uiso 1 1 calc R . . C19 C 0.5391(2) 0.7037(2) 1.25044(9) 0.0626(5) Uani 1 1 d . . . H19 H 0.5235 0.7635 1.2864 0.075 Uiso 1 1 calc R . . C20 C 0.6417(2) 0.6111(2) 1.25518(9) 0.0646(5) Uani 1 1 d . . . H20 H 0.6969 0.6067 1.2943 0.077 Uiso 1 1 calc R . . C21 C 0.6658(2) 0.5236(2) 1.20335(9) 0.0610(5) Uani 1 1 d . . . H21 H 0.7372 0.4586 1.2067 0.073 Uiso 1 1 calc R . . C22 C 0.58468(17) 0.53138(17) 1.14602(8) 0.0455(4) Uani 1 1 d . . . H22 H 0.6012 0.4715 1.1101 0.055 Uiso 1 1 calc R . . Cl1 Cl 0.36483(8) 0.65284(5) 0.61309(2) 0.0846(2) Uani 1 1 d . . . N1 N 0.45202(12) 0.60555(12) 1.02199(5) 0.0307(3) Uani 1 1 d . . . H2 H 0.5371 0.5738 1.0238 0.037 Uiso 1 1 calc R . . O1 O 0.27135(10) 0.68170(11) 1.08435(6) 0.0440(3) Uani 1 1 d . . . S1 S 0.64539(4) 0.51457(4) 0.92063(2) 0.04274(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 0.0590(10) 0.0343(8) 0.0384(8) -0.0013(6) -0.0010(8) 0.0087(7) C2 0.0298(7) 0.0312(7) 0.0254(7) -0.0029(5) -0.0011(5) 0.0033(6) C3 0.0275(7) 0.0301(7) 0.0317(7) -0.0041(5) -0.0003(6) -0.0051(5) C4 0.0326(7) 0.0328(7) 0.0270(7) -0.0033(6) -0.0008(6) 0.0019(6) C5 0.0418(8) 0.0429(8) 0.0327(7) 0.0001(6) -0.0044(7) -0.0079(7) C6 0.0614(11) 0.0453(9) 0.0350(8) -0.0036(7) -0.0139(8) -0.0075(8) C7 0.0818(13) 0.0422(9) 0.0258(8) 0.0001(6) -0.0066(8) -0.0007(9) C8 0.0768(13) 0.0549(11) 0.0365(9) 0.0069(8) 0.0056(9) -0.0184(10) C9 0.0486(9) 0.0512(10) 0.0367(9) 0.0000(7) 0.0007(7) -0.0135(8) C10 0.0271(7) 0.0476(8) 0.0213(7) -0.0045(6) 0.0004(5) -0.0023(6) C11 0.0526(9) 0.0451(9) 0.0289(8) 0.0055(6) -0.0080(7) -0.0129(8) C12 0.0982(16) 0.0689(12) 0.0303(9) 0.0045(8) -0.0060(10) -0.0488(11) C13 0.0667(14) 0.129(2) 0.0401(11) -0.0181(12) 0.0089(10) -0.0636(15) C14 0.0279(9) 0.139(2) 0.0742(16) -0.0372(16) 0.0016(9) -0.0139(12) C15 0.0305(8) 0.0786(12) 0.0592(11) -0.0197(9) -0.0043(8) 0.0077(8) C16 0.0369(8) 0.0300(7) 0.0304(7) -0.0034(6) 0.0025(6) -0.0029(6) C17 0.0387(8) 0.0351(8) 0.0273(7) 0.0008(6) 0.0025(6) -0.0092(6) C18 0.0596(11) 0.0507(10) 0.0352(9) -0.0073(7) 0.0011(8) -0.0048(8) C19 0.0849(15) 0.0712(13) 0.0317(9) -0.0089(9) -0.0081(9) -0.0122(11) C20 0.0749(14) 0.0845(14) 0.0344(9) 0.0116(9) -0.0184(9) -0.0180(13) C21 0.0663(12) 0.0685(12) 0.0481(11) 0.0178(9) -0.0119(9) 0.0047(10) C22 0.0534(10) 0.0475(9) 0.0356(8) 0.0027(7) -0.0029(7) 0.0042(8) Cl1 0.1544(6) 0.0699(3) 0.0296(2) 0.0081(2) -0.0207(3) -0.0179(4) N1 0.0260(6) 0.0384(7) 0.0276(6) -0.0058(5) -0.0034(5) 0.0011(5) O1 0.0382(6) 