# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Min Shi' _publ_contact_author_email MSHI@MAIL.SIOC.AC.CN _publ_section_title ; Asymmetric Catalytic aza-Morita-Baylis-Hillman Reaction (aza-MBH): A Remarkable Functional Group-Caused Reversal Asymmetric Induction ; loop_ _publ_author_name 'Min Shi.' 'Xu-Guang Liu.' 'Ming-Juan Qi.' # Attachment 'cd2677.cif' data_cd2677 _database_code_depnum_ccdc_archive 'CCDC 601323' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H21 N O5 S' _chemical_formula_weight 387.44 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 8.8105(13) _cell_length_b 9.4689(13) _cell_length_c 12.1148(17) _cell_angle_alpha 90.00 _cell_angle_beta 103.853(2) _cell_angle_gamma 90.00 _cell_volume 981.3(2) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2402 _cell_measurement_theta_min 4.762 _cell_measurement_theta_max 50.254 _exptl_crystal_description ? _exptl_crystal_colour colorless _exptl_crystal_size_max 0.510 _exptl_crystal_size_mid 0.485 _exptl_crystal_size_min 0.228 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.311 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 408 _exptl_absorpt_coefficient_mu 0.195 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.53634 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _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 5737 _diffrn_reflns_av_R_equivalents 0.1286 _diffrn_reflns_av_sigmaI/netI 0.0950 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.73 _diffrn_reflns_theta_max 27.00 _reflns_number_total 4019 _reflns_number_gt 3149 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.0919P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.10(10) _chemical_absolute_configuration ad _refine_ls_number_reflns 4019 _refine_ls_number_parameters 255 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0727 _refine_ls_R_factor_gt 0.0636 _refine_ls_wR_factor_ref 0.1580 _refine_ls_wR_factor_gt 0.1529 _refine_ls_goodness_of_fit_ref 0.977 _refine_ls_restrained_S_all 0.976 _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 -0.05286(10) 0.95794(9) 1.01874(6) 0.0523(2) Uani 1 1 d . . . O1 O 0.1466(3) 1.2099(3) 0.7557(2) 0.0563(6) Uani 1 1 d . . . O2 O 0.2616(4) 0.7528(4) 0.7491(3) 0.0828(9) Uani 1 1 d . . . O3 O 0.3283(3) 1.1888(4) 0.6561(2) 0.0801(9) Uani 1 1 d . . . O4 O -0.1038(3) 0.8208(3) 0.9779(2) 0.0633(7) Uani 1 1 d . . . O5 O -0.1659(3) 1.0623(3) 1.0292(2) 0.0667(7) Uani 1 1 d . . . N1 N 0.0469(4) 1.0214(4) 0.9365(3) 0.0625(8) Uani 1 1 d D . . C1 C 0.3734(6) 1.0203(6) 0.9529(4) 0.0856(13) Uani 1 1 d . . . H1A H 0.4815 1.0128 0.9661 0.103 Uiso 1 1 calc R . . H1B H 0.3294 1.0827 0.9957 0.103 Uiso 1 1 calc R . . C2 C 0.2833(4) 0.9431(5) 0.8743(3) 0.0593(8) Uani 1 1 d . . . C3 C 0.1052(4) 0.9413(4) 0.8535(2) 0.0536(8) Uani 1 1 d . . . C4 C 0.0224(4) 0.9861(4) 0.7338(3) 0.0500(8) Uani 1 1 d . . . C5 C 0.0480(4) 1.1113(4) 0.6864(3) 0.0505(8) Uani 1 1 d . . . C6 C -0.0285(5) 1.1504(5) 0.5782(3) 0.0650(10) Uani 1 1 d . . . H6 H -0.0072 1.2367 0.5485 0.078 Uiso 1 1 calc R . . C7 C -0.1376(5) 1.0597(6) 0.5143(3) 0.0734(12) Uani 1 1 d . . . H7 H -0.1888 1.0834 0.4402 0.088 Uiso 1 1 calc R . . C8 C -0.1699(4) 0.9353(6) 0.5602(3) 0.0769(13) Uani 1 1 d . . . H8 H -0.2452 0.8753 0.5177 0.092 Uiso 1 1 calc R . . C9 C -0.0921(4) 0.8968(5) 0.6694(3) 0.0647(9) Uani 1 1 d . . . H9 H -0.1158 0.8119 0.6999 0.078 Uiso 1 1 calc R . . C10 C 0.3455(5) 0.8414(5) 0.8029(3) 0.0666(10) Uani 1 1 d . . . C11 C 0.5146(5) 0.8516(8) 0.7973(4) 0.1048(18) Uani 1 1 d . . . H11A H 0.5315 0.7932 0.7366 0.157 Uiso 1 1 calc R . . H11B H 0.5806 0.8202 0.8680 0.157 Uiso 1 1 calc R . . H11C H 0.5391 0.9479 0.7837 0.157 Uiso 1 1 calc R . . C12 C 0.2829(4) 1.2464(4) 0.7284(3) 0.0594(9) Uani 1 1 d . . . C13 C 0.3588(6) 1.3632(6) 0.8016(5) 0.0920(15) Uani 1 1 d . . . H13A H 0.4251 1.3254 0.8698 0.138 Uiso 1 1 calc R . . H13B H 0.2804 1.4222 0.8208 0.138 Uiso 1 1 calc R . . H13C H 0.4204 1.4180 0.7618 0.138 Uiso 1 1 calc R . . C14 C 0.0741(4) 0.9365(4) 1.1537(3) 0.0477(7) Uani 1 1 d . . . C15 C 0.1847(4) 0.8304(4) 1.1705(3) 0.0553(8) Uani 1 1 d . . . H15 H 0.1931 0.7711 1.1111 0.066 Uiso 1 1 calc R . . C16 C 0.2826(4) 0.8141(4) 1.2773(3) 0.0611(9) Uani 1 1 d . . . H16 H 0.3566 0.7422 1.2894 0.073 Uiso 1 1 calc R . . C17 C 0.2736(4) 0.9019(5) 1.3666(3) 0.0632(10) Uani 1 1 d . . . C18 C 0.1606(5) 1.0063(4) 1.3469(3) 0.0682(10) Uani 1 1 d . . . H18 H 0.1520 1.0660 1.4061 0.082 Uiso 1 1 calc R . . C19 C 0.0596(4) 1.0239(4) 1.2408(3) 0.0604(9) Uani 1 1 d . . . H19 H -0.0166 1.0939 1.2289 0.073 Uiso 1 1 calc R . . C20 C 0.3789(5) 0.8811(7) 1.4827(4) 0.0913(14) Uani 1 1 d . . . H20A H 0.4519 0.8067 1.4800 0.137 Uiso 1 1 calc R . . H20B H 0.3173 0.8563 1.5353 0.137 Uiso 1 1 calc R . . H20C H 0.4348 0.9670 1.5070 0.137 Uiso 1 1 calc R . . H1 H 0.060(5) 1.109(2) 0.940(4) 0.070(13) Uiso 1 1 d D . . H3 H 0.070(4) 0.850(4) 0.877(3) 0.060(11) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 S1 0.0500(4) 0.0614(5) 0.0435(4) 0.0057(4) 0.0072(3) -0.0042(4) O1 0.0500(13) 0.0675(15) 0.0526(13) -0.0073(11) 0.0148(11) -0.0044(12) O2 0.0698(19) 0.098(2) 0.080(2) -0.0164(17) 0.0165(16) 0.0054(18) O3 0.0480(15) 0.122(3) 0.0712(18) -0.0260(17) 0.0168(14) -0.0088(16) O4 0.0617(15) 0.0703(16) 0.0523(13) 0.0067(12) 0.0027(12) -0.0039(13) O5 0.0611(16) 0.0741(16) 0.0636(15) 0.0130(13) 0.0127(12) 0.0105(14) N1 0.085(2) 0.0529(17) 0.0533(17) -0.0045(14) 0.0246(16) -0.0053(16) C1 0.069(3) 0.110(3) 0.062(2) -0.002(2) -0.013(2) 0.000(3) C2 0.0484(17) 0.080(2) 0.0416(15) 0.0085(18) -0.0036(13) 0.000(2) C3 0.0525(18) 0.066(2) 0.0403(14) 0.0012(16) 0.0073(13) -0.0015(18) C4 0.0404(15) 0.067(2) 0.0407(14) -0.0029(14) 0.0053(12) 0.0042(14) C5 0.0414(17) 0.068(2) 0.0416(16) -0.0056(15) 0.0094(13) 0.0022(15) C6 0.054(2) 0.093(3) 0.0480(19) 0.0081(19) 0.0134(17) 0.011(2) C7 0.054(2) 0.115(4) 0.0431(18) -0.003(2) -0.0056(16) 0.017(2) C8 0.0463(19) 0.114(4) 0.059(2) -0.025(2) -0.0108(16) -0.001(2) C9 0.051(2) 0.075(2) 0.062(2) -0.0077(18) 0.0011(17) -0.0059(18) C10 0.052(2) 0.093(3) 0.0495(18) 0.013(2) 0.0002(16) 0.011(2) C11 0.047(2) 0.174(6) 0.086(3) 0.004(3) 0.000(2) 0.019(3) C12 0.0447(19) 0.075(2) 0.059(2) -0.0010(18) 0.0122(16) 0.0013(17) C13 