# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Ken Tanaka' _publ_contact_author_email TANAKA-K@CC.TUAT.AC.JP _publ_section_title ; Rhodium-Catalyzed Enantio- and Diastereoselective Intramolecular [2 + 2 + 2] Cycloaddition of Unsymmetrical Dienynes ; loop_ _publ_author_name 'Ken Tanaka' 'Masao Hirano' 'Keiichi Noguchi' 'Hiromi Sagae' data_I _database_code_depnum_ccdc_archive 'CCDC 673294' _chemical_name_systematic ; ? ; _chemical_name_common ; (+)-3a,5a-Dimethyl-8-(toluene-4-sulfonyl)- 1,3,3a,4,5,5a,6,7,8,9-decahydro-furo(3,4-h)isoquinoline ; _chemical_melting_point ? _chemical_formula_moiety 'C20 H27 N O3 S' _chemical_formula_sum 'C20 H27 N O3 S' _chemical_formula_weight 361.49 _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 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' _symmetry_space_group_name_Hall 'P 2ac 2ab' _symmetry_Int_Tables_number 19 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 1/2+X,1/2-Y,-Z 3 -X,1/2+Y,1/2-Z 4 1/2-X,-Y,1/2+Z _cell_length_a 22.5760(4) _cell_length_b 8.40396(10) _cell_length_c 9.89489(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1877.34(4) _cell_formula_units_Z 4 _cell_measurement_temperature 193 _cell_measurement_reflns_used 27232 _cell_measurement_theta_min 3.9 _cell_measurement_theta_max 68.2 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.279 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 776 _exptl_absorpt_coefficient_mu 1.677 _exptl_absorpt_correction_type numerical _exptl_absorpt_process_details ; Higashi, T. (1999). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.568 _exptl_absorpt_correction_T_max 0.920 _exptl_special_details ; ? ; _diffrn_ambient_temperature 193 _diffrn_radiation_wavelength 1.54187 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 34420 _diffrn_reflns_av_R_equivalents 0.0291 _diffrn_reflns_av_sigmaI/netI 0.0151 _diffrn_reflns_limit_h_min -27 _diffrn_reflns_limit_h_max 27 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 3.92 _diffrn_reflns_theta_max 68.22 _reflns_number_total 3420 _reflns_number_gt 3314 _reflns_threshold_expression >2sigma(I) _computing_data_collection PROCESS-AUTO _computing_cell_refinement PROCESS-AUTO _computing_data_reduction CrystalStructure _computing_structure_solution SIR2004 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0491P)^2^+0.2151P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0028(3) _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 1444 Friedel Pairs' _refine_ls_abs_structure_Flack -0.008(12) _refine_ls_number_reflns 3420 _refine_ls_number_parameters 230 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0273 _refine_ls_R_factor_gt 0.0265 _refine_ls_wR_factor_ref 0.0733 _refine_ls_wR_factor_gt 0.0727 _refine_ls_goodness_of_fit_ref 1.073 _refine_ls_restrained_S_all 1.073 _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 0.060340(15) 0.73465(4) 0.15655(3) 0.02987(11) Uani 1 1 d . . . O1 O 0.19505(5) 1.26465(15) 0.53314(12) 0.0428(3) Uani 1 1 d . . . O2 O 0.08507(5) 0.87373(14) 0.09386(11) 0.0400(3) Uani 1 1 d . . . O3 O -0.00059(5) 0.69551(14) 0.13650(12) 0.0408(3) Uani 1 1 d . . . N1 N 0.06949(5) 0.75681(14) 0.32018(12) 0.0275(3) Uani 1 1 d . . . C1 C 0.16862(7) 1.1509(2) 0.44307(16) 0.0365(4) Uani 1 1 d . . . H1A H 0.1994 1.0957 0.3895 0.044 Uiso 1 1 calc R . . H1B H 0.1408 1.2041 0.3803 0.044 Uiso 1 1 calc R . . C2 C 0.13604(6) 1.03416(17) 0.53261(14) 0.0261(3) Uani 1 1 d . . . C3 C 0.12070(6) 0.88465(17) 