0.0557(7) 0.0380(6) -0.0081(5) 0.0032(5) 0.0110(5) S1 0.02661(17) 0.0656(3) 0.0360(2) -0.00534(17) -0.00061(16) 0.00768(17) _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 C2 1.5400(19) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 N1 1.4590(17) . ? C2 C10 1.5333(19) . ? C2 C3 1.5364(18) . ? C3 C4 1.4922(19) . ? C3 S1 1.6252(14) . ? C4 C9 1.388(2) . ? C4 C5 1.3914(19) . ? C5 C6 1.389(2) . ? C5 H5 0.9500 . ? C6 C7 1.369(2) . ? C6 H6 0.9500 . ? C7 C8 1.369(2) . ? C7 Cl1 1.7434(16) . ? C8 C9 1.385(2) . ? C8 H8 0.9500 . ? C9 H9 0.9500 . ? C10 C15 1.378(2) . ? C10 C11 1.396(2) . ? C11 C12 1.384(2) . ? C11 H11 0.9500 . ? C12 C13 1.368(3) . ? C12 H12 0.9500 . ? C13 C14 1.359(4) . ? C13 H13 0.9500 . ? C14 C15 1.395(3) . ? C14 H14 0.9500 . ? C15 H15 0.9500 . ? C16 O1 1.2264(17) . ? C16 N1 1.3554(17) . ? C16 C17 1.4966(19) . ? C17 C22 1.383(2) . ? C17 C18 1.395(2) . ? C18 C19 1.375(2) . ? C18 H18 0.9500 . ? C19 C20 1.358(3) . ? C19 H19 0.9500 . ? C20 C21 1.380(3) . ? C20 H20 0.9500 . ? C21 C22 1.393(2) . ? C21 H21 0.9500 . ? C22 H22 0.9500 . ? N1 H2 0.8800 . ? 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 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? N1 C2 C10 109.66(11) . . ? N1 C2 C3 108.87(11) . . ? C10 C2 C3 106.91(10) . . ? N1 C2 C1 109.73(11) . . ? C10 C2 C1 114.62(13) . . ? C3 C2 C1 106.85(11) . . ? C4 C3 C2 117.41(11) . . ? C4 C3 S1 119.13(10) . . ? C2 C3 S1 123.38(10) . . ? C9 C4 C5 118.70(14) . . ? C9 C4 C3 118.30(13) . . ? C5 C4 C3 122.96(13) . . ? C6 C5 C4 120.67(15) . . ? C6 C5 H5 119.7 . . ? C4 C5 H5 119.7 . . ? C7 C6 C5 119.04(15) . . ? C7 C6 H6 120.5 . . ? C5 C6 H6 120.5 . . ? C6 C7 C8 121.61(15) . . ? C6 C7 Cl1 118.78(14) . . ? C8 C7 Cl1 119.61(14) . . ? C7 C8 C9 119.37(16) . . ? C7 C8 H8 120.3 . . ? C9 C8 H8 120.3 . . ? C8 C9 C4 120.57(16) . . ? C8 C9 H9 119.7 . . ? C4 C9 H9 119.7 . . ? C15 C10 C11 119.13(15) . . ? C15 C10 C2 122.61(14) . . ? C11 C10 C2 118.17(13) . . ? C12 C11 C10 120.10(18) . . ? C12 C11 H11 120.0 . . ? C10 C11 H11 120.0 . . ? C13 C12 C11 120.5(2) . . ? C13 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? C14 C13 C12 119.53(18) . . ? C14 C13 H13 120.2 . . ? C12 C13 H13 120.2 . . ? C13 C14 C15 121.4(2) . . ? C13 C14 H14 119.3 . . ? C15 C14 H14 119.3 . . ? C10 C15 C14 119.3(2) . . ? C10 C15 H15 120.3 . . ? C14 C15 H15 120.3 . . ? O1 C16 N1 123.52(14) . . ? O1 C16 C17 121.37(13) . . ? N1 C16 C17 115.09(12) . . ? C22 C17 C18 118.69(15) . . ? C22 C17 C16 122.97(13) . . ? C18 