# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Coldham, I.' _publ_contact_author_email i.coldham@sheffield.ac.uk _publ_section_title ; Synthesis of the core ring system of the stemona alkaloids by cascade condensation, cyclization, intramolecular cycloaddition ; loop_ _publ_author_name I.Coldham A.Burrell L.Watson N.Martin N.Oram data_oic66_0m _database_code_depnum_ccdc_archive 'CCDC 782368' #TrackingRef 'oic66_0m.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C22 H31 Br Cl N O2' _chemical_formula_weight 456.84 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 '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)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 7.8562(4) _cell_length_b 11.9575(6) _cell_length_c 23.0397(11) _cell_angle_alpha 90.00 _cell_angle_beta 95.316(3) _cell_angle_gamma 90.00 _cell_volume 2155.05(19) _cell_formula_units_Z 4 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 9902 _cell_measurement_theta_min 2.46 _cell_measurement_theta_max 24.96 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.32 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.408 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 952 _exptl_absorpt_coefficient_mu 2.048 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5602 _exptl_absorpt_correction_T_max 0.6730 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 296(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 100 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 63019 _diffrn_reflns_av_R_equivalents 0.0281 _diffrn_reflns_av_sigmaI/netI 0.0198 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -32 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 29.85 _reflns_number_total 6158 _reflns_number_gt 4094 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0496P)^2^+1.3699P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 6158 _refine_ls_number_parameters 245 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0754 _refine_ls_R_factor_gt 0.0433 _refine_ls_wR_factor_ref 0.1262 _refine_ls_wR_factor_gt 0.1096 _refine_ls_goodness_of_fit_ref 1.030 _refine_ls_restrained_S_all 1.030 _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 Br1 Br 0.23305(5) 0.29296(3) 1.048197(14) 0.08648(15) Uani 1 1 d . . . Cl1 Cl 0.48958(8) 0.58989(4) 0.22662(3) 0.05585(17) Uani 1 1 d . . . O1 O 0.3640(2) 0.66960(13) 0.83931(7) 0.0469(4) Uani 1 1 d . . . O2 O 0.2775(4) 0.79401(17) 0.90253(10) 0.0838(7) Uani 1 1 d . . . N1 N 0.59577(19) 0.64881(13) 0.73888(7) 0.0322(3) Uani 1 1 d . . . H1A H 0.5834 0.5733 0.7408 0.039 Uiso 1 1 calc R . . C1 C 0.4178(3) 0.70210(17) 0.74114(10) 0.0384(4) Uani 1 1 d . . . H1 H 0.3329 0.6427 0.7329 0.046 Uiso 1 1 calc R . . C2 C 0.4010(3) 0.7820(2) 0.68969(11) 0.0492(5) Uani 1 1 d . . . H2A H 0.2819 0.7959 0.6767 