0.50542(14) 0.0245(3) Uani 1 1 d . . . C4 C 0.12793(6) 0.81611(18) 0.36561(15) 0.0293(3) Uani 1 1 d . . . H4A H 0.1425 0.8990 0.3028 0.035 Uiso 1 1 calc R . . H4B H 0.1570 0.7279 0.3672 0.035 Uiso 1 1 calc R . . C5 C 0.04693(6) 0.62848(18) 0.40831(15) 0.0295(3) Uani 1 1 d . . . H5A H 0.0756 0.5394 0.4110 0.035 Uiso 1 1 calc R . . H5B H 0.0089 0.5876 0.3727 0.035 Uiso 1 1 calc R . . C6 C 0.03805(6) 0.69589(19) 0.54999(16) 0.0309(3) Uani 1 1 d . . . H6A H 0.0248 0.6090 0.6105 0.037 Uiso 1 1 calc R . . H6B H 0.0061 0.7765 0.5469 0.037 Uiso 1 1 calc R . . C7 C 0.09420(6) 0.77329(18) 0.61093(14) 0.0266(3) Uani 1 1 d . . . C8 C 0.07682(7) 0.86597(19) 0.73912(15) 0.0336(3) Uani 1 1 d . . . H8A H 0.0386 0.9208 0.7232 0.040 Uiso 1 1 calc R . . H8B H 0.0711 0.7899 0.8144 0.040 Uiso 1 1 calc R . . C9 C 0.12352(7) 0.98926(19) 0.78040(15) 0.0326(3) Uani 1 1 d . . . H9A H 0.1115 1.0415 0.8657 0.039 Uiso 1 1 calc R . . H9B H 0.1620 0.9358 0.7957 0.039 Uiso 1 1 calc R . . C10 C 0.12997(6) 1.11373(17) 0.66902(16) 0.0286(3) Uani 1 1 d . . . C11 C 0.18792(6) 1.20870(19) 0.66913(17) 0.0344(3) Uani 1 1 d . . . H11A H 0.1855 1.2992 0.7329 0.041 Uiso 1 1 calc R . . H11B H 0.2216 1.1401 0.6956 0.041 Uiso 1 1 calc R . . C12 C 0.13935(7) 0.64325(19) 0.64866(18) 0.0361(3) Uani 1 1 d . . . H12A H 0.1218 0.5715 0.7157 0.043 Uiso 1 1 calc R . . H12B H 0.1749 0.6929 0.6866 0.043 Uiso 1 1 calc R . . H12C H 0.1500 0.5826 0.5676 0.043 Uiso 1 1 calc R . . C13 C 0.07720(7) 1.22964(19) 0.66767(18) 0.0383(4) Uani 1 1 d . . . H13A H 0.0755 1.2867 0.7539 0.046 Uiso 1 1 calc R . . H13B H 0.0404 1.1699 0.6544 0.046 Uiso 1 1 calc R . . H13C H 0.0822 1.3061 0.5938 0.046 Uiso 1 1 calc R . . C14 C 0.10377(6) 0.56907(18) 0.10939(15) 0.0283(3) Uani 1 1 d . . . C15 C 0.16194(7) 0.5899(2) 0.06646(17) 0.0346(3) Uani 1 1 d . . . H15 H 0.1776 0.6936 0.0531 0.041 Uiso 1 1 calc R . . C16 C 0.19667(7) 0.4569(2) 0.04351(18) 0.0363(4) Uani 1 1 d . . . H16 H 0.2363 0.4705 0.0133 0.044 Uiso 1 1 calc R . . C17 C 0.17497(6) 0.3038(2) 0.06368(15) 0.0318(3) Uani 1 1 d . . . C18 C 0.11614(6) 0.28620(19) 0.10490(16) 0.0322(3) Uani 1 1 d . . . H18 H 0.1003 0.1825 0.1172 0.039 Uiso 1 1 calc R . . C19 C 0.08063(6) 0.41792(18) 0.12814(16) 0.0309(3) Uani 1 1 d . . . H19 H 0.0408 0.4047 0.1567 0.037 Uiso 1 1 calc R . . C20 C 0.21359(7) 0.1597(2) 0.0457(2) 0.0421(4) Uani 1 1 d . . . H20A H 0.1888 0.0641 0.0420 0.051 Uiso 1 1 calc R . . H20B H 0.2411 0.1515 0.1220 0.051 Uiso 1 1 calc R . . H20C H 0.2361 0.1695 -0.0386 0.051 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 0.03561(18) 0.02541(18) 0.02858(18) -0.00330(13) -0.00290(13) 0.00349(14) O1 0.0545(6) 0.0336(6) 0.0403(6) -0.0032(6) 0.0039(5) -0.0191(6) O2 0.0592(7) 0.0282(6) 0.0326(6) 0.0016(5) -0.0001(5) 0.0034(5) O3 0.0353(5) 0.0442(7) 0.0429(6) -0.0098(5) -0.0096(5) 0.0086(5) N1 0.0290(5) 0.0250(6) 0.0285(6) -0.0028(5) 0.0002(4) -0.0027(5) C1 0.0475(9) 0.0283(8) 0.0336(8) 0.0001(7) 0.0026(7) -0.0103(7) C2 0.0259(6) 0.0249(7) 0.0275(7) 0.0012(6) 0.0001(5) -0.0004(6) C3 0.0226(6) 0.0236(7) 0.0272(7) 0.0001(5) 0.0005(5) -0.0001(5) C4 0.0294(7) 0.0285(7) 0.0300(8) -0.0047(6) 0.0038(6) -0.0044(6) C5 0.0299(7) 0.0263(7) 0.0323(7) -0.0015(6) 0.0011(6) -0.0054(6) C6 0.0308(7) 0.0299(8) 0.0319(8) -0.0016(6) 0.0035(6) -0.0047(6) C7 0.0284(6) 0.0238(7) 0.0275(7) 0.0009(6) 0.0006(5) -0.0035(6) C8 0.0420(8) 0.0298(8) 0.0291(7) -0.0011(6) 0.0060(6) -0.0082(7) C9 0.0405(8) 0.0318(8) 0.0256(7) -0.0022(6) 