Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Paul Wyatt' 'Jonathan P. H. Charmant' 'Andrew Hudson' 'A. Guy Orpen' 'Hirihattaya Phetmung' _publ_contact_author_name 'Paul Wyatt' _publ_contact_author_address ; School of Chemistry University of Bristol Cantock's Close Bristol BS8 1TS UNITED KINGDOM ; _publ_contact_author_email PAUL.WYATT@BRIS.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Synthesis and Chemistry of Enantiomerically Pure 10,11-dihydrodibenzo[b,f]thiepines ; # Attachment 'sulfideCIF.txt' data_ah1 _database_code_depnum_ccdc_archive 'CCDC 290626' _audit_creation_method SHELXL-97 _chemical_formula_moiety 'C16 H14 F2 O2 S' _chemical_formula_sum 'C16 H14 F2 O2 S' _chemical_formula_weight 308.33 _chemical_absolute_configuration ad loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 '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 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 7.8387(15) _cell_length_b 11.645(2) _cell_length_c 15.4763(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1412.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 7051 _cell_measurement_theta_min 3 _cell_measurement_theta_max 25 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.20 _exptl_crystal_density_diffrn 1.450 _exptl_crystal_density_method none _exptl_crystal_F_000 640 _exptl_absorpt_coefficient_mu 0.253 _exptl_absorpt_correction_type none _exptl_absorpt_correction_t_max ? _exptl_absorpt_correction_t_min ? _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'Frames, each covering 0.3 \% in \w' _diffrn_detector_area_resol_mean 8.2 _diffrn_standards_decay_% 0 _diffrn_reflns_number 9132 _diffrn_reflns_av_R_equivalents 0.0336 _diffrn_reflns_av_sigmaI/netI 0.0254 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.19 _diffrn_reflns_theta_max 27.48 _reflns_number_total 3223 _reflns_number_gt 3041 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker, 1995)' _computing_cell_refinement 'SAINT (Bruker, 1995)' _computing_data_reduction 'SAINT (Bruker, 1995)' _computing_structure_solution 'SHELXTL (Bruker, 2001)' _computing_structure_refinement 'SHELXTL (Bruker, 2001)' _computing_molecular_graphics 'SHELXTL (Bruker, 2001)' _computing_publication_material 'SHELXTL (Bruker, 2001)' _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^)+(0.0327P)^2^+0.2496P] 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 SHELXL _refine_ls_extinction_coef 0.0074(14) _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 0.02(6) _refine_ls_number_reflns 3223 _refine_ls_number_parameters 194 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0295 _refine_ls_R_factor_gt 0.0264 _refine_ls_wR_factor_ref 0.0667 _refine_ls_wR_factor_gt 0.0644 _refine_ls_goodness_of_fit_ref 1.092 _refine_ls_restrained_S_all 1.092 _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 -0.02170(18) 0.01078(12) 0.61316(9) 0.0200(3) Uani 1 1 d . . . C2 C -0.09615(19) 0.00272(14) 0.69511(10) 0.0252(3) Uani 1 1 d . . . C3 C -0.1505(2) -0.09820(16) 0.73133(10) 0.0314(4) Uani 1 1 d . . . H3 H -0.2011 -0.0993 0.7871 0.038 Uiso 1 1 calc R . . C4 C -0.1298(2) -0.19828(15) 0.68458(11) 0.0324(4) Uani 1 1 d . . . H4 H -0.1634 -0.2699 0.7085 0.039 Uiso 1 1 calc R . . C5 C -0.0594(2) -0.19332(13) 0.60249(10) 0.0281(3) Uani 1 1 d . . . H5 H -0.0458 -0.2627 0.5709 0.034 Uiso 1 1 calc R . . C6 C -0.00767(17) -0.09021(12) 0.56443(9) 0.0213(3) Uani 1 1 d . . . C7 C 0.04470(19) -0.10161(12) 0.46930(9) 0.0218(3) Uani 1 1 d . . . H7 H 0.1253 -0.1679 0.4643 0.026 Uiso 1 1 calc R . . C8 C 0.12627(18) 0.00190(12) 0.42466(9) 0.0218(3) Uani 1 1 d . . . H8 H 0.0400 0.0648 0.4200 0.026 Uiso 1 1 calc R . . C9 C 0.28093(19) 0.04621(12) 