0.059 Uiso 1 1 calc R . . H2B H 0.4570 0.8527 0.6996 0.059 Uiso 1 1 calc R . . C3 C 0.4896(3) 0.7206(2) 0.64345(10) 0.0466(5) Uani 1 1 d . . . H3 H 0.5210 0.7741 0.6140 0.056 Uiso 1 1 calc R . . C4 C 0.3789(3) 0.6282(3) 0.61378(12) 0.0619(7) Uani 1 1 d . . . H4A H 0.3243 0.5868 0.6432 0.074 Uiso 1 1 calc R . . H4B H 0.2897 0.6619 0.5875 0.074 Uiso 1 1 calc R . . C5 C 0.4813(4) 0.5478(3) 0.57970(12) 0.0687(8) Uani 1 1 d . . . H5A H 0.4075 0.4887 0.5630 0.082 Uiso 1 1 calc R . . H5B H 0.5290 0.5872 0.5482 0.082 Uiso 1 1 calc R . . C6 C 0.6240(3) 0.4980(2) 0.62055(12) 0.0565(6) Uani 1 1 d . . . H6A H 0.6872 0.4450 0.5989 0.068 Uiso 1 1 calc R . . H6B H 0.5739 0.4570 0.6511 0.068 Uiso 1 1 calc R . . C7 C 0.7499(3) 0.58526(17) 0.64896(10) 0.0411(5) Uani 1 1 d . . . C8 C 0.8804(3) 0.52458(19) 0.69180(11) 0.0495(6) Uani 1 1 d . . . H8A H 0.8205 0.4658 0.7106 0.059 Uiso 1 1 calc R . . H8B H 0.9632 0.4886 0.6692 0.059 Uiso 1 1 calc R . . C9 C 0.9785(3) 0.5935(2) 0.73939(12) 0.0502(6) Uani 1 1 d . . . H9A H 1.0869 0.5572 0.7507 0.060 Uiso 1 1 calc R . . H9B H 1.0027 0.6666 0.7238 0.060 Uiso 1 1 calc R . . C10 C 0.8830(3) 0.6088(2) 0.79321(11) 0.0527(6) Uani 1 1 d . . . H10A H 0.9625 0.6388 0.8240 0.063 Uiso 1 1 calc R . . H10B H 0.8482 0.5355 0.8057 0.063 Uiso 1 1 calc R . . C11 C 0.7261(3) 0.68363(19) 0.78742(10) 0.0428(5) Uani 1 1 d . . . H11A H 0.6735 0.6826 0.8239 0.051 Uiso 1 1 calc R . . H11B H 0.7616 0.7598 0.7805 0.051 Uiso 1 1 calc R . . C12 C 0.6528(3) 0.67765(16) 0.67861(9) 0.0356(4) Uani 1 1 d . . . H12 H 0.7307 0.7416 0.6841 0.043 Uiso 1 1 calc R . . C13 C 0.3799(3) 0.75694(19) 0.79712(11) 0.0466(5) Uani 1 1 d . . . H13A H 0.4717 0.8076 0.8105 0.056 Uiso 1 1 calc R . . H13B H 0.2744 0.7994 0.7913 0.056 Uiso 1 1 calc R . . C14 C 0.3093(3) 0.6995(2) 0.89050(11) 0.0496(5) Uani 1 1 d . . . C15 C 0.2939(3) 0.6005(2) 0.92853(10) 0.0476(5) Uani 1 1 d . . . C16 C 0.3447(4) 0.4953(2) 0.91227(11) 0.0563(6) Uani 1 1 d . . . H16 H 0.3901 0.4855 0.8767 0.068 Uiso 1 1 calc R . . C17 C 0.3285(4) 0.4046(2) 0.94845(12) 0.0614(7) Uani 1 1 d . . . H17 H 0.3631 0.3339 0.9375 0.074 Uiso 1 1 calc R . . C18 C 0.2609(4) 0.4196(2) 1.00061(11) 0.0589(6) Uani 1 1 d . . . C19 C 0.2120(4) 0.5241(3) 1.01824(12) 0.0735(8) Uani 1 1 d . . . H19 H 0.1681 0.5334 1.0541 0.088 Uiso 1 1 calc R . . C20 C 0.2288(4) 0.6146(3) 0.98214(12) 0.0649(7) Uani 1 1 d . . . H20 H 0.1965 0.6854 0.9937 0.078 Uiso 1 1 calc R . . C21 C 0.8471(3) 0.6478(2) 0.60295(11) 0.0532(6) Uani 1 1 d . . . H21A H 0.7691 0.7010 0.5829 0.064 Uiso 1 1 calc R . . H21B H 0.9392 0.6903 0.6234 0.064 Uiso 1 1 calc R . . C22 C 0.9226(4) 0.5753(3) 0.55722(13) 0.0722(8) Uani 1 1 d . . . H22A H 0.9975 0.5204 0.5763 0.108 Uiso 1 1 calc R . . H22B H 0.9858 0.6215 0.5328 0.108 Uiso 1 1 calc R . . H22C