0.0002(6) -0.0060(6) C10 0.0322(7) 0.0229(7) 0.0308(7) -0.0042(6) -0.0005(6) -0.0026(6) C11 0.0372(8) 0.0309(8) 0.0352(8) -0.0051(6) 0.0004(6) -0.0082(6) C12 0.0373(8) 0.0276(8) 0.0435(9) 0.0039(7) -0.0061(7) -0.0013(6) C13 0.0389(7) 0.0288(8) 0.0472(9) -0.0058(7) 0.0031(7) 0.0025(6) C14 0.0316(7) 0.0263(8) 0.0270(7) -0.0046(6) -0.0004(6) 0.0002(6) C15 0.0350(8) 0.0294(8) 0.0393(9) -0.0021(6) 0.0047(6) -0.0060(6) C16 0.0277(7) 0.0387(9) 0.0426(9) -0.0056(8) 0.0065(6) -0.0029(6) C17 0.0306(7) 0.0329(8) 0.0320(8) -0.0056(6) -0.0057(6) 0.0019(6) C18 0.0339(7) 0.0266(8) 0.0361(8) -0.0045(6) -0.0002(6) -0.0044(6) C19 0.0288(7) 0.0298(8) 0.0340(8) -0.0061(6) 0.0030(6) -0.0039(6) C20 0.0347(8) 0.0401(9) 0.0514(10) -0.0099(8) -0.0052(7) 0.0055(7) _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 O3 1.4281(11) . ? S1 O2 1.4362(12) . ? S1 N1 1.6429(12) . ? S1 C14 1.7649(15) . ? O1 C11 1.434(2) . ? O1 C1 1.4369(19) . ? N1 C5 1.4774(18) . ? N1 C4 1.4803(17) . ? C1 C2 1.513(2) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 C3 1.331(2) . ? C2 C10 1.513(2) . ? C3 C4 1.5074(19) . ? C3 C7 1.5244(19) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C6 1.525(2) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 C7 1.5470(19) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C8 1.5393(19) . ? C7 C12 1.540(2) . ? C8 C9 1.534(2) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? C9 C10 1.526(2) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C11 1.5326(19) . ? C10 C13 1.539(2) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 C19 1.386(2) . ? C14 C15 1.391(2) . ? C15 C16 1.384(2) . ? C15 H15 0.9500 . ? C16 C17 1.391(2) . ? C16 H16 0.9500 . ? C17 C18 1.397(2) . ? C17 C20 1.503(2) . ? C18 C19 1.386(2) . ? C18 H18 0.9500 . ? C19 H19 0.9500 . ? 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 O3 S1 O2 120.13(7) . . ? O3 S1 N1 106.50(6) . . ? O2 S1 N1 106.53(7) . . ? O3 S1 C14 108.46(7) . . ? O2 S1 C14 108.15(7) . . ? N1 S1 C14 106.27(7) . . ? C11 O1 C1 108.49(12) . . ? C5 N1 C4 111.95(11) . . ? C5 N1 S1 117.10(10) . . ? C4 N1 S1 116.71(9) . . ? O1 C1 C2 105.67(12) . . ? O1 C1 H1A 110.6 . . ? C2 C1 H1A 110.6 . . ? O1 C1 H1B 110.6 . . ? C2 C1 H1B 110.6 . . ? H1A C1 H1B 108.7 . . ? C3 C2 C10 125.05(13) . . ? C3 C2 C1 128.34(14) . . ? C10 C2 C1 106.27(12) . . ? C2 C3 C4 121.20(13) . . ? C2 C3 C7 122.91(13) . . ? C4 C3 C7 115.88(12) . . ? N1 C4 C3 108.10(11) . . ? N1 C4 H4A 110.1 . . ? C3 C4 H4A 110.1 . . ? N1 C4 H4B 110.1 . . ? C3 C4 H4B 110.1 . . ? H4A C4 H4B 108.4 . . ? N1 C5 C6 108.46(12) . . ? N1 C5 H5A 110.0 . . ? C6 C5 H5A 110.0 . . ? N1 C5 H5B 110.0 . . ? C6 C5 H5B 110.0 . . ? H5A C5 H5B 108.4 . . ? C5 C6 C7 114.00(12) . . ? C5 C6 H6A 108.8 . . ? C7 C6 H6A 108.8 . . ? C5 C6 H6B 108.8 . . ? C7 C6 H6B 108.8 . . ? H6A C6 H6B 107.6 . . ? C3 C7 C8 110.71(12) . . ? C3 C7 C12 109.99(11) . . ? C8 C7 C12 109.15(12) . . ? C3 C7 C6 108.22(12) . . ? C8 C7 C6 108.97(11) . . ? C12 C7 C6 109.78(12) . . ? C9 C8 C7 112.71(12) . . ? C9 C8 H8A 109.0 . . ? C7 C8 H8A 109.0 . . ? C9 C8 H8B 109.0 . . ? C7 C8 H8B 109.0 . . ? H8A C8 H8B 107.8 . . ? C10 C9 C8 109.65(12) . . ? C10 C9 H9A 109.7 . . ? C8 C9 H9A 109.7 . . ? C10 C9 H9B 109.7 . . ? C8 C9 H9B 109.7 . . ? H9A C9 H9B 108.2 . . ? C2 C10 C9 110.48(12) . . ? C2 C10 C11 98.83(12) . . ? C9 C10 C11 115.96(13) . . ? C2 C10 C13 110.02(12) . . ? C9 C10 C13 111.49(13) . . ? C11 C10 C13 109.34(12) . . ? O1 C11 C10 105.41(12) . . ? O1 C11 