0.062(3) 0.106(3) 0.109(4) -0.035(3) 0.023(3) -0.017(3) C14 0.0435(16) 0.0557(19) 0.0441(14) 0.0042(14) 0.0112(12) -0.0050(14) C15 0.0503(19) 0.070(2) 0.0464(17) -0.0050(16) 0.0130(14) 0.0025(17) C16 0.0420(17) 0.082(3) 0.0563(19) 0.0052(18) 0.0066(15) 0.0086(18) C17 0.0480(19) 0.090(3) 0.0484(18) 0.0034(17) 0.0057(15) -0.0070(19) C18 0.076(3) 0.080(2) 0.0471(18) -0.0147(17) 0.0117(18) -0.002(2) C19 0.057(2) 0.069(2) 0.0537(19) -0.0005(17) 0.0094(17) 0.0033(18) C20 0.066(3) 0.137(4) 0.058(2) -0.005(3) -0.011(2) 0.000(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 O4 1.424(3) . ? S1 O5 1.430(3) . ? S1 N1 1.596(3) . ? S1 C14 1.758(3) . ? O1 C12 1.364(4) . ? O1 C5 1.408(4) . ? O2 C10 1.202(5) . ? O3 C12 1.180(4) . ? N1 C3 1.448(4) . ? N1 H1 0.834(19) . ? C1 C2 1.307(6) . ? C1 H1A 0.9300 . ? C1 H1B 0.9300 . ? C2 C10 1.485(6) . ? C2 C3 1.529(5) . ? C3 C4 1.519(4) . ? C3 H3 0.98(4) . ? C4 C5 1.359(5) . ? C4 C9 1.401(5) . ? C5 C6 1.373(5) . ? C6 C7 1.381(6) . ? C6 H6 0.9300 . ? C7 C8 1.362(7) . ? C7 H7 0.9300 . ? C8 C9 1.384(6) . ? C8 H8 0.9300 . ? C9 H9 0.9300 . ? C10 C11 1.510(6) . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 C13 1.474(6) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 C19 1.370(5) . ? C14 C15 1.380(5) . ? C15 C16 1.381(5) . ? C15 H15 0.9300 . ? C16 C17 1.382(5) . ? C16 H16 0.9300 . ? C17 C18 1.383(6) . ? C17 C20 1.501(5) . ? C18 C19 1.387(5) . ? C18 H18 0.9300 . ? C19 H19 0.9300 . ? C20 H20A 0.9600 . ? C20 H20B 0.9600 . ? C20 H20C 0.9600 . ? 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 O4 S1 O5 119.53(17) . . ? O4 S1 N1 107.54(16) . . ? O5 S1 N1 107.14(17) . . ? O4 S1 C14 107.18(15) . . ? O5 S1 C14 107.37(16) . . ? N1 S1 C14 107.56(17) . . ? C12 O1 C5 118.5(3) . . ? C3 N1 S1 125.2(3) . . ? C3 N1 H1 119(3) . . ? S1 N1 H1 116(3) . . ? C2 C1 H1A 120.0 . . ? C2 C1 H1B 120.0 . . ? H1A C1 H1B 120.0 . . ? C1 C2 C10 122.9(4) . . ? C1 C2 C3 123.2(4) . . ? C10 C2 C3 113.8(3) . . ? N1 C3 C4 110.3(3) . . ? N1 C3 C2 113.6(3) . . ? C4 C3 C2 113.2(3) . . ? N1 C3 H3 94(2) . . ? C4 C3 H3 114(2) . . ? C2 C3 H3 110(2) . . ? C5 C4 C9 117.4(3) . . ? C5 C4 C3 123.8(3) . . ? C9 C4 C3 118.7(3) . . ? C4 C5 C6 123.0(3) . . ? C4 C5 O1 117.9(3) . . ? C6 C5 O1 118.8(3) . . ? C5 C6 C7 118.9(4) . . ? C5 C6 H6 120.5 . . ? C7 C6 H6 120.5 . . ? C8 C7 C6 119.7(4) . . ? C8 C7 H7 120.2 . . ? C6 C7 H7 120.2 . . ? C7 C8 C9 120.9(4) . . ? C7 C8 H8 119.5 . . ? C9 C8 H8 119.5 . . ? C8 C9 C4 119.9(4) . . ? C8 C9 H9 120.0 . . ? C4 C9 H9 120.0 . . ? O2 C10 C2 120.3(4) . . ? O2 C10 C11 120.4(4) . . ? C2 C10 C11 119.4(4) . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? O3 C12 O1 122.6(4) . . ? O3 C12 C13 127.4(4) . . ? O1 C12 C13 110.1(3) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C19 C14 C15 121.2(3) . . ? C19 C14 S1 119.4(3) . . ? C15 C14 S1 119.4(2) . . ? C14 C15 C16 118.7(3) . . ? C14 C15 H15 120.6 . . ? C16 C15 H15 120.6 . . ? C15 C16 C17 121.7(3) . . ? C15 C16 H16 119.1 . . ? C17 C16 H16 119.1 . . ? C16 C17 C18 118.0(3) . . ? C16 C17 C20 121.1(4) . . ? C18 C17 C20 120.9(4) . . ? C17 C18 C19 121.4(3) . . ? C17 C18 H18 119.3 . . ? C19 C18 H18 119.3 . . ? C14 C19 C18 119.0(4) . . ? C14 C19 H19 120.5 . . ? C18 C19 H19 120.5 . . ? C17 C20 H20A 109.5 . . ? C17 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C17 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? 