H 0.8319 0.5383 0.5339 0.108 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 Br1 0.1126(3) 0.0917(3) 0.05502(19) 0.02046(16) 0.00689(17) -0.0157(2) Cl1 0.0635(4) 0.0316(2) 0.0768(4) -0.0006(3) 0.0298(3) -0.0074(2) O1 0.0566(9) 0.0395(8) 0.0475(9) -0.0037(7) 0.0197(7) -0.0003(7) O2 0.133(2) 0.0536(12) 0.0697(13) -0.0113(10) 0.0380(13) 0.0196(12) N1 0.0327(8) 0.0254(7) 0.0394(9) -0.0002(6) 0.0069(7) -0.0011(6) C1 0.0312(9) 0.0366(10) 0.0481(11) -0.0011(9) 0.0082(8) 0.0027(8) C2 0.0480(12) 0.0447(12) 0.0559(14) 0.0071(10) 0.0099(10) 0.0125(10) C3 0.0496(12) 0.0473(12) 0.0431(12) 0.0063(9) 0.0059(10) 0.0081(10) C4 0.0535(14) 0.0771(18) 0.0526(15) -0.0065(13) -0.0077(12) 0.0031(13) C5 0.0754(18) 0.0778(19) 0.0520(15) -0.0188(14) 0.0009(13) -0.0131(15) C6 0.0673(16) 0.0441(12) 0.0603(15) -0.0171(11) 0.0176(13) -0.0046(11) C7 0.0447(11) 0.0334(10) 0.0472(12) -0.0043(9) 0.0141(9) 0.0007(8) C8 0.0498(12) 0.0355(11) 0.0662(15) 0.0051(10) 0.0211(11) 0.0084(9) C9 0.0325(10) 0.0466(12) 0.0725(16) 0.0126(11) 0.0089(10) 0.0024(9) C10 0.0382(11) 0.0626(15) 0.0557(14) 0.0057(12) -0.0044(10) -0.0028(10) C11 0.0392(10) 0.0466(12) 0.0423(11) -0.0041(9) 0.0028(9) -0.0055(9) C12 0.0385(10) 0.0302(9) 0.0393(10) 0.0020(8) 0.0102(8) -0.0014(8) C13 0.0503(12) 0.0348(10) 0.0574(14) -0.0020(10) 0.0188(10) 0.0012(9) C14 0.0502(13) 0.0525(13) 0.0471(12) -0.0132(10) 0.0107(10) 0.0002(10) C15 0.0477(12) 0.0546(13) 0.0412(11) -0.0095(10) 0.0078(10) -0.0054(10) C16 0.0717(16) 0.0539(14) 0.0460(13) -0.0067(11) 0.0190(12) -0.0044(12) C17 0.0784(18) 0.0542(15) 0.0529(15) -0.0045(12) 0.0128(13) -0.0065(13) C18 0.0669(16) 0.0693(17) 0.0396(12) 0.0024(12) 0.0005(11) -0.0125(13) C19 0.092(2) 0.090(2) 0.0405(14) -0.0061(14) 0.0207(14) -0.0025(18) C20 0.0804(19) 0.0676(17) 0.0490(14) -0.0124(13) 0.0179(13) 0.0027(14) C21 0.0588(14) 0.0543(14) 0.0499(13) 0.0009(11) 0.0224(11) 0.0030(11) C22 0.0759(19) 0.085(2) 0.0606(17) -0.0127(15) 0.0328(15) 0.0001(16) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 C18 1.894(3) . ? O1 C14 1.340(3) . ? O1 C13 1.440(3) . ? O2 C14 1.196(3) . ? N1 C11 1.503(3) . ? N1 C12 1.537(3) . ? N1 C1 1.542(2) . ? N1 H1A 0.9100 . ? C1 C13 1.501(3) . ? C1 C2 1.519(3) . ? C1 H1 0.9800 . ? C2 C3 1.515(3) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 C4 1.528(4) . ? C3 C12 1.540(3) . ? C3 H3 0.9800 . ? C4 C5 1.518(4) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 C6 1.517(4) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C7 1.541(3) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C8 1.538(3) . ? C7 C12 1.538(3) . ? C7 C21 1.555(3) . ? C8 C9 1.523(4) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 C10 1.518(4) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C11 1.519(3) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12 0.9800 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 C15 1.484(4) . ? C15 C16 1.382(3) . ? C15 C20 1.390(4) . ? C16 C17 1.381(4) . ? C16 H16 0.9300 . ? C17 C18 1.370(4) . ? C17 H17 0.9300 . ? C18 C19 1.380(4) . ? C19 C20 1.379(4) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? C21 C22 1.527(3) . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 H22A 0.9600 . ? C22 H22B 0.9600 . ? C22 H22C 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 C14 O1 C13 117.10(18) . . ? C11 N1 C12 111.98(15) . . ? C11 N1 C1 114.70(16) . . ? C12 N1 C1 106.19(15) . . ? C11 N1 H1A 107.9 . . ? C12 N1 H1A 107.9 . . ? C1 N1 H1A 107.9 . . ? C13 C1 C2 112.71(18) . . ? C13 C1 N1 117.53(18) . . ? C2 C1 N1 104.30(16) . . ? C13 C1 H1 107.3 . . ? C2 C1 H1 107.3 . . ? N1 C1 H1 107.3 . . ? C3 C2 C1 103.38(17) . . ? C3 C2 H2A 111.1 . . ? C1 C2 H2A 111.1 . . ? C3 C2 H2B 111.1 . . ? C1 C2 H2B 111.1 . . ? H2A C2 H2B 109.1 . . ? C2 C3 C4 112.7(2) . . ? C2 C3 C12 101.89(18) . . ? C4 C3 C12 113.97(19) . . ? C2 C3 H3 109.4 . . ? C4 C3 H3 109.4 . . ? C12 C3 H3 109.4 . . ? C5 C4 C3 112.5(2) . . ? C5 C4 H4A 109.1 . . ? C3 C4 H4A 109.1 . . ? C5 C4 H4B 109.1 . . ? C3 C4 H4B 109.1 . . ? H4A C4 H4B 107.8 . . ? C6 C5 C4 108.9(2) . . ? C6 C5 H5A 109.9 . . ? C4 C5 H5A 109.9 . . ? C6 C5 H5B 109.9 . . ? C4 C5 H5B 109.9 . . ? H5A C5 H5B 108.3 . . ? C5 C6 C7 113.9(2) . . ? C5 C6 H6A 108.8 . . ? C7 C6 H6A 108.8 . . ? C5 C6 H6B 108.8 . . ? C7 C6 H6B 108.8 . . ? H6A C6 H6B 107.7 . . ? C8 C7 C12 112.49(18) . . ? C8 C7 C6 108.45(19) . . ? C12 C7 C6 110.48(18) . . ? C8 C7 C21 108.93(19) . . ? C12 C7 C21 104.61(17) . . ? C6 C7 C21 111.9(2) . . ? C9 C8 C7 118.00(18) . . ? C9 C8 H8A 107.8 . . ? C7 C8 H8A 107.8 . . ? C9 C8 H8B 107.8 . . ? C7 C8 H8B 107.8 . . ? H8A C8 H8B 107.1 . . ? C10 C9 C8 113.45(19) . . ? C10 C9 H9A 108.9 . . ? C8 C9 H9A 108.9 . . ? C10 C9 H9B 108.9 . . ? C8 C9 H9B 108.9 . . ? H9A C9 H9B 107.7 . . ? C9 C10 C11 117.2(2) . . ? C9 C10 H10A 108.0 . . ? C11 C10 H10A 108.0 . . ? C9 C10 H10B 108.0 . . ? C11 C10 H10B 108.0 . . ? H10A C10 H10B 107.2 . . ? N1 C11 C10 113.18(18) . . ? N1 C11 H11A 108.9 . . ? C10 C11 H11A 108.9 . . ? N1 C11 H11B 108.9 . . ? C10 C11 H11B 108.9 . . ? H11A C11 H11B 107.8 . . ? N1 C12 C7 115.98(16) . . ? N1 C12 C3 104.60(16) . . ? C7 C12 C3 115.39(18) . . ? N1 C12 H12 106.8 . . ? C7 C12 H12 106.8 . . ? C3 C12 H12 106.8 . . ? O1 C13 C1 107.44(17) . . ? O1 C13 H13A 110.2 . . ? C1 C13 H13A 110.2 . . ? O1 C13 H13B 110.2 . . ? C1 C13 H13B 110.2 . . ? H13A C13 H13B 108.5 . . ? O2 C14 O1 123.1(2) . . ? O2 C14 C15 125.9(2) . . ? O1 C14 C15 110.9(2) . . ? C16 C15 C20 119.4(2) . . ? C16 C15 C14 121.6(2) . . ? C20 C15 C14 119.0(2) . . ? C17 C16 C15 120.4(2) . . ? C17 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? C18 