H11A 110.7 . . ? C10 C11 H11A 110.7 . . ? O1 C11 H11B 110.7 . . ? C10 C11 H11B 110.7 . . ? H11A C11 H11B 108.8 . . ? C7 C12 H12A 109.5 . . ? C7 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C7 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C19 C14 C15 120.77(14) . . ? C19 C14 S1 118.55(11) . . ? C15 C14 S1 120.40(12) . . ? C16 C15 C14 118.92(15) . . ? C16 C15 H15 120.5 . . ? C14 C15 H15 120.5 . . ? C15 C16 C17 121.58(13) . . ? C15 C16 H16 119.2 . . ? C17 C16 H16 119.2 . . ? C16 C17 C18 118.34(14) . . ? C16 C17 C20 121.61(13) . . ? C18 C17 C20 120.03(15) . . ? C19 C18 C17 120.91(14) . . ? C19 C18 H18 119.5 . . ? C17 C18 H18 119.5 . . ? C14 C19 C18 119.46(13) . . ? C14 C19 H19 120.3 . . ? C18 C19 H19 120.3 . . ? 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 O3 S1 N1 C5 50.09(11) . . . . ? O2 S1 N1 C5 179.44(10) . . . . ? C14 S1 N1 C5 -65.41(11) . . . . ? O3 S1 N1 C4 -173.23(10) . . . . ? O2 S1 N1 C4 -43.88(12) . . . . ? C14 S1 N1 C4 71.27(12) . . . . ? C11 O1 C1 C2 8.88(17) . . . . ? O1 C1 C2 C3 -156.82(15) . . . . ? O1 C1 C2 C10 16.60(16) . . . . ? C10 C2 C3 C4 179.44(13) . . . . ? C1 C2 C3 C4 -8.3(2) . . . . ? C10 C2 C3 C7 0.4(2) . . . . ? C1 C2 C3 C7 172.64(14) . . . . ? C5 N1 C4 C3 -61.83(14) . . . . ? S1 N1 C4 C3 159.35(10) . . . . ? C2 C3 C4 N1 -123.63(14) . . . . ? C7 C3 C4 N1 55.52(15) . . . . ? C4 N1 C5 C6 62.56(14) . . . . ? S1 N1 C5 C6 -158.79(10) . . . . ? N1 C5 C6 C7 -55.72(16) . . . . ? C2 C3 C7 C8 11.25(18) . . . . ? C4 C3 C7 C8 -167.89(12) . . . . ? C2 C3 C7 C12 -109.46(15) . . . . ? C4 C3 C7 C12 71.41(15) . . . . ? C2 C3 C7 C6 130.62(14) . . . . ? C4 C3 C7 C6 -48.52(15) . . . . ? C5 C6 C7 C3 48.03(16) . . . . ? C5 C6 C7 C8 168.50(12) . . . . ? C5 C6 C7 C12 -72.02(16) . . . . ? C3 C7 C8 C9 -42.24(16) . . . . ? C12 C7 C8 C9 78.96(15) . . . . ? C6 C7 C8 C9 -161.16(13) . . . . ? C7 C8 C9 C10 62.42(17) . . . . ? C3 C2 C10 C9 18.6(2) . . . . ? C1 C2 C10 C9 -155.08(12) . . . . ? C3 C2 C10 C11 140.68(14) . . . . ? C1 C2 C10 C11 -33.02(14) . . . . ? C3 C2 C10 C13 -104.90(16) . . . . ? C1 C2 C10 C13 81.40(15) . . . . ? C8 C9 C10 C2 -47.88(16) . . . . ? C8 C9 C10 C11 -159.24(13) . . . . ? C8 C9 C10 C13 74.78(16) . . . . ? C1 O1 C11 C10 -30.75(16) . . . . ? C2 C10 C11 O1 38.73(14) . . . . ? C9 C10 C11 O1 156.73(13) . . . . ? C13 C10 C11 O1 -76.21(15) . . . . ? O3 S1 C14 C19 -31.97(14) . . . . ? O2 S1 C14 C19 -163.76(12) . . . . ? N1 S1 C14 C19 82.20(13) . . . . ? O3 S1 C14 C15 154.01(13) . . . . ? O2 S1 C14 C15 22.23(15) . . . . ? N1 S1 C14 C15 -91.82(13) . . . . ? C19 C14 C15 C16 -0.4(2) . . . . ? S1 C14 C15 C16 173.45(13) . . . . ? C14 C15 C16 C17 -0.7(3) . . . . ? C15 C16 C17 C18 1.6(2) . . . . ? C15 C16 C17 C20 -176.77(16) . . . . ? C16 C17 C18 C19 -1.4(2) . . . . ? C20 C17 C18 C19 176.95(15) . . . . ? C15 C14 C19 C18 0.6(2) . . . . ? S1 C14 C19 C18 -173.42(12) . . . . ? C17 C18 C19 C14 0.4(2) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 68.22 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.220 _refine_diff_density_min -0.220 _refine_diff_density_rms 0.043 data_III _database_code_depnum_ccdc_archive 'CCDC 673295' _chemical_name_systematic ; ? ; _chemical_name_common ; (+)-5a-Methyl-2-(toluene-4-sulfonyl)-1,2,3,3a,4,5,5a,6- octahydro-7-oxa-2-aza-cyclopenta(c)phenanthrene ; _chemical_melting_point ? _chemical_formula_moiety 'C23 H25 N O3 S' _chemical_formula_sum 'C23 H25 N O3 S' _chemical_formula_weight 395.50 _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 0.0181 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' O O 0.0492 0.0322 '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' S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21 1' _symmetry_space_group_name_Hall 'P 2yb' _symmetry_Int_Tables_number 4 loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 +X,+Y,+Z 2 -X,1/2+Y,-Z _cell_length_a 6.41237(12) _cell_length_b 7.61490(14) _cell_length_c 20.4737(4) _cell_angle_alpha 90.00 _cell_angle_beta 96.7050(10) _cell_angle_gamma 90.00 _cell_volume 992.88(3) _cell_formula_units_Z 2 _cell_measurement_temperature 193 _cell_measurement_reflns_used 16763 _cell_measurement_theta_min 4.3 _cell_measurement_theta_max 68.2 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.323 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 420 _exptl_absorpt_coefficient_mu 1.640 _exptl_absorpt_correction_type numerical _exptl_absorpt_process_details ; Higashi, T. (1999). Program for Absorption Correction. Rigaku Corporation, Tokyo, Japan. ; _exptl_absorpt_correction_T_min 0.641 _exptl_absorpt_correction_T_max 0.921 _exptl_special_details ; ? ; _diffrn_ambient_temperature 193 _diffrn_radiation_wavelength 1.54187 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku RAXIS-RAPID' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 10.00 _diffrn_reflns_number 17696 _diffrn_reflns_av_R_equivalents 0.0293 _diffrn_reflns_av_sigmaI/netI 0.0240 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 4.35 _diffrn_reflns_theta_max 68.19 _reflns_number_total 3537 _reflns_number_gt 3443 _reflns_threshold_expression >2sigma(I) _computing_data_collection PROCESS-AUTO _computing_cell_refinement PROCESS-AUTO _computing_data_reduction CrystalStructure _computing_structure_solution SIR2004 _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0454P)^2^+0.1036P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _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, 876-881-1606 Friedel Pairs' _refine_ls_abs_structure_Flack 0.008(12) _refine_ls_number_reflns 3537 _refine_ls_number_parameters 255 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0288 _refine_ls_R_factor_gt 0.0278 _refine_ls_wR_factor_ref 0.0750 _refine_ls_wR_factor_gt 0.0719 _refine_ls_goodness_of_fit_ref 1.087 _refine_ls_restrained_S_all 1.087 _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 0.91801(6) 0.54072(6) 0.348865(17) 0.03310(11) Uani 1 1 d . . . O1 O 0.8359(2) 0.70418(17) 0.32194(6) 0.0438(3) Uani 1 1 d . . . O2 O 1.13927(19) 0.5108(2) 0.35730(6) 0.0463(4) Uani 1 1 d . . . O3 O 0.3640(2) 0.24840(19) 0.03488(5) 0.0415(3) Uani 1 1 d . . . N2 N 0.8149(2) 0.38814(19) 0.30036(6) 0.0312(3) Uani 1 1 d . . . C1 C 0.8839(3) 0.2046(2) 0.31095(9) 0.0385(4) Uani 1 1 d . . . H1A H 0.8646 0.1651 0.3559 0.046 Uiso 1 1 calc R . . H1B H 1.0335 0.1912 0.3043 0.046 Uiso 1 1 calc R . . C2 C 0.7430(3) 0.1010(2) 0.25947(8) 0.0321(4) Uani 1 1 d . . . H2 H 0.6777 0.0008 0.2813 0.039 Uiso 1 1 calc R . . C3 C 0.5734(2) 0.2290(2) 0.23280(7) 0.0267(3) Uani 1 1 d . . . C4 C 0.5886(2) 0.3911(2) 0.27550(7) 0.0283(3) Uani 1 1 d . . . H4A H 0.5501 0.4984 0.2496 0.034 Uiso 1 1 calc R . . H4B H 0.4995 0.3815 0.3117 0.034 Uiso 1 1 calc R . . C5 C 0.8520(3) 0.0318(3) 0.20239(8) 0.0355(4) Uani 1 1 d . . . H5A H 0.9171 0.1299 0.1804 0.043 Uiso 1 1 calc R . . H5B H 0.9636 -0.0525 0.2187 0.043 Uiso 1 1 calc R . . C6 C 0.6879(3) -0.0591(3) 0.15398(9) 0.0385(4) Uani 1 1 d . . . H6A