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 O4 S1 N1 C3 -13.4(4) . . . . ? O5 S1 N1 C3 -143.0(3) . . . . ? C14 S1 N1 C3 101.8(3) . . . . ? S1 N1 C3 C4 112.3(4) . . . . ? S1 N1 C3 C2 -119.4(4) . . . . ? C1 C2 C3 N1 -6.1(6) . . . . ? C10 C2 C3 N1 169.6(3) . . . . ? C1 C2 C3 C4 120.7(4) . . . . ? C10 C2 C3 C4 -63.6(4) . . . . ? N1 C3 C4 C5 72.5(4) . . . . ? C2 C3 C4 C5 -56.0(5) . . . . ? N1 C3 C4 C9 -104.6(4) . . . . ? C2 C3 C4 C9 126.8(4) . . . . ? C9 C4 C5 C6 -2.4(5) . . . . ? C3 C4 C5 C6 -179.6(3) . . . . ? C9 C4 C5 O1 171.4(3) . . . . ? C3 C4 C5 O1 -5.8(5) . . . . ? C12 O1 C5 C4 116.4(4) . . . . ? C12 O1 C5 C6 -69.5(4) . . . . ? C4 C5 C6 C7 0.5(5) . . . . ? O1 C5 C6 C7 -173.3(3) . . . . ? C5 C6 C7 C8 1.6(6) . . . . ? C6 C7 C8 C9 -1.5(6) . . . . ? C7 C8 C9 C4 -0.5(6) . . . . ? C5 C4 C9 C8 2.4(5) . . . . ? C3 C4 C9 C8 179.8(3) . . . . ? C1 C2 C10 O2 164.6(5) . . . . ? C3 C2 C10 O2 -11.2(5) . . . . ? C1 C2 C10 C11 -16.3(6) . . . . ? C3 C2 C10 C11 167.9(4) . . . . ? C5 O1 C12 O3 -7.5(6) . . . . ? C5 O1 C12 C13 172.8(4) . . . . ? O4 S1 C14 C19 -135.5(3) . . . . ? O5 S1 C14 C19 -5.9(3) . . . . ? N1 S1 C14 C19 109.1(3) . . . . ? O4 S1 C14 C15 43.4(3) . . . . ? O5 S1 C14 C15 173.0(3) . . . . ? N1 S1 C14 C15 -72.0(3) . . . . ? C19 C14 C15 C16 -0.5(5) . . . . ? S1 C14 C15 C16 -179.4(3) . . . . ? C14 C15 C16 C17 -0.7(5) . . . . ? C15 C16 C17 C18 1.2(6) . . . . ? C15 C16 C17 C20 178.9(4) . . . . ? C16 C17 C18 C19 -0.5(6) . . . . ? C20 C17 C18 C19 -178.1(4) . . . . ? C15 C14 C19 C18 1.2(5) . . . . ? S1 C14 C19 C18 -179.9(3) . . . . ? C17 C18 C19 C14 -0.7(6) . . . . ? 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 N1 H1 O4 0.834(19) 2.23(3) 3.019(4) 157(4) 2_557 _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.471 _refine_diff_density_min -0.339 _refine_diff_density_rms 0.077 # Attachment 'cd26535.cif' data_cd26535 _database_code_depnum_ccdc_archive 'CCDC 632081' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C25 H22 Br N O5 S' _chemical_formula_weight 528.41 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' Br Br -0.2901 2.4595 '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 8.9781(11) _cell_length_b 10.3536(12) _cell_length_c 25.647(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2384.0(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 3651 _cell_measurement_theta_min 4.807 _cell_measurement_theta_max 43.350 _exptl_crystal_description prismatic _exptl_crystal_colour colorless _exptl_crystal_size_max 0.506 _exptl_crystal_size_mid 0.422 _exptl_crystal_size_min 0.347 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.472 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1080 _exptl_absorpt_coefficient_mu 1.848 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.64925 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _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 