C17 C16 119.5(3) . . ? C18 C17 H17 120.3 . . ? C16 C17 H17 120.3 . . ? C17 C18 C19 121.2(3) . . ? C17 C18 Br1 118.6(2) . . ? C19 C18 Br1 120.2(2) . . ? C20 C19 C18 119.2(2) . . ? C20 C19 H19 120.4 . . ? C18 C19 H19 120.4 . . ? C19 C20 C15 120.3(3) . . ? C19 C20 H20 119.8 . . ? C15 C20 H20 119.8 . . ? C22 C21 C7 116.3(2) . . ? C22 C21 H21A 108.2 . . ? C7 C21 H21A 108.2 . . ? C22 C21 H21B 108.2 . . ? C7 C21 H21B 108.2 . . ? H21A C21 H21B 107.4 . . ? C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 29.85 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.827 _refine_diff_density_min -0.806 _refine_diff_density_rms 0.049 # Attachment '- oic70_0m 2.cif' data_oic70_0m _database_code_depnum_ccdc_archive 'CCDC 782369' #TrackingRef '- oic70_0m 2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C20 H29 N O2 S' _chemical_formula_weight 347.50 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)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.1393(7) _cell_length_b 7.7782(4) _cell_length_c 17.9896(9) _cell_angle_alpha 90.00 _cell_angle_beta 102.927(3) _cell_angle_gamma 90.00 _cell_volume 1791.94(16) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 4646 _cell_measurement_theta_min 2.32 _cell_measurement_theta_max 25.69 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.288 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 752 _exptl_absorpt_coefficient_mu 0.193 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9303 _exptl_absorpt_correction_T_max 0.9923 _exptl_absorpt_process_details sadabs _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(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 100 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 40116 _diffrn_reflns_av_R_equivalents 0.0738 _diffrn_reflns_av_sigmaI/netI 0.0389 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.59 _diffrn_reflns_theta_max 27.65 _reflns_number_total 4150 _reflns_number_gt 3179 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0465P)^2^+0.4528P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4150 _refine_ls_number_parameters 218 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0615 _refine_ls_R_factor_gt 0.0421 _refine_ls_wR_factor_ref 0.1058 _refine_ls_wR_factor_gt 0.0981 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.067 _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 0.10845(3) 0.91875(5) 0.17374(2) 0.02391(12) Uani 1 1 d . . . N1 N 0.24060(10) 0.51191(17) 0.26803(7) 0.0215(3) Uani 1 1 d . . . O1 O 0.20160(9) 0.93909(16) 0.14543(7) 0.0308(3) Uani 1 1 d . . . O2 O 0.06805(9) 1.06739(15) 0.20557(7) 0.0310(3) Uani 1 1 d . . . C1 C 0.15042(13) 0.5796(2) 0.21259(9) 0.0252(4) Uani 1 1 d . . . H1A H 0.0909 0.5032 0.2078 0.030 Uiso 1 1 calc R . . H1B H 0.1667 0.5927 0.1629 0.030 Uiso 