# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Paul Evans' _publ_contact_author_email PAUL.EVANS@UCD.IE _publ_section_title ; The Thio-adduct Facilitated, Enzymatic Kinetic Resolution of 4-Hydroxycyclopentenone and 4-Hydroxycyclohexenone ; loop_ _publ_author_name 'Paul Evans' 'Cian Murray' 'Dearbhle Keegan' 'Ben S. Morgan' "Aisling O'Byrne" 'Carole Palacio' # Attachment 'eva311.cif' data_eva31 _database_code_depnum_ccdc_archive 'CCDC 742464' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H18 O4 S' _chemical_formula_sum 'C14 H18 O4 S' _chemical_formula_weight 282.34 _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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting trigonal _symmetry_space_group_name_H-M 'P 32' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z+2/3' '-x+y, -x, z+1/3' _cell_length_a 11.6708(9) _cell_length_b 11.6708(9) _cell_length_c 8.9661(14) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 1057.6(2) _cell_formula_units_Z 3 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2257 _cell_measurement_theta_min 3.04 _cell_measurement_theta_max 23.17 _exptl_crystal_description rod _exptl_crystal_colour colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.330 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 450 _exptl_absorpt_coefficient_mu 0.237 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8670 _exptl_absorpt_correction_T_max 0.9767 _exptl_absorpt_process_details ; SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) for selected reflections was 0.023 before and 0.016 after correction. The Ratio of minimum to maximum transmission is 0.774880. The \l/2 correction factor is 0.0015 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5383 _diffrn_reflns_av_R_equivalents 0.0168 _diffrn_reflns_av_sigmaI/netI 0.0255 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.01 _diffrn_reflns_theta_max 24.89 _reflns_number_total 2316 _reflns_number_gt 2113 _reflns_threshold_expression I>2\s(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 '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^)+(0.0467P)^2^+0.0000P] 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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.12(7) _refine_ls_number_reflns 2316 _refine_ls_number_parameters 178 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0359 _refine_ls_R_factor_gt 0.0315 _refine_ls_wR_factor_ref 0.0735 _refine_ls_wR_factor_gt 0.0720 _refine_ls_goodness_of_fit_ref 1.045 _refine_ls_restrained_S_all 1.044 _refine_ls_shift/su_max 0.002 _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 O1 O 0.65124(19) -0.14847(17) 0.98917(19) 0.0505(4) Uani 1 1 d . . . H1O1 H 0.580(3) -0.188(3) 1.028(3) 0.054(8) Uiso 1 1 d . . . C1 C 0.6613(2) -0.0347(2) 0.9199(3) 0.0404(5) Uani 1 1 d . . . H1 H 0.6740 0.0337 0.9921 0.048 Uiso 1 1 calc R . . C2 C 0.7762(2) 0.0121(2) 0.8113(3) 0.0480(6) Uani 1 1 d . . . H2A H 0.8058 0.1017 0.7778 0.058 Uiso 