14054 _diffrn_reflns_av_R_equivalents 0.0543 _diffrn_reflns_av_sigmaI/netI 0.0712 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -32 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.12 _diffrn_reflns_theta_max 26.99 _reflns_number_total 5149 _reflns_number_gt 3331 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _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^)+(0.0386P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0101(6) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.002(7) _chemical_absolute_configuration ad _refine_ls_number_reflns 5149 _refine_ls_number_parameters 309 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0653 _refine_ls_R_factor_gt 0.0407 _refine_ls_wR_factor_ref 0.0830 _refine_ls_wR_factor_gt 0.0785 _refine_ls_goodness_of_fit_ref 0.847 _refine_ls_restrained_S_all 0.847 _refine_ls_shift/su_max 0.028 _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 Br Br 0.43697(5) 0.43098(5) 0.964304(16) 0.0928(2) Uani 1 1 d . . . S1 S 0.33058(8) 0.19770(7) 0.63980(3) 0.0416(2) Uani 1 1 d . . . O1 O -0.0059(3) 0.6504(2) 0.76646(8) 0.0557(6) Uani 1 1 d . . . O2 O 0.0145(2) 0.44055(19) 0.74644(7) 0.0394(5) Uani 1 1 d . . . O3 O 0.2333(3) 0.6856(2) 0.63146(11) 0.0871(9) Uani 1 1 d . . . O4 O 0.3721(2) 0.0983(2) 0.67568(8) 0.0596(6) Uani 1 1 d . . . O5 O 0.4413(2) 0.2753(2) 0.61483(8) 0.0541(6) Uani 1 1 d . . . N1 N 0.2260(3) 0.2954(2) 0.67204(9) 0.0395(6) Uani 1 1 d D . . C1 C -0.0529(3) 0.4637(3) 0.69803(11) 0.0371(7) Uani 1 1 d . . . C2 C -0.2058(3) 0.4837(3) 0.69560(13) 0.0485(8) Uani 1 1 d . . . H2 H -0.2624 0.4889 0.7259 0.058 Uiso 1 1 calc R . . C3 C -0.2706(4) 0.4955(4) 0.64800(15) 0.0653(10) Uani 1 1 d . . . H3 H -0.3731 0.5068 0.6456 0.078 Uiso 1 1 calc R . . C4 C -0.1863(4) 0.4908(3) 0.60335(14) 0.0639(10) Uani 1 1 d . . . H4 H -0.2313 0.4997 0.5709 0.077 Uiso 1 1 calc R . . C5 C -0.0348(4) 0.4729(3) 0.60690(11) 0.0520(9) Uani 1 1 d . . . H5 H 0.0217 0.4710 0.5765 0.062 Uiso 1 1 calc R . . C6 C 0.0355(3) 0.4576(3) 0.65434(10) 0.0359(7) Uani 1 1 d . . . C7 C 0.2016(3) 0.4300(3) 0.65660(11) 0.0338(6) Uani 1 1 d . . . C8 C 0.2911(3) 0.5224(3) 0.69003(11) 0.0361(7) Uani 1 1 d . . . C9 C 0.3713(3) 0.4846(3) 0.73010(12) 0.0505(8) Uani 1 1 d . . . H9A H 0.4306 0.5436 0.7479 0.061 Uiso 1 1 calc R . . H9B H 0.3687 0.3987 0.7407 0.061 Uiso 1 1 calc R . . C10 C 0.2920(4) 0.6572(3) 0.67205(14) 0.0529(9) Uani 1 1 d . . . C11 C 0.3690(6) 0.7589(4) 0.70436(18) 0.1044(16) Uani 1 1 d . . . H11A H 0.4722 0.7365 0.7084 0.127 Uiso 1 1 calc R . . H11B H 0.3227 0.7639 0.7380 0.127 Uiso 1 1 calc R . . H11C H 0.3613 0.8410 0.6872 0.127 Uiso 1 1 calc R . . C12 C 0.0370(3) 0.5449(3) 0.77772(11) 0.0406(7) Uani 1 1 d . . . C13 C 0.1245(3) 0.5096(3) 0.82439(11) 0.0434(8) Uani 1 1 d . . . C14 C 0.1749(4) 0.6108(3) 0.85509(12) 0.0512(8) Uani 1 1 d . . . H14 H 0.1478 0.6952 0.8471 0.061 Uiso 1 1 calc R . . C15 C 0.2651(4) 0.5866(4) 0.89747(13) 0.0608(10) Uani 1 1 d . . . H15 H 0.2985 0.6541 0.9183 0.073 Uiso 1 1 calc R . . C16 C 0.3044(4) 0.4634(4) 0.90835(12) 0.0555(9) Uani 1 1 d . . . C17 C 0.2547(4) 0.3612(4) 0.87895(13) 0.0652(10) Uani 1 1 d . . . H17 H 0.2819 0.2771 0.8875 0.078 Uiso 1 1 calc R . . C18 C 0.1635(4) 0.3851(3) 0.83652(12) 0.0550(9) Uani 1 1 d . . . H18 H 0.1288 0.3169 0.8163 0.066 Uiso 1 1 calc R . . C19 C 0.2225(3) 0.1247(3) 0.59069(11) 0.0401(7) Uani 1 1 d . . . C20 C 0.1755(3) 0.1960(3) 0.54854(11) 0.0515(8) Uani 1 1 d . . . H20 H 0.2031 0.2823 0.5455 0.062 Uiso 1 1 calc R . . C21 C 0.0879(4) 0.1401(3) 0.51109(12) 0.0569(9) Uani 1 1 d . . . H21 H 0.0546 0.1898 0.4833 0.068 Uiso 1 1 calc R . . C22 C 0.0487(4) 0.0132(3) 0.51370(13) 0.0519(8) Uani 1 1 d . . . C23 C 0.0981(3) -0.0590(3) 0.55541(12) 0.0543(9) Uani 1 1 d . . . H23 H 0.0735 -0.1461 0.5575 0.065 Uiso 1 1 calc R . . C24 C 0.1833(4) -0.0038(3) 0.59401(13) 0.0471(8) Uani 1 1 d . . . H24 H 0.2144 -0.0531 0.6223 0.057 Uiso 1 1 calc R . . C25 C -0.0475(4) -0.0478(4) 0.47204(13) 0.0745(11) Uani 1 1 d . . . H25A H -0.0203 -0.1369 0.4679 0.112 Uiso 1 1 calc R . . H25B H -0.0331 -0.0031 0.4396 0.112 Uiso 1 1 calc R . . H25C H -0.1503 -0.0421 0.4821 0.112 Uiso 1 1 calc R . . H7 H 0.240(2) 0.436(2) 0.6229(8) 0.058(5) Uiso 1 1 d . . . H1 H 0.164(3) 0.260(3) 0.6900(9) 0.042(9) Uiso 1 1 d 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 Br 0.0800(3) 0.1334(4) 0.0650(3) 0.0020(3) -0.0192(2) 0.0060(3) S1 0.0405(4) 0.0355(4) 0.0489(4) -0.0016(4) 0.0005(4) 0.0059(4) O1 0.0790(16) 0.0353(13) 0.0528(14) -0.0057(10) 0.0007(12) 0.0149(12) O2 0.0494(11) 0.0332(11) 0.0355(10) -0.0018(9) 0.0012(9) 0.0017(10) O3 0.128(2) 0.0450(16) 0.089(2) 0.0188(14) -0.0292(18) -0.0097(16) O4 0.0717(15) 0.0441(14) 0.0630(14) 0.0041(11) -0.0185(12) 0.0124(12) O5 0.0401(11) 0.0537(14) 0.0684(14) -0.0071(11) 0.0148(11) -0.0003(11) N1 0.0452(14) 0.0294(14) 0.0438(15) 0.0048(12) 0.0112(12) -0.0009(13) C1 0.0449(17) 0.0267(16) 0.0396(16) -0.0031(12) 0.0002(15) -0.0001(14) C2 0.0371(18) 0.050(2) 0.059(2) -0.0011(16) 0.0060(16) -0.0018(15) C3 0.0395(18) 0.072(3) 0.084(3) -0.001(2) -0.012(2) 0.0056(17) C4 0.059(2) 0.078(3) 0.055(2) 0.0017(19) -0.020(2) 0.008(2) C5 0.051(2) 0.066(2) 0.0391(18) -0.0012(16) -0.0049(15) 0.0049(17) C6 0.0393(15) 0.0307(16) 0.0378(16) 0.0003(12) -0.0030(13) -0.0006(13) C7 0.0395(16) 0.0321(16) 0.0298(15) 0.0029(13) 0.0043(12) 0.0000(14) C8 0.0329(15) 0.0371(18) 0.0381(17) -0.0014(13) 0.0038(13) 0.0021(13) C9 0.0442(18) 0.050(2) 0.057(2) -0.0036(16) -0.0036(16) -0.0021(15) C10 0.055(2) 0.044(2) 0.059(2) -0.0012(17) 0.0009(18) -0.0008(17) C11 0.144(4) 0.050(3) 0.119(4) -0.012(2) -0.036(3) -0.024(3) C12 0.0411(17) 0.044(2) 0.0372(16) -0.0071(15) 0.0093(14) -0.0027(16) C13 0.0538(19) 0.0406(19) 0.0359(17) -0.0063(15) 0.0120(15) 0.0002(15) C14 0.0588(19) 0.042(2) 0.052(2) -0.0051(16) 0.0092(19) -0.0064(17) C15 0.062(2) 0.072(3) 0.049(2) -0.0133(19) 0.0043(18) -0.022(2) C16 0.056(2) 0.071(3) 0.0403(18) -0.0052(19) 0.0002(16) 0.003(2) C17 0.087(3) 0.063(3) 0.046(2) 0.0062(19) 0.001(2) 0.011(2) C18 0.078(2) 0.044(2) 0.0432(19) -0.0032(15) 0.0011(18) 0.0017(19) C19 0.0455(17) 0.0415(19) 0.0333(16) -0.0027(14) 0.0077(14) 0.0075(14) C20 0.070(2) 0.0390(18) 