Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_soja _database_code_CSD 171200 # 1. SUBMISSION DETAILS _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name _publ_author_address 'Fietz-Razavian, Sonja' ; Institut fur Organische Chemie Technische Universitat Braunschweig Postfach 3329 38023 Braunschweig Germany ; 'Schulz, Stefan' ; Institut fur Organische Chemie Technische Universitat Braunschweig Postfach 3329 38023 Braunschweig Germany ; _publ_contact_author_name 'Prof Stefan Schulz' _publ_contact_author_address ; Institut fur Organische Chemie Technische Universitat Braunschweig Hagenring 30 Braunschweig D-38108 GERMANY ; _publ_contact_author_email 'STEFAN.SCHULZ@TU-BS.DE' _publ_section_title ; Revision of the absolute configuration of the tricyclic sesquiterpene (+)-kelsoene by chemical correlation and enantiospecific total synthesis of enantiomer. ; _publ_contact_author_phone '049 531 391-5382' _publ_contact_author_fax '049 531 391-5387' _publ_contact_author_email STEFAN.SCHULZ@TU-BS.DE _publ_requested_journal 'Chem. Comm.' #============================================================================== _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H26 O3 S' _chemical_formula_weight 334.46 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' 'S' 'S' 0.1246 0.1234 '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' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 9.1578(8) _cell_length_b 11.7038(10) _cell_length_c 16.1527(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1731.3(3) _cell_formula_units_Z 4 _cell_measurement_temperature 143(2) _cell_measurement_reflns_used 6289 _cell_measurement_theta_min 2 _cell_measurement_theta_max 28 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.16 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.283 _exptl_crystal_density_method ? _exptl_crystal_F_000 720 _exptl_absorpt_coefficient_mu 0.200 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 143(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 'Bruker SMART 1000 CCD' _diffrn_measurement_method '\w-scan & \f-scan' _diffrn_detector_area_resol_mean 8.192 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 26944 _diffrn_reflns_av_R_equivalents 0.0405 _diffrn_reflns_av_sigmaI/netI 0.0263 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 2.15 _diffrn_reflns_theta_max 28.52 _reflns_number_total 4388 _reflns_number_gt 4047 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Siemens XP' _computing_publication_material SHELXL-97 _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^)+(0.0557P)^2^+0.0593P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.07(5) _refine_ls_number_reflns 4388 _refine_ls_number_parameters 211 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0358 _refine_ls_R_factor_gt 0.0318 _refine_ls_wR_factor_ref 0.0834 _refine_ls_wR_factor_gt 0.0811 