1 1 calc R . . H2B H 0.8501 0.0090 0.8565 0.058 Uiso 1 1 calc R . . C3 C 0.7193(3) -0.0836(2) 0.6857(3) 0.0486(6) Uani 1 1 d . . . O2 O 0.7791(2) -0.1152(2) 0.6007(2) 0.0728(6) Uani 1 1 d . . . C4 C 0.5700(3) -0.1405(3) 0.6839(3) 0.0508(6) Uani 1 1 d . . . H4A H 0.5237 -0.2355 0.6997 0.061 Uiso 1 1 calc R . . H4B H 0.5413 -0.1218 0.5901 0.061 Uiso 1 1 calc R . . C5 C 0.5459(2) -0.0696(2) 0.8135(2) 0.0389(5) Uani 1 1 d . . . H5 H 0.5539 0.0129 0.7757 0.047 Uiso 1 1 calc R . . S S 0.38242(5) -0.16856(5) 0.89328(7) 0.04386(16) Uani 1 1 d . . . C6 C 0.3744(2) -0.0469(3) 1.0157(3) 0.0473(6) Uani 1 1 d . . . H6A H 0.2852 -0.0851 1.0548 0.057 Uiso 1 1 calc R . . H6B H 0.4333 -0.0299 1.0997 0.057 Uiso 1 1 calc R . . C7 C 0.4110(2) 0.0833(2) 0.9422(2) 0.0380(5) Uani 1 1 d . . . C8 C 0.3344(2) 0.0915(2) 0.8267(2) 0.0375(5) Uani 1 1 d . . . H8 H 0.2591 0.0151 0.7948 0.045 Uiso 1 1 calc R . . C9 C 0.3688(2) 0.2110(2) 0.7595(2) 0.0376(5) Uani 1 1 d . . . O3 O 0.30107(16) 0.22866(15) 0.64660(18) 0.0499(4) Uani 1 1 d . . . C13 C 0.1771(2) 0.1191(3) 0.6056(3) 0.0570(7) Uani 1 1 d . . . H13A H 0.1890 0.0466 0.5764 0.086 Uiso 1 1 calc R . . H13B H 0.1407 0.1436 0.5237 0.086 Uiso 1 1 calc R . . H13C H 0.1177 0.0931 0.6890 0.086 Uiso 1 1 calc R . . C10 C 0.4840(2) 0.3267(2) 0.8052(2) 0.0376(5) Uani 1 1 d . . . O4 O 0.51304(16) 0.43873(16) 0.72799(19) 0.0525(4) Uani 1 1 d . . . C14 C 0.6317(3) 0.5562(2) 0.7652(3) 0.0625(7) Uani 1 1 d . . . H14A H 0.6224 0.5868 0.8613 0.094 Uiso 1 1 calc R . . H14B H 0.6495 0.6229 0.6917 0.094 Uiso 1 1 calc R . . H14C H 0.7036 0.5384 0.7676 0.094 Uiso 1 1 calc R . . C11 C 0.5579(2) 0.3188(2) 0.9204(3) 0.0420(5) Uani 1 1 d . . . H11 H 0.6330 0.3949 0.9533 0.050 Uiso 1 1 calc R . . C12 C 0.5211(2) 0.1981(2) 0.9878(2) 0.0425(5) Uani 1 1 d . . . H12 H 0.5721 0.1948 1.0656 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 O1 0.0433(10) 0.0542(10) 0.0544(10) 0.0205(8) 0.0029(8) 0.0245(9) C1 0.0426(13) 0.0341(12) 0.0451(12) 0.0009(9) -0.0016(10) 0.0197(10) C2 0.0464(14) 0.0378(13) 0.0616(16) 0.0125(11) 0.0074(11) 0.0224(11) C3 0.0652(16) 0.0416(13) 0.0490(13) 0.0135(11) 0.0158(12) 0.0343(13) O2 0.0844(14) 0.0747(14) 0.0748(14) 0.0021(10) 0.0253(11) 0.0513(12) C4 0.0615(16) 0.0551(15) 0.0442(14) -0.0037(11) -0.0054(11) 0.0355(13) C5 0.0480(13) 0.0374(12) 0.0392(12) 0.0074(9) 0.0017(9) 0.0273(11) S 0.0425(3) 0.0396(3) 0.0513(3) 0.0015(3) -0.0047(3) 0.0219(3) C6 0.0517(14) 0.0576(15) 0.0394(12) 0.0057(11) 0.0038(10) 0.0324(13) C7 0.0396(12) 0.0471(13) 0.0359(12) -0.0067(9) 0.0024(9) 0.0280(11) C8 0.0350(11) 0.0375(12) 0.0392(11) -0.0067(9) 0.0007(9) 0.0174(10) C9 0.0396(12) 0.0414(13) 0.0352(11) -0.0079(9) -0.0024(9) 0.0229(10) O3 0.0498(10) 0.0420(9) 0.0511(10) -0.0017(7) -0.0174(8) 0.0178(8) C13 0.0490(15) 0.0539(16) 0.0621(15) -0.0056(13) -0.0219(12) 0.0211(13) C10 0.0397(12) 0.0357(12) 0.0378(11) -0.0083(9) -0.0002(9) 0.0192(10) O4 0.0548(10) 0.0385(9) 0.0574(10) -0.0034(7) -0.0105(8) 