C17 C16 118.34(14) . . ? C19 C18 C17 120.10(18) . . ? C19 C18 H18 120.0 . . ? C17 C18 H18 119.9 . . ? C20 C19 C18 120.95(18) . . ? C20 C19 H19 119.5 . . ? C18 C19 H19 119.5 . . ? C19 C20 C21 120.25(18) . . ? C19 C20 H20 119.9 . . ? C21 C20 H20 119.9 . . ? C20 C21 C22 119.44(19) . . ? C20 C21 H21 120.3 . . ? C22 C21 H21 120.3 . . ? C17 C22 C21 120.56(16) . . ? C17 C22 H22 119.7 . . ? C21 C22 H22 119.7 . . ? C16 N1 C2 124.87(11) . . ? C16 N1 H2 117.6 . . ? C2 N1 H2 117.6 . . ? 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 N1 C2 C3 C4 -172.57(11) . . . . ? C10 C2 C3 C4 69.03(14) . . . . ? C1 C2 C3 C4 -54.13(15) . . . . ? N1 C2 C3 S1 4.15(15) . . . . ? C10 C2 C3 S1 -114.24(12) . . . . ? C1 C2 C3 S1 122.60(12) . . . . ? C2 C3 C4 C9 116.60(15) . . . . ? S1 C3 C4 C9 -60.27(17) . . . . ? C2 C3 C4 C5 -65.59(17) . . . . ? S1 C3 C4 C5 117.54(14) . . . . ? C9 C4 C5 C6 1.9(2) . . . . ? C3 C4 C5 C6 -175.93(14) . . . . ? C4 C5 C6 C7 -1.8(3) . . . . ? C5 C6 C7 C8 0.1(3) . . . . ? C5 C6 C7 Cl1 -179.95(13) . . . . ? C6 C7 C8 C9 1.4(3) . . . . ? Cl1 C7 C8 C9 -178.50(15) . . . . ? C7 C8 C9 C4 -1.3(3) . . . . ? C5 C4 C9 C8 -0.3(3) . . . . ? C3 C4 C9 C8 177.61(15) . . . . ? N1 C2 C10 C15 123.93(15) . . . . ? C3 C2 C10 C15 -118.19(15) . . . . ? C1 C2 C10 C15 0.0(2) . . . . ? N1 C2 C10 C11 -59.60(16) . . . . ? C3 C2 C10 C11 58.28(16) . . . . ? C1 C2 C10 C11 176.48(12) . . . . ? C15 C10 C11 C12 0.5(2) . . . . ? C2 C10 C11 C12 -176.13(13) . . . . ? C10 C11 C12 C13 0.0(3) . . . . ? C11 C12 C13 C14 -0.7(3) . . . . ? C12 C13 C14 C15 0.9(4) . . . . ? C11 C10 C15 C14 -0.3(3) . . . . ? C2 C10 C15 C14 176.15(16) . . . . ? C13 C14 C15 C10 -0.4(3) . . . . ? O1 C16 C17 C22 151.43(15) . . . . ? N1 C16 C17 C22 -30.4(2) . . . . ? O1 C16 C17 C18 -28.8(2) . . . . ? N1 C16 C17 C18 149.33(14) . . . . ? C22 C17 C18 C19 0.7(2) . . . . ? C16 C17 C18 C19 -179.12(15) . . . . ? C17 C18 C19 C20 -0.6(3) . . . . ? C18 C19 C20 C21 0.1(3) . . . . ? C19 C20 C21 C22 0.3(3) . . . . ? C18 C17 C22 C21 -0.2(2) . . . . ? C16 C17 C22 C21 179.52(15) . . . . ? C20 C21 C22 C17 -0.2(3) . . . . ? O1 C16 N1 C2 1.7(2) . . . . ? C17 C16 N1 C2 -176.42(12) . . . . ? C10 C2 N1 C16 -65.45(16) . . . . ? C3 C2 N1 C16 177.91(12) . . . . ? C1 C2 N1 C16 61.28(17) . . . . ? _diffrn_measured_fraction_theta_max 0.947 _diffrn_reflns_theta_full 28.39 _diffrn_measured_fraction_theta_full 0.947 _refine_diff_density_max 0.524 _refine_diff_density_min -0.411 _refine_diff_density_rms 0.158