0.0455(19) 0.0043(16) 0.0025(17) -0.001(2) C21 0.076(3) 0.055(2) 0.0400(18) 0.0044(16) -0.0016(18) 0.005(2) C22 0.0504(19) 0.056(2) 0.0488(19) -0.0040(17) 0.0031(17) 0.0023(18) C23 0.061(2) 0.042(2) 0.060(2) -0.0077(18) 0.0075(17) -0.0103(18) C24 0.0545(19) 0.0348(18) 0.0521(19) 0.0050(15) 0.0023(17) 0.0037(16) C25 0.072(2) 0.081(3) 0.070(2) -0.015(2) -0.006(2) -0.016(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 Br C16 1.894(3) . ? S1 O4 1.430(2) . ? S1 O5 1.430(2) . ? S1 N1 1.609(3) . ? S1 C19 1.760(3) . ? O1 C12 1.194(3) . ? O2 C12 1.360(3) . ? O2 C1 1.402(3) . ? O3 C10 1.204(4) . ? N1 C7 1.466(4) . ? N1 H1 0.813(17) . ? C1 C6 1.375(4) . ? C1 C2 1.390(4) . ? C2 C3 1.358(4) . ? C2 H2 0.9300 . ? C3 C4 1.374(5) . ? C3 H3 0.9300 . ? C4 C5 1.376(5) . ? C4 H4 0.9300 . ? C5 C6 1.380(4) . ? C5 H5 0.9300 . ? C6 C7 1.519(4) . ? C7 C8 1.516(4) . ? C7 H7 0.93(2) . ? C8 C9 1.314(4) . ? C8 C10 1.469(4) . ? C9 H9A 0.9300 . ? C9 H9B 0.9300 . ? C10 C11 1.508(5) . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 C13 1.478(4) . ? C13 C18 1.371(4) . ? C13 C14 1.387(4) . ? C14 C15 1.378(4) . ? C14 H14 0.9300 . ? C15 C16 1.353(5) . ? C15 H15 0.9300 . ? C16 C17 1.374(5) . ? C17 C18 1.384(4) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? C19 C20 1.376(4) . ? C19 C24 1.379(4) . ? C20 C21 1.369(4) . ? C20 H20 0.9300 . ? C21 C22 1.362(4) . ? C21 H21 0.9300 . ? C22 C23 1.378(4) . ? C22 C25 1.512(4) . ? C23 C24 1.375(4) . ? C23 H23 0.9300 . ? C24 H24 0.9300 . ? C25 H25A 0.9600 . ? C25 H25B 0.9600 . ? C25 H25C 0.9600 . ? 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 O4 S1 O5 120.79(13) . . ? O4 S1 N1 105.88(14) . . ? O5 S1 N1 106.41(14) . . ? O4 S1 C19 107.16(14) . . ? O5 S1 C19 107.69(13) . . ? N1 S1 C19 108.43(13) . . ? C12 O2 C1 116.8(2) . . ? C7 N1 S1 123.1(2) . . ? C7 N1 H1 119(2) . . ? S1 N1 H1 114(2) . . ? C6 C1 C2 122.7(3) . . ? C6 C1 O2 117.7(2) . . ? C2 C1 O2 119.4(3) . . ? C3 C2 C1 118.5(3) . . ? C3 C2 H2 120.8 . . ? C1 C2 H2 120.8 . . ? C2 C3 C4 120.7(3) . . ? C2 C3 H3 119.7 . . ? C4 C3 H3 119.7 . . ? C3 C4 C5 119.6(3) . . ? C3 C4 H4 120.2 . . ? C5 C4 H4 120.2 . . ? C4 C5 C6 121.7(3) . . ? C4 C5 H5 119.1 . . ? C6 C5 H5 119.1 . . ? C1 C6 C5 116.7(3) . . ? C1 C6 C7 123.0(2) . . ? C5 C6 C7 120.3(2) . . ? N1 C7 C8 111.6(2) . . ? N1 C7 C6 109.6(2) . . ? C8 C7 C6 115.1(2) . . ? N1 C7 H7 105.1(14) . . ? C8 C7 H7 106.4(13) . . ? C6 C7 H7 108.5(12) . . ? C9 C8 C10 121.7(3) . . ? C9 C8 C7 123.0(3) . . ? C10 C8 C7 115.1(3) . . ? C8 C9 H9A 120.0 . . ? C8 C9 H9B 120.0 . . ? H9A C9 H9B 120.0 . . ? O3 C10 C8 120.1(3) . . ? O3 C10 C11 120.4(3) . . ? C8 C10 C11 119.6(3) . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? O1 C12 O2 122.4(3) . . ? O1 C12 C13 126.4(3) . . ? O2 C12 C13 111.1(3) . . ? C18 C13 C14 119.9(3) . . ? C18 C13 C12 123.5(3) . . ? C14 C13 C12 116.5(3) . . ? C15 C14 C13 120.1(3) . . ? C15 C14 H14 119.9 . . ? C13 C14 H14 119.9 . . ? C16 C15 C14 119.2(3) . . ? C16 C15 H15 120.4 . . ? C14 C15 H15 120.4 . . ? C15 C16 C17 121.9(3) . . ? C15 C16 Br 119.2(3) . . ? C17 C16 Br 118.9(3) . . ? C16 C17 C18 119.1(3) . . ? C16 C17 