0.0181(8) C14 0.0650(18) 0.0389(14) 0.0674(18) -0.0057(12) -0.0100(13) 0.0138(13) C11 0.0367(12) 0.0439(13) 0.0450(12) -0.0146(10) -0.0049(10) 0.0197(11) C12 0.0431(13) 0.0555(15) 0.0379(12) -0.0106(10) -0.0071(10) 0.0315(12) _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 O1 C1 1.416(3) . ? O1 H1O1 0.80(3) . ? C1 C2 1.521(3) . ? C1 C5 1.530(3) . ? C1 H1 0.9800 . ? C2 C3 1.488(3) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 O2 1.209(3) . ? C3 C4 1.523(4) . ? C4 C5 1.532(3) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 S 1.811(2) . ? C5 H5 0.9800 . ? S C6 1.834(3) . ? C6 C7 1.509(3) . ? C6 H6A 0.9700 . ? C6 H6B 0.9700 . ? C7 C12 1.376(3) . ? C7 C8 1.402(3) . ? C8 C9 1.382(3) . ? C8 H8 0.9300 . ? C9 O3 1.362(3) . ? C9 C10 1.407(3) . ? O3 C13 1.419(3) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C10 O4 1.364(3) . ? C10 C11 1.378(3) . ? O4 C14 1.418(3) . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C11 C12 1.390(3) . ? C11 H11 0.9300 . ? C12 H12 0.9300 . ? 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 C1 O1 H1O1 108(2) . . ? O1 C1 C2 105.21(18) . . ? O1 C1 C5 112.01(18) . . ? C2 C1 C5 101.38(19) . . ? O1 C1 H1 112.5 . . ? C2 C1 H1 112.5 . . ? C5 C1 H1 112.5 . . ? C3 C2 C1 103.40(19) . . ? C3 C2 H2A 111.1 . . ? C1 C2 H2A 111.1 . . ? C3 C2 H2B 111.1 . . ? C1 C2 H2B 111.1 . . ? H2A C2 H2B 109.0 . . ? O2 C3 C2 126.6(3) . . ? O2 C3 C4 124.7(3) . . ? C2 C3 C4 108.6(2) . . ? C3 C4 C5 103.6(2) . . ? C3 C4 H4A 111.0 . . ? C5 C4 H4A 111.0 . . ? C3 C4 H4B 111.0 . . ? C5 C4 H4B 111.0 . . ? H4A C4 H4B 109.0 . . ? C1 C5 C4 103.98(19) . . ? C1 C5 S 115.46(15) . . ? C4 C5 S 111.98(17) . . ? C1 C5 H5 108.4 . . ? C4 C5 H5 108.4 . . ? S C5 H5 108.4 . . ? C5 S C6 100.82(10) . . ? C7 C6 S 114.81(15) . . ? C7 C6 H6A 108.6 . . ? S C6 H6A 108.6 . . ? C7 C6 H6B 108.6 . . ? S C6 H6B 108.6 . . ? H6A C6 H6B 107.5 . . ? C12 C7 C8 118.1(2) . . ? C12 C7 C6 120.4(2) . . ? C8 C7 C6 121.5(2) . . ? C9 C8 C7 121.1(2) . . ? C9 C8 H8 119.4 . . ? C7 C8 H8 119.4 . . ? O3 C9 C8 125.3(2) . . ? O3 C9 C10 114.80(18) . . ? C8 C9 C10 119.8(2) . . ? C9 O3 C13 117.64(18) . . ? O3 C13 H13A 109.5 . . ? O3 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? O3 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? O4 C10 C11 125.46(19) . . ? O4 C10 C9 115.61(19) . . ? C11 C10 C9 118.9(2) . . ? C10 O4 C14 117.51(19) . . ? O4 C14 H14A 109.5 . . ? O4 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? O4 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C10 C11 C12 120.5(2) . . ? C10 C11 H11 119.8 . . ? C12 C11 H11 119.8 . . ? C7 C12 C11 121.5(2) . . ? C7 C12 H12 119.2 . . ? C11 C12 H12 119.2 . . ? 