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _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 S S 0.57878(4) 0.42688(3) 0.79001(2) 0.02026(8) Uani 1 1 d . . . O1 O 0.73023(10) 0.45998(7) 0.75040(6) 0.0194(2) Uani 1 1 d . . . O2 O 0.52726(12) 0.51905(9) 0.84069(6) 0.0278(2) Uani 1 1 d . . . O3 O 0.60372(12) 0.31658(8) 0.82520(6) 0.0283(2) Uani 1 1 d . . . C6 C 0.93095(14) 0.58868(10) 0.72306(8) 0.0182(2) Uani 1 1 d . . . H6 H 0.9709 0.5211 0.6927 0.022 Uiso 1 1 calc R . . C5 C 1.01653(15) 0.60907(12) 0.80477(9) 0.0219(3) Uani 1 1 d . . . H5 H 1.1123 0.5685 0.8004 0.026 Uiso 1 1 calc R . . C4 C 1.0472(2) 0.74000(13) 0.80555(10) 0.0346(4) Uani 1 1 d . . . H4A H 1.0225 0.7730 0.8602 0.042 Uiso 1 1 calc R . . H4B H 1.1514 0.7553 0.7938 0.042 Uiso 1 1 calc R . . C3 C 0.95019(17) 0.79158(12) 0.73785(9) 0.0269(3) Uani 1 1 d . . . H3A H 0.9922 0.8637 0.7164 0.032 Uiso 1 1 calc R . . H3B H 0.8505 0.8067 0.7588 0.032 Uiso 1 1 calc R . . C2 C 0.94888(15) 0.69861(11) 0.67092(8) 0.0207(3) Uani 1 1 d . . . H2 H 1.0443 0.6974 0.6408 0.025 Uiso 1 1 calc R . . C1 C 0.82213(16) 0.69928(12) 0.60923(9) 0.0243(3) Uani 1 1 d . . . C10 C 0.8407(2) 0.61092(16) 0.53815(10) 0.0359(4) Uani 1 1 d . . . H10A H 0.8168 0.6420 0.4828 0.043 Uiso 1 1 calc R . . H10B H 0.9376 0.5734 0.5377 0.043 Uiso 1 1 calc R . . C9 C 0.7185(2) 0.53543(14) 0.57502(9) 0.0342(4) Uani 1 1 d . . . H9A H 0.7521 0.4585 0.5919 0.041 Uiso 1 1 calc R . . H9B H 0.6307 0.5302 0.5395 0.041 Uiso 1 1 calc R . . C8 C 0.70134(15) 0.61993(12) 0.64839(9) 0.0227(3) Uani 1 1 d . . . H8 H 0.6027 0.6561 0.6525 0.027 Uiso 1 1 calc R . . C7 C 0.76382(14) 0.58047(10) 0.73053(8) 0.0173(2) Uani 1 1 d . . . H7 H 0.7287 0.6313 0.7761 0.021 Uiso 1 1 calc R . . C12 C 0.94106(16) 0.56887(13) 0.88396(9) 0.0256(3) Uani 1 1 d . . . H12A H 1.0058 0.5817 0.9314 0.031 Uiso 1 1 calc R . . H12B H 0.9186 0.4872 0.8795 0.031 Uiso 1 1 calc R . . H12C H 0.8503 0.6120 0.8918 0.031 Uiso 1 1 calc R . . C11 C 0.7748(2) 0.81716(14) 0.58025(11) 0.0381(4) Uani 1 1 d . . . H11A H 0.7506 0.8645 0.6284 0.046 Uiso 1 1 calc R . . H11B H 0.6888 0.8101 0.5445 0.046 Uiso 1 1 calc R . . H11C H 0.8546 0.8529 0.5492 0.046 Uiso 1 1 calc R . . C1' C 0.46107(14) 0.41118(11) 0.70482(8) 0.0196(3) Uani 1 1 d . . . C2' C 0.36885(16) 0.50041(12) 0.68157(9) 0.0236(3) Uani 1 1 d . . . H2' H 0.3666 0.5696 0.7123 0.028 Uiso 1 1 calc R . . C3' C 0.28010(16) 0.48577(13) 0.61230(10) 0.0264(3) Uani 1 1 d . . . H3' H 0.2176 0.5463 0.5956 0.032 Uiso 1 1 calc R . . C4' C 0.28083(16) 0.38482(13) 0.56707(9) 0.0247(3) Uani 1 1 d . . . C5' C 0.37362(16) 0.29644(12) 0.59243(9) 0.0238(3) Uani 1 1 d . . . H5' H 0.3749 0.2267 0.5623 0.029 Uiso 1 1 calc R . . C6' C 0.46366(15) 0.30891(11) 0.66073(9) 0.0213(3) Uani 1 1 d . . . H6' H 0.5264 0.2485 0.6773 0.026 Uiso 1 1 calc R . . C7' C 0.18394(18) 0.37057(16) 0.49211(10) 0.0359(4) Uani 1 1 d . . . H7'A H 0.0897 0.4076 0.5024 0.043 Uiso 1 1 calc R . . H7'B H 