H 0.6367 -0.1645 0.1755 0.046 Uiso 1 1 calc R . . H6B H 0.7564 -0.0993 0.1158 0.046 Uiso 1 1 calc R . . C7 C 0.4965(2) 0.0559(2) 0.12857(7) 0.0313(4) Uani 1 1 d . . . C8 C 0.4587(2) 0.2083(2) 0.17441(7) 0.0262(3) Uani 1 1 d . . . C9 C 0.3039(3) -0.0637(3) 0.11572(10) 0.0421(4) Uani 1 1 d . . . H9A H 0.3308 -0.1546 0.0839 0.050 Uiso 1 1 calc R . . H9B H 0.1819 0.0062 0.0980 0.050 Uiso 1 1 calc R . . H9C H 0.2758 -0.1191 0.1570 0.050 Uiso 1 1 calc R . . C10 C 0.5385(3) 0.1443(3) 0.06415(9) 0.0383(4) Uani 1 1 d . . . H10A H 0.6637 0.2205 0.0728 0.046 Uiso 1 1 calc R . . H10B H 0.5703 0.0526 0.0325 0.046 Uiso 1 1 calc R . . C11 C 0.2539(3) 0.3428(2) 0.07662(8) 0.0323(4) Uani 1 1 d . . . C12 C 0.0909(3) 0.4450(3) 0.04723(8) 0.0389(4) Uani 1 1 d . . . H12 H 0.0636 0.4493 0.0006 0.047 Uiso 1 1 calc R . . C13 C -0.0322(3) 0.5407(3) 0.08521(8) 0.0381(4) Uani 1 1 d . . . H13 H -0.1452 0.6095 0.0649 0.046 Uiso 1 1 calc R . . C14 C 0.0097(3) 0.5360(3) 0.15360(8) 0.0336(3) Uani 1 1 d . . . H14 H -0.0726 0.6035 0.1801 0.040 Uiso 1 1 calc R . . C15 C 0.1714(2) 0.4326(2) 0.18253(7) 0.0286(3) Uani 1 1 d . . . H15 H 0.1976 0.4288 0.2291 0.034 Uiso 1 1 calc R . . C16 C 0.2986(2) 0.3328(2) 0.14531(7) 0.0262(3) Uani 1 1 d . . . C17 C 0.8276(2) 0.5159(2) 0.42663(7) 0.0297(3) Uani 1 1 d . . . C18 C 0.6292(3) 0.5772(2) 0.43575(8) 0.0374(4) Uani 1 1 d . . . H18 H 0.5402 0.6259 0.4000 0.045 Uiso 1 1 calc R . . C19 C 0.5627(3) 0.5664(3) 0.49745(9) 0.0413(4) Uani 1 1 d . . . H19 H 0.4267 0.6081 0.5037 0.050 Uiso 1 1 calc R . . C20 C 0.6905(3) 0.4959(2) 0.55075(8) 0.0375(4) Uani 1 1 d . . . C21 C 0.8857(3) 0.4316(3) 0.53994(8) 0.0362(4) Uani 1 1 d . . . H21 H 0.9736 0.3806 0.5755 0.043 Uiso 1 1 calc R . . C22 C 0.9556(3) 0.4400(2) 0.47852(8) 0.0333(4) Uani 1 1 d . . . H22 H 1.0895 0.3944 0.4719 0.040 Uiso 1 1 calc R . . C23 C 0.6171(4) 0.4913(3) 0.61781(10) 0.0532(6) Uani 1 1 d . . . H23A H 0.4712 0.4506 0.6140 0.064 Uiso 1 1 calc R . . H23B H 0.6261 0.6094 0.6369 0.064 Uiso 1 1 calc R . . H23C H 0.7060 0.4109 0.6462 0.064 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 0.0322(2) 0.0390(2) 0.02725(18) -0.00092(17) -0.00008(14) -0.00418(18) O1 0.0585(9) 0.0357(7) 0.0348(6) 0.0020(5) -0.0046(6) -0.0069(6) O2 0.0311(6) 0.0712(10) 0.0364(6) -0.0056(7) 0.0029(5) -0.0068(7) O3 0.0443(7) 0.0542(8) 0.0263(6) -0.0060(5) 0.0050(5) 0.0062(6) N2 0.0288(8) 0.0340(8) 0.0294(7) -0.0015(6) -0.0024(6) 0.0039(6) C1 0.0367(10) 0.0377(10) 0.0392(9) 0.0031(8) -0.0039(7) 0.0104(8) C2 0.0320(9) 0.0297(9) 0.0350(8) 0.0051(7) 0.0054(7) 0.0060(7) C3 0.0270(8) 0.0242(8) 0.0297(7) 0.0011(6) 0.0070(6) 0.0018(7) C4 0.0277(8) 0.0290(8) 0.0273(7) -0.0011(6) -0.0006(6) 0.0030(6) C5 0.0300(8) 0.0332(9) 0.0444(8) -0.0014(9) 0.0090(7) 0.0064(8) C6 0.0364(10) 0.0310(9) 0.0496(10) -0.0097(8) 0.0116(8) 0.0033(8) C7 0.0294(8) 0.0299(9) 0.0356(8) -0.0080(8) 0.0080(6) -0.0012(8) C8 0.0253(8) 0.0242(8) 0.0300(7) -0.0027(6) 0.0079(6) -0.0003(6) C9 0.0378(10) 0.0346(10) 0.0549(10) -0.0147(9) 0.0105(8) -0.0067(9) C10 0.0371(10) 0.0442(11) 0.0351(9) -0.0096(8) 0.0108(7) 0.0010(8) C11 0.0325(9) 0.0349(9) 0.0297(8) -0.0019(7) 0.0043(7) -0.0039(7) C12 0.0400(10) 0.0460(11) 0.0291(8) 0.0041(8) -0.0027(7) -0.0031(9) C13 0.0344(9) 0.0355(9) 0.0421(8) 0.0059(9) -0.0056(7) 0.0004(9) C14 0.0319(8) 0.0287(8) 0.0401(8) 0.0007(8) 0.0036(6) 0.0055(9) C15 0.0301(8) 0.0278(8) 0.0278(7) -0.0003(7) 0.0036(6) -0.0007(7) C16 0.0256(8) 0.0250(8) 0.0278(7) -0.0003(6) 