0.47307(9) 0.0208(3) Uani 1 1 d . . . C10 C 0.4464(2) 0.01763(13) 0.44836(10) 0.0247(3) Uani 1 1 d . . . H10 H 0.4642 -0.0305 0.3996 0.030 Uiso 1 1 calc R . . C11 C 0.5857(2) 0.05894(14) 0.49446(11) 0.0294(3) Uani 1 1 d . . . H11 H 0.6978 0.0379 0.4774 0.035 Uiso 1 1 calc R . . C12 C 0.5627(2) 0.13048(13) 0.56509(10) 0.0286(3) Uani 1 1 d . . . H12 H 0.6576 0.1595 0.5964 0.034 Uiso 1 1 calc R . . C13 C 0.39758(19) 0.15831(12) 0.58867(9) 0.0236(3) Uani 1 1 d . . . C14 C 0.25565(17) 0.11707(12) 0.54553(9) 0.0204(3) Uani 1 1 d . . . C15 C -0.0947(2) -0.22727(17) 0.36775(11) 0.0377(4) Uani 1 1 d . . . H15A H -0.2072 -0.2460 0.3441 0.057 Uiso 1 1 calc R . . H15B H -0.0505 -0.2934 0.3999 0.057 Uiso 1 1 calc R . . H15C H -0.0164 -0.2086 0.3204 0.057 Uiso 1 1 calc R . . C16 C 0.1745(2) 0.05462(16) 0.27869(10) 0.0360(4) Uani 1 1 d . . . H16A H 0.2101 0.0242 0.2225 0.054 Uiso 1 1 calc R . . H16B H 0.2555 0.1136 0.2976 0.054 Uiso 1 1 calc R . . H16C H 0.0605 0.0885 0.2735 0.054 Uiso 1 1 calc R . . F1 F -0.11437(14) 0.10068(9) 0.74178(6) 0.0378(2) Uani 1 1 d . . . F2 F 0.37523(13) 0.22890(9) 0.65741(6) 0.0338(2) Uani 1 1 d . . . O1 O -0.10896(13) -0.13098(9) 0.42428(7) 0.0287(2) Uani 1 1 d . . . O2 O 0.17060(15) -0.03601(10) 0.34037(7) 0.0285(3) Uani 1 1 d . . . S1 S 0.04639(4) 0.15055(3) 0.58115(2) 0.02200(9) 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 0.0169(6) 0.0220(7) 0.0213(6) 0.0020(5) -0.0008(5) -0.0013(5) C2 0.0223(7) 0.0295(7) 0.0237(7) -0.0019(6) -0.0001(5) -0.0028(6) C3 0.0282(8) 0.0433(9) 0.0228(8) 0.0054(7) 0.0007(6) -0.0092(7) C4 0.0314(9) 0.0307(8) 0.0350(8) 0.0126(7) -0.0015(7) -0.0090(7) C5 0.0285(8) 0.0228(7) 0.0330(8) 0.0027(6) -0.0031(6) -0.0035(6) C6 0.0177(6) 0.0217(7) 0.0244(7) 0.0022(6) -0.0017(5) 0.0005(5) C7 0.0197(7) 0.0205(6) 0.0251(7) -0.0032(5) -0.0007(6) 0.0008(6) C8 0.0231(7) 0.0223(6) 0.0201(6) -0.0013(6) 0.0009(6) 0.0035(5) C9 0.0222(7) 0.0188(6) 0.0213(7) 0.0043(5) 0.0034(5) 0.0012(6) C10 0.0251(7) 0.0225(7) 0.0263(7) 0.0019(5) 0.0054(6) 0.0035(6) C11 0.0210(7) 0.0310(8) 0.0362(8) 0.0055(7) 0.0045(6) 0.0066(6) C12 0.0227(7) 0.0293(8) 0.0340(8) 0.0044(6) -0.0030(6) -0.0010(6) C13 0.0274(7) 0.0207(6) 0.0228(7) 0.0016(6) 0.0012(6) -0.0010(6) C14 0.0202(7) 0.0183(6) 0.0227(7) 0.0035(5) 0.0041(5) 0.0004(5) C15 0.0381(10) 0.0378(9) 0.0372(9) -0.0160(8) -0.0005(7) -0.0079(8) C16 0.0412(10) 0.0440(10) 0.0229(8) 0.0045(7) 0.0060(7) 0.0068(8) F1 0.0456(6) 0.0388(5) 0.0289(5) -0.0099(4) 0.0143(4) -0.0093(5) F2 0.0327(5) 0.0373(5) 0.0315(5) -0.0133(4) 0.0008(4) -0.0047(4) O1 0.0227(5) 0.0339(6) 0.0293(5) -0.0121(5) -0.0022(4) -0.0004(4) O2 0.0369(6) 0.0295(6) 0.0190(5) -0.0025(4) 0.0036(4) 0.0028(5) S1 0.02167(17) 0.01819(15) 0.02613(17) -0.00037(14) 0.00593(14) 0.00154(13) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 C2 1.399(2) . ? C1 C6 1.401(2) . ? C1 S1 1.7831(15) . ? C2 F1 1.3577(19) . ? C2 C3 1.370(2) . ? C3 C4 1.381(3) . ? C3 H3 0.9500 . ? C4 C5 1.386(2) . ? C4 H4 0.9500 . ? C5 C6 1.398(2) . ? C5 H5 0.9500 . ? C6 C7 1.534(2) . ? C7 O1 1.4329(17) . ? C7 C8 1.529(2) . ? C7 H7 1.0000 . ? C8 O2 1.4203(17) . ? C8 C9 1.516(2) . ? C8 H8 1.0000 . ? C9 C10 1.393(2) . ? C9 C14 1.406(2) . ? C10 C11 1.390(2) . ? C10 H10 0.9500 . ? C11 C12 1.386(2) . ? C11 H11 0.9500 . ? C12 C13 1.383(2) . ? C12 H12 0.9500 . ? C13 F2 1.3558(17) . ? C13 C14 1.384(2) . ? C14 S1 1.7739(14) . ? C15 O1 1.427(2) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C16 O2 1.423(2) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 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 C2 C1 C6 117.66(13) . . ? C2 C1 S1 115.96(11) . . ? C6 C1 S1 126.37(11) . . ? F1 C2 C3 118.06(14) . . ? F1 