1 1 calc R . . C2 C 0.12735(13) 0.7541(2) 0.24432(9) 0.0224(3) Uani 1 1 d . . . H2 H 0.0651 0.7451 0.2656 0.027 Uiso 1 1 calc R . . C3 C 0.22384(12) 0.7923(2) 0.30903(9) 0.0219(3) Uani 1 1 d . . . H3 H 0.2471 0.9111 0.3055 0.026 Uiso 1 1 calc R . . C4 C 0.19846(13) 0.7600(2) 0.38696(9) 0.0268(4) Uani 1 1 d . . . H4A H 0.1561 0.8540 0.3986 0.032 Uiso 1 1 calc R . . H4B H 0.1578 0.6552 0.3845 0.032 Uiso 1 1 calc R . . C5 C 0.29620(14) 0.7438(2) 0.45081(9) 0.0296(4) Uani 1 1 d . . . H5A H 0.3327 0.8531 0.4579 0.036 Uiso 1 1 calc R . . H5B H 0.2765 0.7145 0.4981 0.036 Uiso 1 1 calc R . . C6 C 0.36830(13) 0.6054(2) 0.43150(9) 0.0265(4) Uani 1 1 d . . . H6A H 0.3325 0.4955 0.4270 0.032 Uiso 1 1 calc R . . H6B H 0.4297 0.5967 0.4729 0.032 Uiso 1 1 calc R . . C7 C 0.40272(12) 0.6429(2) 0.35710(9) 0.0221(3) Uani 1 1 d . . . C8 C 0.47639(13) 0.5026(2) 0.33841(10) 0.0283(4) Uani 1 1 d . . . H8A H 0.4832 0.5214 0.2864 0.034 Uiso 1 1 calc R . . H8B H 0.5448 0.5216 0.3713 0.034 Uiso 1 1 calc R . . C9 C 0.44902(15) 0.3144(2) 0.34545(10) 0.0347(4) Uani 1 1 d . . . H9A H 0.4432 0.2942 0.3975 0.042 Uiso 1 1 calc R . . H9B H 0.5071 0.2458 0.3371 0.042 Uiso 1 1 calc R . . C10 C 0.34917(14) 0.2472(2) 0.29209(10) 0.0291(4) Uani 1 1 d . . . H10A H 0.3677 0.1484 0.2649 0.035 Uiso 1 1 calc R . . H10B H 0.3026 0.2069 0.3233 0.035 Uiso 1 1 calc R . . C11 C 0.28907(14) 0.3723(2) 0.23371(9) 0.0256(4) Uani 1 1 d . . . H11A H 0.3363 0.4211 0.2049 0.031 Uiso 1 1 calc R . . H11B H 0.2351 0.3100 0.1983 0.031 Uiso 1 1 calc R . . C12 C 0.30561(12) 0.6658(2) 0.29141(9) 0.0208(3) Uani 1 1 d . . . H12 H 0.3289 0.7088 0.2468 0.025 Uiso 1 1 calc R . . C13 C 0.00957(13) 0.8323(2) 0.09970(9) 0.0233(4) Uani 1 1 d . . . C14 C 0.03291(14) 0.7924(2) 0.03028(10) 0.0316(4) Uani 1 1 d . . . H14 H 0.0994 0.8126 0.0223 0.038 Uiso 1 1 calc R . . C15 C -0.04391(15) 0.7220(3) -0.02701(10) 0.0361(4) Uani 1 1 d . . . H15 H -0.0293 0.6957 -0.0740 0.043 Uiso 1 1 calc R . . C16 C -0.14178(15) 0.6909(3) -0.01474(10) 0.0343(4) Uani 1 1 d . . . H16 H -0.1930 0.6427 -0.0533 0.041 Uiso 1 1 calc R . . C17 C -0.16452(14) 0.7310(2) 0.05473(10) 0.0320(4) Uani 1 1 d . . . H17 H -0.2310 0.7098 0.0626 0.038 Uiso 1 1 calc R . . C18 C -0.08910(13) 0.8026(2) 0.11244(9) 0.0287(4) Uani 1 1 d . . . H18 H -0.1043 0.8303 0.1591 0.034 Uiso 1 1 calc R . . C19 C 0.46363(13) 0.8153(2) 0.36216(9) 0.0255(4) Uani 1 1 d . . . H19A H 0.4896 0.8278 0.3160 0.031 Uiso 1 1 calc R . . H19B H 0.4148 0.9084 0.3629 0.031 Uiso 1 1 calc R . . C20 C 0.55541(14) 0.8373(2) 0.43042(10) 0.0330(4) Uani 1 1 d . . . H20A H 0.5300 0.8411 0.4765 0.049 Uiso 1 1 calc R . . H20B H 0.5914 0.9424 0.4251 0.049 Uiso 1 1 calc R . . H20C H 0.6025 0.7421 0.4326 0.049 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 0.0218(2) 