H17 120.5 . . ? C18 C17 H17 120.5 . . ? C13 C18 C17 119.8(3) . . ? C13 C18 H18 120.1 . . ? C17 C18 H18 120.1 . . ? C20 C19 C24 119.2(3) . . ? C20 C19 S1 120.1(3) . . ? C24 C19 S1 120.7(2) . . ? C21 C20 C19 120.0(3) . . ? C21 C20 H20 120.0 . . ? C19 C20 H20 120.0 . . ? C22 C21 C20 121.5(3) . . ? C22 C21 H21 119.3 . . ? C20 C21 H21 119.3 . . ? C21 C22 C23 118.5(3) . . ? C21 C22 C25 121.1(3) . . ? C23 C22 C25 120.4(3) . . ? C24 C23 C22 120.8(3) . . ? C24 C23 H23 119.6 . . ? C22 C23 H23 119.6 . . ? C23 C24 C19 119.9(3) . . ? C23 C24 H24 120.1 . . ? C19 C24 H24 120.1 . . ? C22 C25 H25A 109.5 . . ? C22 C25 H25B 109.5 . . ? H25A C25 H25B 109.5 . . ? C22 C25 H25C 109.5 . . ? H25A C25 H25C 109.5 . . ? H25B C25 H25C 109.5 . . ? 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 O4 S1 N1 C7 158.2(2) . . . . ? O5 S1 N1 C7 28.5(3) . . . . ? C19 S1 N1 C7 -87.1(2) . . . . ? C12 O2 C1 C6 106.3(3) . . . . ? C12 O2 C1 C2 -77.6(3) . . . . ? C6 C1 C2 C3 1.1(5) . . . . ? O2 C1 C2 C3 -174.7(3) . . . . ? C1 C2 C3 C4 -1.5(5) . . . . ? C2 C3 C4 C5 0.6(6) . . . . ? C3 C4 C5 C6 0.9(5) . . . . ? C2 C1 C6 C5 0.3(4) . . . . ? O2 C1 C6 C5 176.1(2) . . . . ? C2 C1 C6 C7 -177.3(3) . . . . ? O2 C1 C6 C7 -1.4(4) . . . . ? C4 C5 C6 C1 -1.3(5) . . . . ? C4 C5 C6 C7 176.3(3) . . . . ? S1 N1 C7 C8 -103.1(2) . . . . ? S1 N1 C7 C6 128.2(2) . . . . ? C1 C6 C7 N1 69.8(3) . . . . ? C5 C6 C7 N1 -107.6(3) . . . . ? C1 C6 C7 C8 -56.9(4) . . . . ? C5 C6 C7 C8 125.6(3) . . . . ? N1 C7 C8 C9 -4.6(4) . . . . ? C6 C7 C8 C9 121.1(3) . . . . ? N1 C7 C8 C10 170.7(2) . . . . ? C6 C7 C8 C10 -63.6(3) . . . . ? C9 C8 C10 O3 170.3(3) . . . . ? C7 C8 C10 O3 -5.1(4) . . . . ? C9 C8 C10 C11 -8.7(5) . . . . ? C7 C8 C10 C11 175.9(3) . . . . ? C1 O2 C12 O1 4.4(4) . . . . ? C1 O2 C12 C13 -173.2(2) . . . . ? O1 C12 C13 C18 176.3(3) . . . . ? O2 C12 C13 C18 -6.2(4) . . . . ? O1 C12 C13 C14 -7.3(5) . . . . ? O2 C12 C13 C14 170.1(3) . . . . ? C18 C13 C14 C15 0.6(5) . . . . ? C12 C13 C14 C15 -175.9(3) . . . . ? C13 C14 C15 C16 0.5(5) . . . . ? C14 C15 C16 C17 -1.3(5) . . . . ? C14 C15 C16 Br 176.6(2) . . . . ? C15 C16 C17 C18 1.0(5) . . . . ? Br C16 C17 C18 -176.9(3) . . . . ? C14 C13 C18 C17 -0.9(5) . . . . ? C12 C13 C18 C17 175.4(3) . . . . ? C16 C17 C18 C13 0.1(5) . . . . ? O4 S1 C19 C20 -175.4(2) . . . . ? O5 S1 C19 C20 -44.1(3) . . . . ? N1 S1 C19 C20 70.7(3) . . . . ? O4 S1 C19 C24 5.0(3) . . . . ? O5 S1 C19 C24 136.3(2) . . . . ? N1 S1 C19 C24 -108.9(3) . . . . ? C24 C19 C20 C21 1.4(5) . . . . ? S1 C19 C20 C21 -178.2(2) . . . . ? C19 C20 C21 C22 -1.7(5) . . . . ? C20 C21 C22 C23 0.5(5) . . . . ? C20 C21 C22 C25 -179.8(3) . . . . ? C21 C22 C23 C24 1.0(5) . . . . ? C25 C22 C23 C24 -178.8(3) . . . . ? C22 C23 C24 C19 -1.2(5) . . . . ? C20 C19 C24 C23 0.0(5) . . . . ? S1 C19 C24 C23 179.6(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 N1 H1 O1 0.813(17) 2.130(18) 2.941(3) 174(3) 3_546 _diffrn_measured_fraction_theta_max 0.997 _diffrn_reflns_theta_full 26.99 _diffrn_measured_fraction_theta_full 0.997 _refine_diff_density_max 0.475 _refine_diff_density_min -0.443 _refine_diff_density_rms 0.049