C2 C1 118.01(13) . . ? C3 C2 C1 123.92(15) . . ? C2 C3 C4 118.22(14) . . ? C2 C3 H3 120.9 . . ? C4 C3 H3 120.9 . . ? C3 C4 C5 119.46(15) . . ? C3 C4 H4 120.3 . . ? C5 C4 H4 120.3 . . ? C4 C5 C6 122.51(15) . . ? C4 C5 H5 118.7 . . ? C6 C5 H5 118.7 . . ? C5 C6 C1 118.13(13) . . ? C5 C6 C7 114.06(13) . . ? C1 C6 C7 127.59(13) . . ? O1 C7 C8 108.66(11) . . ? O1 C7 C6 105.21(11) . . ? C8 C7 C6 118.50(12) . . ? O1 C7 H7 108.0 . . ? C8 C7 H7 108.0 . . ? C6 C7 H7 108.0 . . ? O2 C8 C9 111.36(11) . . ? O2 C8 C7 105.80(11) . . ? C9 C8 C7 112.30(12) . . ? O2 C8 H8 109.1 . . ? C9 C8 H8 109.1 . . ? C7 C8 H8 109.1 . . ? C10 C9 C14 119.38(13) . . ? C10 C9 C8 121.85(13) . . ? C14 C9 C8 118.77(13) . . ? C11 C10 C9 120.52(14) . . ? C11 C10 H10 119.7 . . ? C9 C10 H10 119.7 . . ? C12 C11 C10 120.70(14) . . ? C12 C11 H11 119.6 . . ? C10 C11 H11 119.6 . . ? C13 C12 C11 118.07(14) . . ? C13 C12 H12 121.0 . . ? C11 C12 H12 121.0 . . ? F2 C13 C12 118.03(13) . . ? F2 C13 C14 119.02(13) . . ? C12 C13 C14 122.94(14) . . ? C13 C14 C9 118.37(13) . . ? C13 C14 S1 121.15(11) . . ? C9 C14 S1 120.47(11) . . ? O1 C15 H15A 109.5 . . ? O1 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? O1 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? O2 C16 H16A 109.5 . . ? O2 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O2 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C15 O1 C7 114.82(12) . . ? C8 O2 C16 113.00(12) . . ? C14 S1 C1 99.35(7) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 F1 -178.26(13) . . . . ? S1 C1 C2 F1 1.72(18) . . . . ? C6 C1 C2 C3 2.3(2) . . . . ? S1 C1 C2 C3 -177.75(13) . . . . ? F1 C2 C3 C4 -179.02(14) . . . . ? C1 C2 C3 C4 0.5(3) . . . . ? C2 C3 C4 C5 -1.6(2) . . . . ? C3 C4 C5 C6 0.0(2) . . . . ? C4 C5 C6 C1 2.7(2) . . . . ? C4 C5 C6 C7 -172.38(15) . . . . ? C2 C1 C6 C5 -3.7(2) . . . . ? S1 C1 C6 C5 176.31(11) . . . . ? C2 C1 C6 C7 170.61(13) . . . . ? S1 C1 C6 C7 -9.4(2) . . . . ? C5 C6 C7 O1 66.53(15) . . . . ? C1 C6 C7 O1 -107.98(15) . . . . ? C5 C6 C7 C8 -171.81(13) . . . . ? C1 C6 C7 C8 13.7(2) . . . . ? O1 C7 C8 O2 -63.82(14) . . . . ? C6 C7 C8 O2 176.28(12) . . . . ? O1 C7 C8 C9 174.51(11) . . . . ? C6 C7 C8 C9 54.61(17) . . . . ? O2 C8 C9 C10 -19.30(19) . . . . ? C7 C8 C9 C10 99.14(15) . . . . ? O2 C8 C9 C14 161.45(12) . . . . ? C7 C8 C9 C14 -80.11(16) . . . . ? C14 C9 C10 C11 -0.3(2) . . . . ? C8 C9 C10 C11 -179.52(14) . . . . ? C9 C10 C11 C12 -0.9(2) . . . . ? C10 C11 C12 C13 0.7(2) . . . . ? C11 C12 C13 F2 -179.57(13) . . . . ? C11 C12 C13 C14 0.7(2) . . . . ? F2 C13 C14 C9 178.47(12) . . . . ? C12 C13 C14 C9 -1.8(2) . . . . ? F2 C13 C14 S1 -2.42(19) . . . . ? C12 C13 C14 S1 177.32(12) . . . . ? C10 C9 C14 C13 1.5(2) . . . . ? C8 C9 C14 C13 -179.19(13) . . . . ? C10 C9 C14 S1 -177.57(11) . . . . ? C8 C9 C14 S1 1.70(18) . . . . ? C8 C7 O1 C15 101.76(15) . . . . ? C6 C7 O1 C15 -130.38(13) . . . . ? C9 C8 O2 C16 -84.62(15) . . . . ? C7 C8 O2 C16 153.10(13) . . . . ? C13 C14 S1 C1 -113.71(12) . . . . ? C9 C14 S1 C1 65.38(12) . . . . ? C2 C1 S1 C14 130.95(12) . . . . ? C6 C1 S1 C14 -49.06(14) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.227 _refine_diff_density_min -0.170 _refine_diff_density_rms 0.038 # Attachment 'sulfoxideCIF.txt' data_ah2 _database_code_depnum_ccdc_archive 'CCDC 290627' _audit_creation_method SHELXL-97 _chemical_formula_moiety 'C16 H14 F2 O3 S' _chemical_formula_sum 'C16 H14 F2 O3 S' _chemical_formula_weight 324.33 _chemical_absolute_configuration ad loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 '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 Triclinic _symmetry_space_group_name_H-M 'P 1' _symmetry_space_group_name_Hall 