0.1686 0.2890 0.4814 0.043 Uiso 1 1 calc R . . H7'C H 0.2307 0.4059 0.4439 0.043 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 S 0.02206(15) 0.02065(14) 0.01807(15) 0.00092(12) 0.00052(13) -0.00493(13) O1 0.0193(4) 0.0153(4) 0.0235(5) 0.0008(4) 0.0002(4) -0.0028(3) O2 0.0294(5) 0.0312(5) 0.0229(5) -0.0056(4) 0.0067(4) -0.0061(4) O3 0.0339(6) 0.0255(5) 0.0256(5) 0.0073(4) -0.0055(4) -0.0086(4) C6 0.0181(6) 0.0164(5) 0.0200(6) 0.0008(4) 0.0024(5) -0.0006(5) C5 0.0203(6) 0.0214(6) 0.0240(7) 0.0019(5) -0.0024(5) -0.0036(5) C4 0.0461(10) 0.0260(7) 0.0317(9) 0.0024(6) -0.0094(7) -0.0145(7) C3 0.0344(8) 0.0173(6) 0.0291(7) 0.0006(5) 0.0001(6) -0.0054(5) C2 0.0222(7) 0.0182(6) 0.0218(7) 0.0026(5) 0.0032(5) -0.0009(5) C1 0.0277(7) 0.0250(7) 0.0201(7) 0.0066(5) 0.0013(6) -0.0017(6) C10 0.0442(10) 0.0440(9) 0.0194(7) -0.0039(7) 0.0034(7) -0.0045(8) C9 0.0458(10) 0.0370(8) 0.0198(8) -0.0033(6) -0.0042(7) -0.0097(7) C8 0.0227(7) 0.0238(6) 0.0217(7) 0.0035(5) -0.0021(5) -0.0018(5) C7 0.0194(6) 0.0133(5) 0.0192(6) -0.0005(4) 0.0008(5) -0.0030(5) C12 0.0264(7) 0.0299(7) 0.0204(6) 0.0000(5) -0.0025(6) -0.0028(6) C11 0.0388(9) 0.0326(8) 0.0431(9) 0.0170(7) -0.0061(8) -0.0014(7) C1' 0.0174(6) 0.0214(6) 0.0201(6) 0.0012(5) 0.0005(5) -0.0038(5) C2' 0.0211(6) 0.0210(6) 0.0287(7) 0.0005(5) 0.0039(5) -0.0004(5) C3' 0.0194(7) 0.0296(7) 0.0302(8) 0.0065(6) 0.0020(6) 0.0034(6) C4' 0.0183(6) 0.0344(7) 0.0215(7) 0.0050(6) 0.0005(5) -0.0044(6) C5' 0.0215(7) 0.0262(7) 0.0237(7) -0.0024(5) 0.0011(5) -0.0029(5) C6' 0.0203(6) 0.0200(6) 0.0237(7) 0.0005(5) 0.0011(5) -0.0004(5) C7' 0.0281(8) 0.0510(10) 0.0286(8) 0.0040(7) -0.0069(7) -0.0047(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 S O3 1.4289(10) . ? S O2 1.4340(11) . ? S O1 1.5758(10) . ? S C1' 1.7577(14) . ? O1 C7 1.4786(15) . ? C6 C7 1.5383(18) . ? C6 C2 1.5465(17) . ? C6 C5 1.5535(18) . ? C5 C12 1.5282(19) . ? C5 C4 1.5580(19) . ? C4 C3 1.533(2) . ? C3 C2 1.5340(19) . ? C2 C1 1.530(2) . ? C1 C11 1.520(2) . ? C1 C10 1.555(2) . ? C1 C8 1.5768(19) . ? C10 C9 1.545(2) . ? C9 C8 1.551(2) . ? C8 C7 1.5170(18) . ? C1' C6' 1.3929(18) . ? C1' C2' 1.3946(19) . ? C2' C3' 1.393(2) . ? C3' C4' 1.389(2) . ? C4' C5' 1.400(2) . ? C4' C7' 1.510(2) . ? C5' C6' 1.385(2) . ? 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 S O2 120.34(7) . . ? O3 S O1 104.06(6) . . ? O2 S O1 109.66(6) . . ? O3 S C1' 108.36(6) . . ? O2 S C1' 108.90(6) . . ? O1 S C1' 104.34(6) . . ? C7 O1 S 120.38(8) . . ? C7 C6 C2 101.56(10) . . ? C7 C6 C5 116.42(11) . . ? C2 C6 C5 106.34(10) . . ? C12 C5 C6 115.83(11) . . ? C12 C5 C4 112.17(13) . . ? C6 C5 C4 104.41(11) . . ? C3 C4 C5 106.10(12) . . ? C4 C3 C2 103.18(12) . . ? C1 C2 C3 117.47(12) . . ? C1 C2 C6 106.17(10) . . ? C3 C2 C6 101.96(11) . . ? C11 C1 C2 114.93(12) . . ? C11 C1 C10 114.05(13) . . ? C2 C1 C10 113.24(12) . . ? C11 C1 C8 117.28(13) . . ? C2 C1 C8 105.54(11) . . ? C10 C1 C8 88.92(11) . . ? C9 