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 O1 C1 C2 C3 75.9(2) . . . . ? C5 C1 C2 C3 -40.9(2) . . . . ? C1 C2 C3 O2 -153.0(2) . . . . ? C1 C2 C3 C4 25.1(2) . . . . ? O2 C3 C4 C5 179.2(2) . . . . ? C2 C3 C4 C5 1.1(2) . . . . ? O1 C1 C5 C4 -69.6(2) . . . . ? C2 C1 C5 C4 42.1(2) . . . . ? O1 C1 C5 S 53.4(2) . . . . ? C2 C1 C5 S 165.14(14) . . . . ? C3 C4 C5 C1 -26.7(2) . . . . ? C3 C4 C5 S -152.06(16) . . . . ? C1 C5 S C6 71.51(18) . . . . ? C4 C5 S C6 -169.76(17) . . . . ? C5 S C6 C7 50.23(19) . . . . ? S C6 C7 C12 -115.4(2) . . . . ? S C6 C7 C8 64.9(2) . . . . ? C12 C7 C8 C9 0.6(3) . . . . ? C6 C7 C8 C9 -179.73(18) . . . . ? C7 C8 C9 O3 179.77(19) . . . . ? C7 C8 C9 C10 1.2(3) . . . . ? C8 C9 O3 C13 7.7(3) . . . . ? C10 C9 O3 C13 -173.6(2) . . . . ? O3 C9 C10 O4 -1.6(3) . . . . ? C8 C9 C10 O4 177.18(18) . . . . ? O3 C9 C10 C11 179.02(18) . . . . ? C8 C9 C10 C11 -2.2(3) . . . . ? C11 C10 O4 C14 2.5(3) . . . . ? C9 C10 O4 C14 -176.9(2) . . . . ? O4 C10 C11 C12 -177.8(2) . . . . ? C9 C10 C11 C12 1.6(3) . . . . ? C8 C7 C12 C11 -1.3(3) . . . . ? C6 C7 C12 C11 179.04(19) . . . . ? C10 C11 C12 C7 0.2(3) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H1O1 S 0.80(3) 2.68(3) 3.3337(19) 140(2) 3_655 _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.89 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.220 _refine_diff_density_min -0.114 _refine_diff_density_rms 0.033 # Attachment 'eva421.cif' data_c:\data\eva42\rechnung\eva42 _database_code_depnum_ccdc_archive 'CCDC 742465' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H22 O5 S' _chemical_formula_sum 'C17 H22 O5 S' _chemical_formula_weight 338.41 _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' 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' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' _cell_length_a 7.6102(9) _cell_length_b 8.2782(10) _cell_length_c 8.3471(9) _cell_angle_alpha 111.026(2) _cell_angle_beta 99.798(2) _cell_angle_gamma 115.264(2) _cell_volume 410.05(8) _cell_formula_units_Z 1 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 2736 _cell_measurement_theta_min 2.83 _cell_measurement_theta_max 27.67 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.370 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 180 _exptl_absorpt_coefficient_mu 0.220 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8186 _exptl_absorpt_correction_T_max 0.9170 _exptl_absorpt_process_details ; SADABS v.2.10 (Bruker,2003) was used for absorption correction. R(int) for selected reflections was 0.033 before and 0.027 after correction. The Ratio of minimum to maximum transmission is 0.892723. The \l/2 correction factor is 0.0015 ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7913 _diffrn_reflns_av_R_equivalents 0.0290 _diffrn_reflns_av_sigmaI/netI 0.0461 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.83 _diffrn_reflns_theta_max 28.29 _reflns_number_total 3785 _reflns_number_gt 3513 _reflns_threshold_expression I>2\s(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 '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^)+(0.0435P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment 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 -0.05(5) _refine_ls_number_reflns 3785 _refine_ls_number_parameters 211 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0397 _refine_ls_R_factor_gt 0.0361 _refine_ls_wR_factor_ref 0.0826 _refine_ls_wR_factor_gt 0.0809 _refine_ls_goodness_of_fit_ref 1.050 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0.002 _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 -0.0745(3) -0.1709(3) 0.0372(3) 0.0186(4) Uani 1 1 d . . . H1A H -0.2116 -0.2136 0.0507 0.022 Uiso 1 1 calc R . . H1B H 0.0099 -0.0199 0.0995 0.022 Uiso 1 1 calc R . . C2 C -0.1101(3) -0.2563(3) -0.1665(3) 0.0177(4) Uani 1 1 d . . . O1 O -0.2817(2) -0.3490(2) -0.28798(19) 0.0266(3) Uani 1 1 d . . . C3 C 0.0857(3) -0.2200(3) -0.2055(3) 0.0191(4) Uani 1 1 d . . . H3A H 0.1830 -0.0720 -0.1568 0.023 Uiso 1 1 calc R . . H3B H 0.0482 -0.2901 -0.3414 0.023 Uiso 1 1 calc R . . C4 C 0.1948(3) -0.3013(3) -0.1131(3) 0.0194(4) Uani 1 1 d . . . H4A H 0.1039 -0.4519 -0.1737 0.023 Uiso 1 1 calc R . . H4B H 0.3286 -0.2673 -0.1316 0.023 Uiso 1 1 calc R . . C5 C 0.2400(3) -0.2114(3) 0.0940(3) 0.0174(4) Uani 1 1 d . . . H5 H 0.3010 -0.2754 0.1471 0.021 Uiso 1 1 calc R . . O2 O 0.3915(2) 0.00803(19) 0.18327(18) 0.0193(3) Uani 1 1 d . . . O3 O 0.6483(2) -0.0460(2) 0.2702(2) 0.0318(4) Uani 1 1 d . . . C6 C 0.5947(3) 0.0691(3) 0.2618(3) 0.0219(4) Uani 1 1 d . . . C7 C 0.7390(3) 0.2910(3) 0.3335(3) 0.0334(5) Uani 1 1 d . . . H7A H 0.8821 0.3325 0.4024 0.050 Uiso 1 1 calc R . . H7B H 0.6929 0.3676 0.4162 0.050 Uiso 1 1 calc R . . H7C H 0.7374 0.3195 0.2291 0.050 Uiso 1 1 calc R . . C8 C 0.0402(3) -0.2465(3) 0.1297(2) 0.0172(4) Uani 1 1 d . . . H8 H -0.0569 -0.3982 0.0651 0.021 Uiso 1 1 calc R . . S S 0.07823(6) -0.16269(6) 0.37358(6) 0.02074(12) Uani 1 1 d . . . C9 C 0.1702(3) 0.1080(3) 0.4723(2) 0.0206(4) Uani 1 1 d . . . H9A H 0.3128 0.1849 0.4742 0.025 Uiso 1 1 calc R . . H9B H 0.0746 0.1274 0.3957 0.025 Uiso 1 1 calc R . . C10 C 0.1750(3) 0.1854(3) 0.6677(2) 0.0177(4) Uani 1 1 d . . . C11 C -0.0144(3) 0.1277(3) 0.6955(3) 0.0172(4) Uani 1 1 d . . . H11 H -0.1446 0.0378 0.5916 0.021 Uiso 1 1 calc R . . O4 O -0.1886(2) 0.1616(2) 0.91396(18) 0.0216(3) Uani 1 1 d . . . C16 C -0.3843(3) 0.0334(3) 0.7610(3) 0.0259(4) Uani 1 1 d . . . H16A H -0.3831 0.0903 0.6762 0.039 Uiso 1 1 calc R . . H16B H -0.4974 0.0245 0.8058 0.039 Uiso 1 1 calc R . . H16C H -0.4078 -0.1031 0.6952 0.039 Uiso 1 1 calc R . . C12 C -0.0131(3) 0.2006(3) 0.8729(3) 0.0167(4) Uani 1 1 d . . . C13 C 0.1786(3) 0.3294(3) 1.0277(2) 0.0168(4) Uani 1 1 d . . . O5 O 0.1614(2) 0.3909(2) 1.19625(17) 0.0207(3) Uani 1 1 d . . . C17 C 0.3525(3) 0.5123(3) 1.3563(3) 0.0244(4) Uani 1 1 d . . . H17A H 0.4205 0.4348 1.3550 0.037 Uiso 1 1 calc R . . H17B H 0.3214 0.5483 1.4687 0.037 Uiso 1 1 calc R . . H17C H 0.4467 0.6371 1.3550 0.037 Uiso 1 1 calc R . . C14 C 0.3657(3) 0.3867(3) 1.0003(3) 0.0186(4) Uani 1 1 d . . . H14 H 0.4959 0.4746 1.1041 0.022 Uiso 1 1 calc R . . C15 C 0.3631(3) 0.3152(3) 0.8198(3) 