'P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' _cell_length_a 7.986(3) _cell_length_b 8.7928(16) _cell_length_c 11.254(3) _cell_angle_alpha 89.389(19) _cell_angle_beta 82.07(2) _cell_angle_gamma 67.49(2) _cell_volume 722.3(4) _cell_formula_units_Z 2 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 4630 _cell_measurement_theta_min 2.5 _cell_measurement_theta_max 25.0 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.491 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 336 _exptl_absorpt_coefficient_mu 0.256 _exptl_absorpt_correction_type none _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'Frames, each covering 0.3 \% in \w' _diffrn_detector_area_resol_mean 8.3 _diffrn_standards_decay_% 0 _diffrn_reflns_number 7358 _diffrn_reflns_av_R_equivalents 0.0289 _diffrn_reflns_av_sigmaI/netI 0.0364 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 27.48 _reflns_number_total 5913 _reflns_number_gt 5275 _reflns_threshold_expression >2\s(I) _computing_data_collection 'SMART (Bruker, 1996)' _computing_cell_refinement 'SAINT (Bruker, 1996)' _computing_data_reduction 'SHELXTL (Bruker, 1996)' _computing_structure_solution 'SHELXTL (Bruker, 1996)' _computing_structure_refinement 'SHELXTL (Bruker, 2001)' _computing_molecular_graphics 'SHELXTL (Bruker, 2001)' _computing_publication_material 'SHELXTL (Bruker, 2001)' _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. The value of |E*E-1| = 0.830 for the dataset gives only weak evidence for a non-centrosymmetric space group. A pseudo centre of symmetry exists in the structure which is more or less obeyed by all atoms apart from the methoxy oxygens. A centrosymmetric model in space group P-1 (with just one molecule in the asymmetric unit and the methoxy oxygen atoms O2 and O3 refined with 50:50 disorder) gave final residuals about twice as large as those found in the P1 solution. A solution in P-1 is in any case highly unlikely as the crystals were prepared from a chirally pure sample. ; _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^)+(0.0283P)^2^+0.6808P] 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 SHELXL _refine_ls_extinction_coef 0.0160(19) _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 -0.06(9) _refine_ls_number_reflns 5913 _refine_ls_number_parameters 419 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0540 _refine_ls_R_factor_gt 0.0432 _refine_ls_wR_factor_ref 0.0999 _refine_ls_wR_factor_gt 0.0912 _refine_ls_goodness_of_fit_ref 1.114 _refine_ls_restrained_S_all 1.114 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.4608(5) 0.1520(5) 0.8024(4) 0.0214(8) Uani 1 1 d . . . C2 C 0.6331(5) 0.0654(5) 0.8347(3) 0.0214(8) Uani 1 1 d . . . C3 C 0.7920(6) 0.0708(5) 0.7748(4) 0.0257(9) Uani 1 1 d . . . H3 H 0.9071 0.0091 0.7996 0.031 Uiso 1 1 calc R . . C4 C 0.7789(6) 0.1700(5) 0.6761(4) 0.0294(9) Uani 1 1 d . . . H4 H 0.8861 0.1768 0.6322 0.035 Uiso 1 1 calc R . . C5 C 0.6082(6) 0.2589(5) 0.6423(4) 0.0286(9) Uani 1 1 d . . . H5 H 0.6010 0.3272 0.5757 0.034 Uiso 1 1 calc R . . C6 C 0.4478(5) 0.2511(5) 0.7026(3) 0.0219(8) Uani 1 1 d . . . C7 C 0.2725(5) 0.3474(5) 0.6503(3) 0.0247(8) Uani 1 1 d . . . H7 H 0.302(5) 0.437(4) 0.611(3) 0.024(9) Uiso 1 1 d . . . C8 C 0.0895(5) 0.4300(5) 0.7323(3) 0.0228(8) Uani 1 1 d . . . H8 H 0.029(5) 0.352(5) 0.733(3) 0.026(9) Uiso 1 1 d . . . C9 C 0.0999(5) 0.4778(5) 0.8603(3) 0.0220(8) Uani 1 1 d . . . C10 C 0.0287(6) 0.6417(5) 0.8997(4) 0.0336(10) Uani 1 1 d . . . H10 H -0.0181 0.7253 0.8451 0.040 Uiso 1 1 calc R . . C11 C 0.0253(7) 0.6850(6) 1.0191(4) 0.0388(11) Uani 1 1 d . . . H11 H -0.0259 0.7980 1.0451 0.047 Uiso 1 1 calc R . . C12 C 0.0945(7) 0.5669(6) 