0.0234(2) 0.0252(2) 0.00179(16) 0.00242(16) 0.00124(17) N1 0.0206(7) 0.0188(7) 0.0232(7) -0.0004(5) 0.0012(5) -0.0008(6) O1 0.0240(7) 0.0359(7) 0.0322(7) 0.0049(5) 0.0060(5) -0.0023(5) O2 0.0322(7) 0.0249(7) 0.0339(7) -0.0016(5) 0.0028(5) 0.0047(5) C1 0.0255(9) 0.0218(8) 0.0254(8) 0.0000(6) -0.0003(7) -0.0008(7) C2 0.0202(8) 0.0245(8) 0.0217(8) 0.0018(6) 0.0028(6) -0.0020(7) C3 0.0205(8) 0.0210(8) 0.0231(8) 0.0000(6) 0.0025(6) -0.0012(6) C4 0.0246(9) 0.0315(9) 0.0242(8) -0.0047(7) 0.0052(7) -0.0014(7) C5 0.0288(10) 0.0403(11) 0.0200(8) -0.0027(7) 0.0059(7) -0.0033(8) C6 0.0246(9) 0.0324(10) 0.0208(8) 0.0051(7) 0.0017(7) -0.0019(7) C7 0.0200(8) 0.0237(8) 0.0216(8) 0.0021(6) 0.0026(6) -0.0011(7) C8 0.0223(9) 0.0295(9) 0.0305(9) 0.0003(7) 0.0004(7) 0.0019(7) C9 0.0405(11) 0.0271(9) 0.0323(9) 0.0022(7) -0.0006(8) 0.0092(8) C10 0.0336(10) 0.0219(9) 0.0327(9) 0.0021(7) 0.0093(8) 0.0039(7) C11 0.0287(9) 0.0246(9) 0.0235(8) -0.0030(6) 0.0057(7) 0.0006(7) C12 0.0215(8) 0.0202(8) 0.0207(7) 0.0004(6) 0.0046(6) -0.0017(6) C13 0.0235(9) 0.0221(8) 0.0232(8) 0.0031(6) 0.0024(7) 0.0040(7) C14 0.0266(10) 0.0406(11) 0.0280(9) 0.0014(8) 0.0068(7) 0.0021(8) C15 0.0357(11) 0.0494(12) 0.0227(8) -0.0037(8) 0.0059(8) 0.0021(9) C16 0.0308(10) 0.0406(11) 0.0268(9) -0.0043(8) -0.0035(8) 0.0017(8) C17 0.0214(9) 0.0396(11) 0.0342(9) -0.0025(8) 0.0043(8) 0.0003(8) C18 0.0263(9) 0.0355(10) 0.0240(8) -0.0030(7) 0.0047(7) 0.0028(8) C19 0.0219(9) 0.0269(9) 0.0265(8) 0.0014(7) 0.0026(7) -0.0045(7) C20 0.0285(10) 0.0343(10) 0.0323(9) -0.0001(8) -0.0011(8) -0.0065(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S1 O1 1.4357(12) . ? S1 O2 1.4430(12) . ? S1 C13 1.7720(17) . ? S1 C2 1.7811(16) . ? N1 C11 1.464(2) . ? N1 C1 1.465(2) . ? N1 C12 1.476(2) . ? C1 C2 1.529(2) . ? C1 H1A 0.9700 . ? C1 H1B 0.9700 . ? C2 C3 1.546(2) . ? C2 H2 0.9800 . ? C3 C4 1.533(2) . ? C3 C12 1.541(2) . ? C3 H3 0.9800 . ? C4 C5 1.525(2) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 C6 1.524(2) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C7 1.534(2) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C12 1.543(2) . ? C7 C8 1.544(2) . ? C7 C19 1.554(2) . ? C8 C9 1.520(3) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 C10 1.534(2) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C11 1.517(2) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 H12 0.9800 . ? C13 C18 1.386(2) . ? C13 C14 1.386(2) . ? C14 C15 1.384(3) . ? C14 H14 0.9300 . ? C15 C16 1.374(3) . ? C15 H15 0.9300 . ? C16 C17 1.384(2) . ? C16 H16 0.9300 . ? C17 C18 1.382(2) . ? C17 H17 0.9300 . ? C18 H18 0.9300 . ? C19 C20 1.526(2) . ? C19 H19A 0.9700 . ? C19 H19B 0.9700 . ? 