0.0026(6) -0.0036(6) C17 0.0293(8) 0.0317(9) 0.0274(7) -0.0030(7) -0.0003(6) -0.0008(7) C18 0.0327(9) 0.0400(11) 0.0379(8) -0.0023(7) -0.0024(7) 0.0039(7) C19 0.0296(9) 0.0463(12) 0.0485(9) -0.0092(9) 0.0070(7) 0.0021(8) C20 0.0403(10) 0.0367(11) 0.0362(8) -0.0089(7) 0.0077(7) -0.0094(7) C21 0.0394(10) 0.0361(9) 0.0316(8) 0.0000(7) -0.0021(7) 0.0011(8) C22 0.0307(9) 0.0362(9) 0.0321(8) -0.0013(7) 0.0000(6) 0.0032(8) C23 0.0601(13) 0.0608(15) 0.0415(10) -0.0121(9) 0.0176(9) -0.0146(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S1 O2 1.4274(13) . ? S1 O1 1.4362(14) . ? S1 N2 1.6188(14) . ? S1 C17 1.7670(16) . ? O3 C11 1.373(2) . ? O3 C10 1.443(2) . ? N2 C1 1.474(2) . ? N2 C4 1.481(2) . ? C1 C2 1.526(2) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 C3 1.515(2) . ? C2 C5 1.524(2) . ? C2 H2 1.0000 . ? C3 C8 1.338(2) . ? C3 C4 1.509(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C6 1.525(2) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 C7 1.547(3) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? C7 C8 1.529(2) . ? C7 C10 1.532(2) . ? C7 C9 1.532(2) . ? C8 C16 1.471(2) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 C12 1.383(3) . ? C11 C16 1.404(2) . ? C12 C13 1.379(3) . ? C12 H12 0.9500 . ? C13 C14 1.395(2) . ? C13 H13 0.9500 . ? C14 C15 1.380(2) . ? C14 H14 0.9500 . ? C15 C16 1.403(2) . ? C15 H15 0.9500 . ? C17 C18 1.388(2) . ? C17 C22 1.391(2) . ? C18 C19 1.382(3) . ? C18 H18 0.9500 . ? C19 C20 1.394(3) . ? C19 H19 0.9500 . ? C20 C21 1.386(3) . ? C20 C23 1.503(3) . ? C21 C22 1.385(2) . ? C21 H21 0.9500 . ? C22 H22 0.9500 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 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 O2 S1 O1 119.95(9) . . ? O2 S1 N2 106.79(8) . . ? O1 S1 N2 106.34(7) . . ? O2 S1 C17 107.46(7) . . ? O1 S1 C17 107.12(8) . . ? N2 S1 C17 108.81(8) . . ? C11 O3 C10 117.33(12) . . ? C1 N2 C4 109.28(13) . . ? C1 N2 S1 119.73(11) . . ? C4 N2 S1 120.92(11) . . ? N2 C1 C2 104.20(13) . . ? N2 C1 H1A 110.9 . . ? C2 C1 H1A 110.9 . . ? N2 C1 H1B 110.9 . . ? C2 C1 H1B 110.9 . . ? H1A C1 H1B 108.9 . . ? C3 C2 C5 108.69(13) . . ? C3 C2 C1 104.97(13) . . ? C5 C2 C1 114.91(15) . . ? C3 C2 H2 109.4 . . ? C5 C2 H2 109.4 . . ? C1 C2 H2 109.4 . . ? C8 C3 C4 127.29(14) . . ? C8 C3 C2 122.88(14) . . ? C4 C3 C2 108.82(13) . . ? N2 C4 C3 100.45(13) . . ? N2 C4 H4A 111.7 . . ? C3 C4 H4A 111.7 . . ? N2 C4 H4B 111.7 . . ? C3 C4 H4B 111.7 . . ? H4A C4 H4B 109.5 . . ? C6 C5 C2 108.17(14) . . ? C6 C5 H5A 110.1 . . ? C2 C5 H5A 110.1 . . ? C6 C5 H5B 110.1 . . ? C2 C5 H5B 110.1 . . ? H5A C5 H5B 108.4 . . ? C5 C6 C7 114.96(15) . . ? C5 C6 H6A 108.5 . . ? C7 C6 H6A 108.5 . . ? C5 C6 H6B 108.5 . . ? C7 C6 H6B 108.5 . . ? H6A C6 H6B 107.5 . . ? C8 C7 C10 104.56(14) . . ? C8 C7 C9 111.98(13) . . ? C10 C7 C9 109.40(14) . . ? C8 C7 C6 113.54(13) . . ? C10 C7 C6 109.00(14) . . ? C9 C7 C6 108.24(16) . . ? C3 C8 C16 124.80(14) . . ? C3 C8 C7 121.87(14) . . ? C16 C8 C7 113.16(13) . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? O3 C10 C7 113.15(14) . . ? O3 C10 H10A 108.9 . . ? C7 C10 H10A 108.9 . . ? O3 C10 H10B 108.9 . . ? C7 C10 H10B 108.9 . . ? H10A C10 H10B 107.8 . . ? O3 C11 C12 116.18(14) . . ? O3 C11 C16 122.35(15) . . ? C12 C11 C16 121.45(16) . . ? C13 C12 C11 120.35(15) . . ? C13 C12 H12 119.8 . . ? C11 C12 H12 119.8 . . ? C12 C13 C14 119.77(16) . . ? C12 C13 H13 120.1 . . ? C14 C13 H13 120.1 . . ? C15 C14 C13 119.50(16) . . ? C15 C14 H14 120.2 . . ? C13 C14 H14 120.2 . . ? C14 C15 C16 122.11(14) . . ? C14 C15 H15 118.9 . . ? C16 C15 H15 118.9 . . ? C15 C16 C11 116.80(14) . . ? C15 C16 C8 123.46(13) . . ? C11 C16 C8 119.46(14) . . ? C18 C17 C22 120.38(15) . . ? C18 C17 S1 119.19(12) . . ? C22 C17 S1 120.40(13) . . ? C19 C18 C17 119.26(16) . . ? C19 C18 H18 120.4 . . ? C17 C18 H18 120.4 . . ? C18 C19 C20 121.49(16) . . ? C18 C19 H19 119.3 . . ? C20 C19 H19 119.3 . . ? C21 C20 C19 118.08(16) . . ? C21 C20 C23 121.54(17) . . ? C19 C20 C23 120.39(17) . . ? C22 C21 C20 121.54(16) . . ? C22 C21 H21 119.2 . . ? C20 C21 H21 119.2 . . ? C21 C22 C17 119.20(16) . . ? C21 C22 H22 120.4 . . ? C17 C22 H22 120.4 . . ? C20 C23 H23A 109.5 . . ? C20 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C20 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 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 O2 S1 N2 C1 44.85(15) . . . . ? O1 S1 N2 C1 174.05(13) . . . . ? C17 S1 N2 C1 -70.87(15) . . . . ? O2 S1 N2 C4 -173.40(12) . . . . ? O1 S1 N2 C4 -44.20(14) . . . . ? C17 S1 N2 C4 70.88(14) . . . . ? C4 N2 C1 C2 30.54(18) . . . . ? S1 N2 C1 C2 176.30(11) . . . . ? N2 C1 C2 C3 -11.57(18) . . . . ? N2 C1 C2 C5 107.76(16) . . . . ? C5 C2 C3 C8 35.6(2) . . . . ? C1 C2 C3 C8 159.02(15) . . . . ? C5 C2 C3 C4 -133.69(15) . . . . ? C1 C2 C3 C4 -10.28(17) . . . . ? C1 N2 C4 C3 -35.91(16) . . . . ? S1 N2 C4 C3 178.81(11) . . . . ? C8 C3 C4 N2 -141.21(16) . . . . ? C2 C3 C4 N2 27.48(15) . . . . ? C3 C2 C5 C6 -59.68(19) . . . . ? C1 C2 C5 C6 -176.92(14) . . . . ? C2 C5 C6 C7 55.6(2) . . . . ? C5 C6 C7 C8 -23.0(2) . . . . ? C5 C6 C7 C10 93.06(18) . . . . ? C5 C6 C7 C9 -148.03(15) . . . . ? C4 C3 C8 C16 -10.1(3) . . . . ? C2 C3 C8 C16 -177.34(14) . . . . ? C4 C3 C8 C7 164.81(15) . . . . ? C2 C3 C8 C7 -2.4(2) . . . . ? C10 C7 C8 C3 -123.31(16) . . . . ? C9 C7 C8 C3 118.34(18) . . . . ? C6 C7 C8 C3 -4.6(2) . . . . ? C10 C7 C8 C16 52.15(16) . . . . ? C9 C7 C8 C16 -66.20(18) . . . . ? C6 C7 C8 C16 170.84(14) . . . . ? C11 O3 C10 C7 38.3(2) . . . . ? C8 C7 C10 O3 -60.99(17) . . . . ? C9 C7 C10 O3 59.1(2) . . . . ? C6 C7 C10 O3 177.29(14) . . . . ? C10 O3 C11 C12 178.40(16) . . . . ? C10 O3 C11 C16 -3.6(2) . . . . ? O3 C11 C12 C13 178.22(17) . . . . ? C16 C11 C12 C13 0.2(3) . . . . ? C11 C12 C13 C14 0.8(3) . . . . ? C12 C13 C14 C15 -1.3(3) . . . . ? C13 C14 C15 C16 0.9(3) . . . . ? C14 C15 C16 C11 0.0(2) . . . . ? C14 C15 C16 C8 -173.88(16) . . . . ? O3 C11 C16 C15 -178.52(16) . . . . ? C12 C11 C16 C15 -0.6(2) . . . . ? O3 C11 C16 C8 -4.3(2) . . . . ? C12 C11 C16 C8 173.58(16) . . . . ? C3 C8 C16 C15 -33.7(2) . . . . ? C7 C8 C16 C15 151.03(15) . . . . ? C3 C8 C16 C11 152.58(16) . . . . ? C7 C8 C16 C11 -22.7(2) . . . . ? O2 S1 C17 C18 165.09(14) . . . . ? O1 S1 C17 C18 34.95(16) . . . . ? N2 S1 C17 C18 -79.63(16) . . . . ? O2 S1 C17 C22 -13.30(17) . . . . ? O1 S1 C17 C22 -143.43(14) . . . . ? N2 S1 C17 C22 101.99(15) . . . . ? C22 C17 C18 C19 1.8(3) . . . . ? S1 C17 C18 C19 -176.55(14) . . . . ? C17 C18 C19 C20 0.2(3) . . . . ? C18 C19 C20 C21 -1.8(3) . . . . ? C18 C19 C20 C23 177.95(18) . . . . ? C19 C20 C21 C22 1.4(3) . . . . ? C23 C20 C21 C22 -178.30(17) . . . . ? C20 C21 C22 C17 0.5(3) . . . . ? C18 C17 C22 C21 -2.2(3) . . . . ? S1 C17 C22 C21 176.18(14) . . . . ? _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 68.19 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.124 _refine_diff_density_min -0.311 _refine_diff_density_rms 0.048