1.0998(4) 0.0370(11) Uani 1 1 d . . . H12 H 0.0927 0.5966 1.1810 0.044 Uiso 1 1 calc R . . C13 C 0.1664(6) 0.4048(5) 1.0593(4) 0.0256(9) Uani 1 1 d . . . C14 C 0.1710(5) 0.3564(5) 0.9419(4) 0.0218(8) Uani 1 1 d . . . C15 C 0.3450(7) 0.2161(7) 0.4527(4) 0.0479(13) Uani 1 1 d . . . H15A H 0.2982 0.1611 0.3980 0.072 Uiso 1 1 calc R . . H15B H 0.4722 0.1461 0.4601 0.072 Uiso 1 1 calc R . . H15C H 0.3400 0.3216 0.4207 0.072 Uiso 1 1 calc R . . C16 C -0.2023(6) 0.6143(6) 0.6875(4) 0.0361(10) Uani 1 1 d . . . H16A H -0.2584 0.7007 0.6330 0.054 Uiso 1 1 calc R . . H16B H -0.2519 0.6553 0.7708 0.054 Uiso 1 1 calc R . . H16C H -0.2298 0.5176 0.6713 0.054 Uiso 1 1 calc R . . C17 C 0.5140(5) 0.6698(5) 0.1376(3) 0.0204(8) Uani 1 1 d . . . C18 C 0.5257(6) 0.6208(5) 0.0184(4) 0.0281(9) Uani 1 1 d . . . C19 C 0.5954(6) 0.4556(5) -0.0219(4) 0.0337(10) Uani 1 1 d . . . H19 H 0.6056 0.4255 -0.1042 0.040 Uiso 1 1 calc R . . C20 C 0.6493(7) 0.3372(6) 0.0627(4) 0.0413(11) Uani 1 1 d . . . H20 H 0.6984 0.2235 0.0388 0.050 Uiso 1 1 calc R . . C21 C 0.6313(6) 0.3853(5) 0.1821(4) 0.0331(10) Uani 1 1 d . . . H21 H 0.6642 0.3021 0.2390 0.040 Uiso 1 1 calc R . . C22 C 0.5676(5) 0.5486(5) 0.2230(4) 0.0236(8) Uani 1 1 d . . . C23 C 0.5676(5) 0.5784(5) 0.3556(3) 0.0240(8) Uani 1 1 d . . . H23 H 0.558(5) 0.483(5) 0.390(3) 0.026(9) Uiso 1 1 d . . . C24 C 0.4214(5) 0.7317(5) 0.4249(3) 0.0237(8) Uani 1 1 d . . . H24 H 0.472(4) 0.819(4) 0.418(3) 0.015(8) Uiso 1 1 d . . . C25 C 0.2392(5) 0.7996(5) 0.3775(3) 0.0217(8) Uani 1 1 d . . . C26 C 0.0820(6) 0.7901(5) 0.4407(4) 0.0289(9) Uani 1 1 d . . . H26 H 0.0888 0.7338 0.5135 0.035 Uiso 1 1 calc R . . C27 C -0.0855(6) 0.8617(5) 0.3987(4) 0.0317(10) Uani 1 1 d . . . H27 H -0.1904 0.8506 0.4426 0.038 Uiso 1 1 calc R . . C28 C -0.1034(6) 0.9470(5) 0.2968(4) 0.0280(9) Uani 1 1 d . . . H28 H -0.2191 0.9975 0.2700 0.034 Uiso 1 1 calc R . . C29 C 0.0538(6) 0.9578(5) 0.2331(4) 0.0233(8) Uani 1 1 d . . . C30 C 0.2249(5) 0.8838(5) 0.2690(3) 0.0195(8) Uani 1 1 d . . . C31 C 0.8855(6) 0.4291(6) 0.3740(5) 0.0441(12) Uani 1 1 d . . . H31A H 0.9839 0.4412 0.4114 0.066 Uiso 1 1 calc R . . H31B H 0.9317 0.3881 0.2904 0.066 Uiso 1 1 calc R . . H31C H 0.8431 0.3508 0.4181 0.066 Uiso 1 1 calc R . . C32 C 0.3379(6) 0.8187(6) 0.6307(4) 0.0373(11) Uani 1 1 d . . . H32A H 0.3322 0.7778 0.7119 0.056 Uiso 1 1 calc R . . H32B H 0.2155 0.8948 0.6178 0.056 Uiso 1 1 calc R . . H32C H 0.4221 0.8764 0.6212 0.056 Uiso 1 1 calc R . . F1 F 0.6464(3) -0.0258(3) 0.9335(2) 0.0314(6) Uani 1 1 d . . . F2 F 0.2401(4) 0.2875(3) 1.1374(2) 0.0347(6) Uani 1 1 d . . . F3 F 0.4671(4) 0.7364(3) -0.0625(2) 0.0356(6) Uani 1 1 d . . . F4 F 0.0390(3) 1.0400(3) 0.1301(2) 0.0314(5) Uani 1 1 d . . . O1 O 0.1455(4) 0.1027(3) 0.8277(3) 0.0282(6) Uani 1 1 d . . . O2 O 0.2362(3) 0.2444(3) 0.5671(2) 0.0310(5) Uani 1 1 d . . . O3 O -0.0091(3) 0.5695(3) 0.6694(2) 0.0284(5) Uani 1 1 d . . . O4 O 0.5387(4) 0.9312(4) 0.2424(3) 0.0276(6) Uani 1 1 d . . . O5 O 0.7378(3) 0.5842(3) 0.3771(2) 0.0323(6) Uani 1 1 d . . . O6 O 0.4020(3) 0.6831(3) 0.5447(2) 0.0291(5) Uani 1 1 d . . . S1 S 0.26846(10) 0.13960(9) 0.90140(7) 0.0215(2) Uani 1 1 d . . . S2 S 0.41849(10) 0.88965(9) 0.17001(7) 0.0210(2) 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 0.0196(19) 0.0207(19) 0.023(2) -0.0012(16) 0.0011(15) -0.0083(15) C2 0.023(2) 0.0179(18) 0.023(2) 0.0018(15) -0.0018(15) -0.0073(16) C3 0.021(2) 0.0207(19) 0.033(2) 0.0014(17) -0.0049(16) -0.0052(16) C4 0.023(2) 0.031(2) 0.032(2) -0.0010(19) -0.0003(17) -0.0098(18) C5 0.024(2) 0.031(2) 0.030(2) 0.0036(17) 0.0008(16) -0.0109(16) C6 0.0215(18) 0.0210(17) 0.0212(18) -0.0008(14) -0.0016(14) -0.0065(14) C7 