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 O1 S1 O2 118.09(7) . . ? O1 S1 C13 108.37(8) . . ? O2 S1 C13 109.23(7) . . ? O1 S1 C2 109.76(8) . . ? O2 S1 C2 107.35(7) . . ? C13 S1 C2 103.00(8) . . ? C11 N1 C1 109.96(12) . . ? C11 N1 C12 116.32(13) . . ? C1 N1 C12 103.37(12) . . ? N1 C1 C2 105.21(12) . . ? N1 C1 H1A 110.7 . . ? C2 C1 H1A 110.7 . . ? N1 C1 H1B 110.7 . . ? C2 C1 H1B 110.7 . . ? H1A C1 H1B 108.8 . . ? C1 C2 C3 104.70(13) . . ? C1 C2 S1 112.33(11) . . ? C3 C2 S1 111.04(11) . . ? C1 C2 H2 109.6 . . ? C3 C2 H2 109.6 . . ? S1 C2 H2 109.6 . . ? C4 C3 C12 112.83(13) . . ? C4 C3 C2 110.35(13) . . ? C12 C3 C2 102.39(12) . . ? C4 C3 H3 110.3 . . ? C12 C3 H3 110.3 . . ? C2 C3 H3 110.3 . . ? C5 C4 C3 112.56(14) . . ? C5 C4 H4A 109.1 . . ? C3 C4 H4A 109.1 . . ? C5 C4 H4B 109.1 . . ? C3 C4 H4B 109.1 . . ? H4A C4 H4B 107.8 . . ? C6 C5 C4 110.39(13) . . ? C6 C5 H5A 109.6 . . ? C4 C5 H5A 109.6 . . ? C6 C5 H5B 109.6 . . ? C4 C5 H5B 109.6 . . ? H5A C5 H5B 108.1 . . ? C5 C6 C7 112.61(14) . . ? C5 C6 H6A 109.1 . . ? C7 C6 H6A 109.1 . . ? C5 C6 H6B 109.1 . . ? C7 C6 H6B 109.1 . . ? H6A C6 H6B 107.8 . . ? C6 C7 C12 109.60(13) . . ? C6 C7 C8 112.17(14) . . ? C12 C7 C8 111.47(13) . . ? C6 C7 C19 111.18(13) . . ? C12 C7 C19 105.79(13) . . ? C8 C7 C19 106.42(13) . . ? C9 C8 C7 119.39(15) . . ? C9 C8 H8A 107.5 . . ? C7 C8 H8A 107.5 . . ? C9 C8 H8B 107.5 . . ? C7 C8 H8B 107.5 . . ? H8A C8 H8B 107.0 . . ? C8 C9 C10 117.47(14) . . ? C8 C9 H9A 107.9 . . ? C10 C9 H9A 107.9 . . ? C8 C9 H9B 107.9 . . ? C10 C9 H9B 107.9 . . ? H9A C9 H9B 107.2 . . ? C11 C10 C9 117.04(15) . . ? C11 C10 H10A 108.0 . . ? C9 C10 H10A 108.0 . . ? C11 C10 H10B 108.0 . . ? C9 C10 H10B 108.0 . . ? H10A C10 H10B 107.3 . . ? N1 C11 C10 113.09(13) . . ? N1 C11 H11A 109.0 . . ? C10 C11 H11A 109.0 . . ? N1 C11 H11B 109.0 . . ? C10 C11 H11B 109.0 . . ? H11A C11 H11B 107.8 . . ? N1 C12 C3 101.00(12) . . ? N1 C12 C7 116.83(13) . . ? C3 C12 C7 114.29(13) . . ? N1 C12 H12 108.1 . . ? C3 C12 H12 108.1 . . ? C7 C12 H12 108.1 . . ? C18 C13 C14 121.02(16) . . ? C18 C13 S1 119.66(12) . . ? C14 C13 S1 119.31(13) . . ? C15 C14 C13 119.22(17) . . ? C15 C14 H14 120.4 . . ? C13 C14 H14 120.4 . . ? C16 C15 C14 120.19(16) . . ? C16 C15 H15 119.9 . . ? C14 C15 H15 119.9 . . ? C15 C16 C17 120.28(17) . . ? C15 C16 H16 119.9 . . ? C17 C16 H16 119.9 . . ? C18 C17 C16 120.39(17) . . ? C18 C17 H17 119.8 . . ? C16 C17 H17 119.8 . . ? C17 C18 C13 118.90(16) . . ? C17 C18 H18 120.5 . . ? C13 C18 H18 120.5 . . ? C20 C19 C7 116.60(14) . . ? C20 C19 H19A 108.1 . . ? C7 C19 H19A 108.1 . . ? C20 C19 H19B 108.1 . . ? C7 C19 H19B 108.1 . . ? H19A C19 H19B 107.3 . . ? C19 C20 H20A 109.5 . . ? C19 C20 H20B 109.5 . . ? H20A C20 H20B 109.5 . . ? C19 C20 H20C 109.5 . . ? H20A C20 H20C 109.5 . . ? H20B C20 H20C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.302 _refine_diff_density_min -0.352 _refine_diff_density_rms 0.050