C10 C1 90.95(12) . . ? C10 C9 C8 90.18(12) . . ? C7 C8 C9 115.84(12) . . ? C7 C8 C1 105.40(11) . . ? C9 C8 C1 89.90(11) . . ? O1 C7 C8 113.68(11) . . ? O1 C7 C6 106.47(10) . . ? C8 C7 C6 106.71(11) . . ? C6' C1' C2' 121.07(13) . . ? C6' C1' S 118.67(10) . . ? C2' C1' S 120.26(11) . . ? C3' C2' C1' 118.52(13) . . ? C4' C3' C2' 121.60(13) . . ? C3' C4' C5' 118.52(13) . . ? C3' C4' C7' 120.85(14) . . ? C5' C4' C7' 120.64(14) . . ? C6' C5' C4' 121.10(13) . . ? C5' C6' C1' 119.19(13) . . ? 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 S O1 C7 -161.13(9) . . . . ? O2 S O1 C7 -31.16(11) . . . . ? C1' S O1 C7 85.35(10) . . . . ? C7 C6 C5 C12 25.30(17) . . . . ? C2 C6 C5 C12 137.56(12) . . . . ? C7 C6 C5 C4 -98.56(13) . . . . ? C2 C6 C5 C4 13.69(14) . . . . ? C12 C5 C4 C3 -113.29(14) . . . . ? C6 C5 C4 C3 12.90(16) . . . . ? C5 C4 C3 C2 -34.80(16) . . . . ? C4 C3 C2 C1 158.05(13) . . . . ? C4 C3 C2 C6 42.52(13) . . . . ? C7 C6 C2 C1 -36.21(13) . . . . ? C5 C6 C2 C1 -158.42(11) . . . . ? C7 C6 C2 C3 87.32(12) . . . . ? C5 C6 C2 C3 -34.89(13) . . . . ? C3 C2 C1 C11 39.70(18) . . . . ? C6 C2 C1 C11 152.89(13) . . . . ? C3 C2 C1 C10 173.23(12) . . . . ? C6 C2 C1 C10 -73.57(14) . . . . ? C3 C2 C1 C8 -91.14(14) . . . . ? C6 C2 C1 C8 22.06(14) . . . . ? C11 C1 C10 C9 -117.71(15) . . . . ? C2 C1 C10 C9 108.34(13) . . . . ? C8 C1 C10 C9 1.87(12) . . . . ? C1 C10 C9 C8 -1.90(12) . . . . ? C10 C9 C8 C7 -105.24(14) . . . . ? C10 C9 C8 C1 1.87(12) . . . . ? C11 C1 C8 C7 -128.33(13) . . . . ? C2 C1 C8 C7 1.14(15) . . . . ? C10 C1 C8 C7 114.99(12) . . . . ? C11 C1 C8 C9 114.82(14) . . . . ? C2 C1 C8 C9 -115.71(12) . . . . ? C10 C1 C8 C9 -1.86(12) . . . . ? S O1 C7 C8 -82.35(12) . . . . ? S O1 C7 C6 160.44(8) . . . . ? C9 C8 C7 O1 -43.66(16) . . . . ? C1 C8 C7 O1 -141.20(11) . . . . ? C9 C8 C7 C6 73.41(14) . . . . ? C1 C8 C7 C6 -24.14(14) . . . . ? C2 C6 C7 O1 158.97(10) . . . . ? C5 C6 C7 O1 -86.05(12) . . . . ? C2 C6 C7 C8 37.23(13) . . . . ? C5 C6 C7 C8 152.20(11) . . . . ? O3 S C1' C6' -29.23(12) . . . . ? O2 S C1' C6' -161.77(10) . . . . ? O1 S C1' C6' 81.20(11) . . . . ? O3 S C1' C2' 151.69(11) . . . . ? O2 S C1' C2' 19.15(13) . . . . ? O1 S C1' C2' -97.89(11) . . . . ? C6' C1' C2' C3' -0.8(2) . . . . ? S C1' C2' C3' 178.24(11) . . . . ? C1' C2' C3' C4' 0.6(2) . . . . ? C2' C3' C4' C5' 0.0(2) . . . . ? C2' C3' C4' C7' -179.95(14) . . . . ? C3' C4' C5' C6' -0.4(2) . . . . ? C7' C4' C5' C6' 179.55(13) . . . . ? C4' C5' C6' C1' 0.2(2) . . . . ? C2' C1' C6' C5' 0.4(2) . . . . ? S C1' C6' C5' -178.65(11) . . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 28.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.326 _refine_diff_density_min -0.213 _refine_diff_density_rms 0.046 #============================================================================= # end of cif file #=============================================================================