0.0254(17) 0.0280(19) 0.0191(17) 0.0021(14) -0.0027(13) -0.0086(15) C8 0.0220(17) 0.0206(17) 0.0230(17) 0.0013(14) -0.0056(13) -0.0041(14) C9 0.0169(17) 0.0245(19) 0.0229(19) -0.0015(15) 0.0001(14) -0.0070(15) C10 0.036(2) 0.0221(19) 0.035(2) -0.0017(17) -0.0061(17) -0.0023(16) C11 0.052(3) 0.023(2) 0.037(3) -0.0083(18) -0.007(2) -0.009(2) C12 0.044(3) 0.035(3) 0.027(2) -0.009(2) -0.002(2) -0.010(2) C13 0.027(2) 0.023(2) 0.024(2) -0.0014(16) -0.0012(16) -0.0073(17) C14 0.0188(18) 0.0166(17) 0.026(2) -0.0011(15) 0.0012(15) -0.0040(15) C15 0.042(3) 0.058(3) 0.033(3) -0.012(2) -0.004(2) -0.007(2) C16 0.023(2) 0.037(2) 0.042(3) 0.0065(19) -0.0070(18) -0.0025(18) C17 0.0144(17) 0.0221(19) 0.024(2) -0.0025(16) -0.0021(14) -0.0066(15) C18 0.027(2) 0.032(2) 0.023(2) 0.0020(18) -0.0006(17) -0.0108(18) C19 0.040(3) 0.029(2) 0.028(2) -0.0084(18) -0.0037(19) -0.009(2) C20 0.050(3) 0.023(2) 0.040(3) -0.0072(19) -0.010(2) -0.001(2) C21 0.041(2) 0.0208(19) 0.033(2) 0.0004(17) -0.0108(18) -0.0057(17) C22 0.0204(18) 0.025(2) 0.0234(19) 0.0015(15) -0.0019(14) -0.0066(15) C23 0.0244(18) 0.0198(17) 0.0248(18) 0.0032(14) -0.0051(13) -0.0048(14) C24 0.0221(16) 0.028(2) 0.0191(17) 0.0015(14) -0.0043(13) -0.0067(14) C25 0.0207(18) 0.0206(17) 0.0226(19) -0.0027(14) -0.0023(14) -0.0069(14) C26 0.032(2) 0.029(2) 0.023(2) 0.0043(16) -0.0018(16) -0.0096(17) C27 0.024(2) 0.034(2) 0.040(3) 0.000(2) 0.0050(18) -0.0171(19) C28 0.0176(19) 0.026(2) 0.042(3) -0.0015(18) -0.0054(17) -0.0094(16) C29 0.027(2) 0.0169(19) 0.027(2) -0.0017(16) -0.0078(16) -0.0073(16) C30 0.0155(18) 0.0184(18) 0.024(2) -0.0044(15) -0.0018(15) -0.0061(15) C31 0.022(2) 0.052(3) 0.043(3) 0.012(2) -0.0031(19) 0.001(2) C32 0.032(2) 0.043(3) 0.025(2) -0.0102(19) -0.0031(17) -0.001(2) F1 0.0270(12) 0.0279(12) 0.0383(14) 0.0138(10) -0.0082(10) -0.0086(10) F2 0.0435(14) 0.0349(13) 0.0212(12) 0.0037(11) -0.0070(10) -0.0095(11) F3 0.0506(16) 0.0333(13) 0.0195(12) 0.0036(10) -0.0024(11) -0.0134(12) F4 0.0273(12) 0.0325(13) 0.0318(13) 0.0102(10) -0.0114(9) -0.0066(10) O1 0.0256(15) 0.0244(15) 0.0356(17) -0.0022(12) -0.0048(12) -0.0104(12) O2 0.0307(13) 0.0364(14) 0.0245(12) -0.0061(10) -0.0063(10) -0.0103(11) O3 0.0197(11) 0.0310(12) 0.0274(12) 0.0087(10) -0.0035(9) -0.0023(9) O4 0.0239(15) 0.0320(15) 0.0325(16) -0.0034(13) -0.0021(12) -0.0174(13) O5 0.0205(11) 0.0368(14) 0.0346(13) -0.0014(11) -0.0097(9) -0.0036(10) O6 0.0344(13) 0.0282(12) 0.0184(11) 0.0015(9) -0.0045(9) -0.0048(10) S1 0.0202(4) 0.0206(4) 0.0229(5) 0.0010(4) -0.0008(3) -0.0078(4) S2 0.0200(4) 0.0196(4) 0.0230(5) 0.0012(4) -0.0016(3) -0.0076(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 C1 C2 1.391(5) . ? C1 C6 1.404(6) . ? C1 S1 1.808(4) . ? C2 F1 1.356(4) . ? C2 C3 1.369(6) . ? C3 C4 1.396(6) . ? C3 H3 0.9500 . ? C4 C5 1.391(6) . ? C4 H4 0.9500 . ? C5 C6 1.391(6) . ? C5 H5 0.9500 . ? C6 C7 1.527(5) . ? C7 O2 1.440(4) . ? C7 C8 1.531(5) . ? C7 H7 0.99(4) . ? C8 O3 1.421(4) . ? C8 C9 1.528(5) . ? C8 H8 0.98(4) . ? C9 C10 1.383(6) . ? C9 C14 1.401(6) . ? C10 C11 1.394(6) . ? C10 H10 0.9500 . ? C11 C12 1.373(7) . ? C11 H11 0.9500 . ? C12 C13 1.372(6) . ? C12 H12 0.9500 . ? C13 F2 1.357(5) . ? C13 C14 1.384(6) . ? C14 S1 1.798(4) . ? C15 O2 1.418(5) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C16 O3 1.424(5) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C17 C18 1.394(5) . ? C17 C22 1.409(6) . ? C17 S2 1.806(4) . ? C18 F3 1.348(5) . ? C18 C19 1.396(6) . ? C19 C20 1.387(7) . ? C19 H19 0.9500 . ? C20 C21 1.385(6) . ? C20 H20 0.9500 . ? C21 C22 1.387(6) . ? C21 H21 0.9500 . ? C22 C23 1.518(5) . ? C23 O5 1.433(4) . ? C23 C24 1.534(5) . ? C23 H23 0.95(4) . ? C24 O6 1.416(4) . ? C24 C25 1.516(5) . ? C24 H24 0.99(3) . ? C25 C26 1.387(6) . ? C25 C30 1.416(5) . ? C26 C27 1.390(6) . ? C26 H26 0.9500 . ? C27 C28 1.357(7) . ? C27 H27 0.9500 . ? C28 C29 1.393(6) . ? C28 H28 0.9500 . ? C29 F4 1.354(5) . ? C29 C30 1.385(5) . ? C30 S2 1.794(4) . ? C31 O5 1.418(5) . ? C31 H31A 0.9800 . ? C31 H31B 0.9800 . ? C31 H31C 0.9800 . ? C32 O6 1.428(5) . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? O1 S1 1.494(3) . ? O4 S2 1.487(3) . ? 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 C6 118.5(3) . . ? C2 C1 S1 116.2(3) . . ? C6 C1 S1 125.1(3) . . ? F1 C2 C3 117.2(3) . . ? F1 C2 C1 118.9(3) . . ? C3 C2 C1 123.8(4) . . ? C2 C3 C4 117.7(4) . . ? C2 C3 H3 121.2 . . ? C4 C3 H3 121.2 . . ? C5 C4 C3 119.7(4) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? C6 C5 C4 122.3(4) . . ? C6 C5 H5 118.9 . . ? C4 C5 H5 118.9 . . ? C5 C6 C1 118.0(4) . . ? C5 C6 C7 116.2(4) . . ? C1 C6 C7 125.8(3) . . ? O2 C7 C6 110.8(3) . . ? O2 C7 C8 104.1(3) . . ? C6 C7 C8 120.9(3) . . ? O2 C7 H7 113(2) . . ? C6 C7 H7 102(2) . . ? C8 C7 H7 106(2) . . ? O3 C8 C9 111.8(3) . . ? O3 C8 C7 104.2(3) . . ? C9 C8 C7 116.3(3) . . ? O3 C8 H8 108(2) . . ? C9 C8 H8 110(2) . . ? C7 C8 H8 106(2) . . ? C10 C9 C14 118.9(4) . . ? C10 C9 C8 120.4(4) . . ? C14 C9 C8 120.6(3) . . ? C9 C10 C11 120.4(4) . . ? C9 C10 H10 119.8 . . ? C11 C10 H10 119.8 . . ? C12 C11 C10 121.1(4) . . ? C12 C11 H11 119.4 . . ? C10 C11 H11 119.4 . . ? C13 C12 C11 117.9(4) . . ? C13 C12 H12 121.1 . . ? C11 C12 H12 121.1 . . ? F2 C13 C12 118.4(4) . . ? F2 C13 C14 118.7(3) . . ? C12 C13 C14 122.9(4) . . ? C13 C14 C9 118.8(3) . . ? C13 C14 S1 118.2(3) . . ? C9 C14 S1 123.1(3) . . ? O2 C15 H15A 109.5 . . ? O2 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? O2 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? O3 C16 H16A 109.5 . . ? O3 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O3 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? C18 C17 C22 119.1(4) . . ? C18 C17 S2 115.5(3) . . ? C22 C17 S2 125.4(3) . . ? F3 C18 C17 119.3(4) . . ? F3 C18 C19 117.8(4) . . ? C17 C18 C19 122.9(4) . . ? C20 C19 C18 117.5(4) . . ? C20 C19 H19 121.2 . . ? C18 C19 H19 121.2 . . ? C21 C20 C19 119.8(4) . . ? C21 C20 H20 120.1 . . ? C19 C20 H20 120.1 . . ? C20 C21 C22 123.4(4) . . ? C20 C21 H21 118.3 . . ? C22 C21 H21 118.3 . . ? C21 C22 C17 117.2(4) . . ? C21 C22 C23 116.3(4) . . ? C17 C22 C23 126.5(3) . . ? O5 C23 C22 111.4(3) . . ? O5 C23 C24 104.2(3) . . ? C22 C23 C24 120.5(3) . . ? O5 C23 H23 108(2) . . ? C22 C23 H23 103(2) . . ? C24 C23 H23 109(2) . . ? O6 C24 C25 111.7(3) . . ? O6 C24 C23 104.6(3) . . ? C25 C24 C23 115.4(3) . . ? O6 C24 H24 111.3(19) . . ? C25 C24 H24 107.2(19) . . ? C23 C24 H24 106.6(18) . . ? C26 C25 C30 118.3(3) . . ? C26 C25 C24 121.9(3) . . ? C30 C25 C24 119.7(3) . . ? C25 C26 C27 120.8(4) . . ? C25 C26 H26 119.6 . . ? C27 C26 H26 119.6 . . ? C28 C27 C26 121.9(4) . . ? C28 C27 H27 119.1 . . ? C26 C27 H27 119.1 . . ? C27 C28 C29 117.7(4) . . ? C27 C28 H28 121.2 . . ? C29 C28 H28 121.2 . . ? F4 C29 C30 118.9(4) . . ? F4 C29 C28 118.5(4) . . ? C30 C29 C28 122.6(4) . . ? C29 C30 C25 118.7(3) . . ? C29 C30 S2 117.7(3) . . ? C25 C30 S2 123.5(3) . . ? O5 C31 H31A 109.5 . . ? O5 C31 H31B 109.5 . . ? H31A C31 H31B 109.5 . . ? O5 C31 H31C 109.5 . . ? H31A C31 H31C 109.5 . . ? H31B C31 H31C 109.5 . . ? O6 C32 H32A 109.5 . . ? O6 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? O6 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? C15 O2 C7 114.9(3) . . ? C8 O3 C16 114.5(3) . . ? C31 O5 C23 115.3(3) . . ? C24 O6 C32 112.8(3) . . ? O1 S1 C14 108.32(18) . . ? O1 S1 C1 108.86(18) . . ? C14 S1 C1 93.75(19) . . ? O4 S2 C30 108.66(17) . . ? O4 S2 C17 108.60(17) . . ? C30 S2 C17 93.25(18) . . ? 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 C6 C1 C2 F1 177.6(3) . . . . ? S1 C1 C2 F1 2.4(5) . . . . ? C6 C1 C2 C3 0.0(6) . . . . ? S1 C1 C2 C3 -175.2(3) . . . . ? F1 C2 C3 C4 -177.3(4) . . . . ? C1 C2 C3 C4 0.4(6) . . . . ? C2 C3 C4 C5 0.1(6) . . . . ? C3 C4 C5 C6 -1.0(7) . . . . ? C4 C5 C6 C1 1.3(6) . . . . ? C4 C5 C6 C7 -176.4(4) . . . . ? C2 C1 C6 C5 -0.8(6) . . . . ? S1 C1 C6 C5 173.9(3) . . . . ? C2 C1 C6 C7 176.7(4) . . . . ? S1 C1 C6 C7 -8.6(6) . . . . ? C5 C6 C7 O2 92.3(4) . . . . ? C1 C6 C7 O2 -85.2(4) . . . . ? C5 C6 C7 C8 -145.6(4) . . . . ? C1 C6 C7 C8 36.8(6) . . . . ? O2 C7 C8 O3 -85.1(3) . . . . ? C6 C7 C8 O3 149.6(3) . . . . ? O2 C7 C8 C9 151.3(3) . . . . ? C6 C7 C8 C9 26.1(5) . . . . ? O3 C8 C9 C10 -4.1(5) . . . . ? C7 C8 C9 C10 115.4(4) . . . . ? O3 C8 C9 C14 172.0(3) . . . . ? C7 C8 C9 C14 -68.5(5) . . . . ? C14 C9 C10 C11 -1.0(7) . . . . ? C8 C9 C10 C11 175.0(4) . . . . ? C9 C10 C11 C12 1.0(8) . . . . ? C10 C11 C12 C13 -0.3(8) . . . . ? C11 C12 C13 F2 178.1(4) . . . . ? C11 C12 C13 C14 -0.3(7) . . . . ? F2 C13 C14 C9 -178.1(3) . . . . ? C12 C13 C14 C9 0.2(7) . . . . ? F2 C13 C14 S1 1.9(5) . . . . ? C12 C13 C14 S1 -179.7(4) . . . . ? C10 C9 C14 C13 0.4(6) . . . . ? C8 C9 C14 C13 -175.6(4) . . . . ? C10 C9 C14 S1 -179.6(3) . . . . ? C8 C9 C14 S1 4.3(5) . . . . ? C22 C17 C18 F3 177.1(4) . . . . ? S2 C17 C18 F3 0.0(5) . . . . ? C22 C17 C18 C19 -2.6(6) . . . . ? S2 C17 C18 C19 -179.7(3) . . . . ? F3 C18 C19 C20 -177.7(4) . . . . ? C17 C18 C19 C20 2.0(7) . . . . ? C18 C19 C20 C21 0.5(8) . . . . ? C19 C20 C21 C22 -2.6(8) . . . . ? C20 C21 C22 C17 2.0(7) . . . . ? C20 C21 C22 C23 -176.4(4) . . . . ? C18 C17 C22 C21 0.6(6) . . . . ? S2 C17 C22 C21 177.4(3) . . . . ? C18 C17 C22 C23 178.8(4) . . . . ? S2 C17 C22 C23 -4.4(6) . . . . ? C21 C22 C23 O5 89.5(4) . . . . ? C17 C22 C23 O5 -88.8(5) . . . . ? C21 C22 C23 C24 -148.1(4) . . . . ? C17 C22 C23 C24 33.6(6) . . . . ? O5 C23 C24 O6 -82.7(3) . . . . ? C22 C23 C24 O6 151.5(3) . . . . ? O5 C23 C24 C25 154.1(3) . . . . ? C22 C23 C24 C25 28.3(5) . . . . ? O6 C24 C25 C26 -8.7(5) . . . . ? C23 C24 C25 C26 110.6(4) . . . . ? O6 C24 C25 C30 167.6(3) . . . . ? C23 C24 C25 C30 -73.0(5) . . . . ? C30 C25 C26 C27 -0.2(6) . . . . ? C24 C25 C26 C27 176.2(4) . . . . ? C25 C26 C27 C28 -1.8(7) . . . . ? C26 C27 C28 C29 1.4(7) . . . . ? C27 C28 C29 F4 178.9(4) . . . . ? C27 C28 C29 C30 0.8(6) . . . . ? F4 C29 C30 C25 179.2(3) . . . . ? C28 C29 C30 C25 -2.7(6) . . . . ? F4 C29 C30 S2 -4.4(5) . . . . ? C28 C29 C30 S2 173.6(3) . . . . ? C26 C25 C30 C29 2.3(6) . . . . ? C24 C25 C30 C29 -174.2(4) . . . . ? C26 C25 C30 S2 -173.8(3) . . . . ? C24 C25 C30 S2 9.7(5) . . . . ? C6 C7 O2 C15 -77.1(4) . . . . ? C8 C7 O2 C15 151.5(3) . . . . ? C9 C8 O3 C16 -85.8(4) . . . . ? C7 C8 O3 C16 147.8(3) . . . . ? C22 C23 O5 C31 -77.1(4) . . . . ? C24 C23 O5 C31 151.5(3) . . . . ? C25 C24 O6 C32 -80.2(4) . . . . ? C23 C24 O6 C32 154.3(3) . . . . ? C13 C14 S1 O1 135.3(3) . . . . ? C9 C14 S1 O1 -44.7(4) . . . . ? C13 C14 S1 C1 -113.4(3) . . . . ? C9 C14 S1 C1 66.6(4) . . . . ? C2 C1 S1 O1 -132.6(3) . . . . ? C6 C1 S1 O1 52.6(4) . . . . ? C2 C1 S1 C14 116.6(3) . . . . ? C6 C1 S1 C14 -58.3(4) . . . . ? C29 C30 S2 O4 136.4(3) . . . . ? C25 C30 S2 O4 -47.5(4) . . . . ? C29 C30 S2 C17 -112.7(3) . . . . ? C25 C30 S2 C17 63.4(3) . . . . ? C18 C17 S2 O4 -132.5(3) . . . . ? C22 C17 S2 O4 50.5(4) . . . . ? C18 C17 S2 C30 116.5(3) . . . . ? C22 C17 S2 C30 -60.4(4) . . . . ? _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.359 _refine_diff_density_min -0.334 _refine_diff_density_rms 0.055