0.0193(4) Uani 1 1 d . . . H15 H 0.4921 0.3564 0.8019 0.023 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 C1 0.0213(10) 0.0218(10) 0.0166(9) 0.0099(8) 0.0079(8) 0.0136(8) C2 0.0209(10) 0.0155(9) 0.0159(9) 0.0086(8) 0.0053(8) 0.0087(8) O1 0.0207(7) 0.0286(8) 0.0208(7) 0.0104(7) 0.0029(6) 0.0086(6) C3 0.0220(10) 0.0188(9) 0.0165(9) 0.0100(8) 0.0084(8) 0.0094(8) C4 0.0259(10) 0.0190(9) 0.0180(10) 0.0094(8) 0.0120(8) 0.0140(8) C5 0.0203(10) 0.0145(9) 0.0178(9) 0.0070(7) 0.0066(7) 0.0105(8) O2 0.0180(7) 0.0183(7) 0.0215(7) 0.0085(6) 0.0067(6) 0.0106(6) O3 0.0279(8) 0.0384(9) 0.0323(8) 0.0141(7) 0.0088(7) 0.0236(7) C6 0.0214(10) 0.0290(11) 0.0135(9) 0.0064(9) 0.0077(8) 0.0148(9) C7 0.0209(11) 0.0289(12) 0.0327(12) 0.0035(10) 0.0090(9) 0.0093(9) C8 0.0224(10) 0.0163(9) 0.0129(9) 0.0071(7) 0.0079(8) 0.0098(8) S 0.0322(3) 0.0195(2) 0.0148(2) 0.00971(18) 0.01142(19) 0.0150(2) C9 0.0289(11) 0.0165(9) 0.0185(10) 0.0090(8) 0.0118(9) 0.0123(9) C10 0.0246(10) 0.0155(9) 0.0190(9) 0.0099(8) 0.0119(8) 0.0127(8) C11 0.0195(9) 0.0141(9) 0.0146(8) 0.0051(7) 0.0031(7) 0.0090(8) O4 0.0179(7) 0.0240(7) 0.0185(7) 0.0059(6) 0.0076(6) 0.0109(6) C16 0.0182(10) 0.0279(11) 0.0252(11) 0.0085(9) 0.0074(8) 0.0112(9) C12 0.0186(9) 0.0140(9) 0.0207(9) 0.0091(8) 0.0097(8) 0.0099(8) C13 0.0237(10) 0.0157(9) 0.0139(9) 0.0072(7) 0.0073(7) 0.0125(8) O5 0.0228(7) 0.0200(7) 0.0139(6) 0.0049(6) 0.0058(6) 0.0103(6) C17 0.0289(11) 0.0238(11) 0.0137(9) 0.0075(9) 0.0053(9) 0.0112(9) C14 0.0179(9) 0.0144(9) 0.0192(9) 0.0066(8) 0.0031(8) 0.0080(8) C15 0.0193(10) 0.0171(9) 0.0240(10) 0.0105(8) 0.0108(8) 0.0102(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 C1 C2 1.510(3) . ? C1 C8 1.528(2) . ? C1 H1A 0.9900 . ? C1 H1B 0.9900 . ? C2 O1 1.208(2) . ? C2 C3 1.506(3) . ? C3 C4 1.540(3) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 C5 1.522(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 O2 1.460(2) . ? C5 C8 1.525(2) . ? C5 H5 1.0000 . ? O2 C6 1.351(2) . ? O3 C6 1.204(2) . ? C6 C7 1.485(3) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? C8 S 1.8227(18) . ? C8 H8 1.0000 . ? S C9 1.8246(19) . ? C9 C10 1.511(2) . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C10 C15 1.381(3) . ? C10 C11 1.402(3) . ? C11 C12 1.380(3) . ? C11 H11 0.9500 . ? O4 C12 1.368(2) . ? O4 C16 1.416(2) . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C12 C13 1.406(3) . ? C13 O5 1.364(2) . ? C13 C14 1.384(2) . ? O5 C17 1.427(2) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C14 C15 1.400(3) . ? C14 H14 0.9500 . ? C15 H15 0.9500 . ? 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 C8 110.66(15) . . ? C2 C1 H1A 109.5 . . ? C8 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? C8 C1 H1B 109.5 . . ? H1A C1 H1B 108.1 . . ? O1 C2 C3 122.83(17) . . ? O1 C2 C1 122.76(17) . . ? C3 C2 C1 114.39(16) . . ? C2 C3 C4 110.03(15) . . ? C2 C3 H3A 109.7 . . ? C4 C3 H3A 109.7 . . ? C2 C3 H3B 109.7 . . ? C4 C3 H3B 109.7 . . ? H3A C3 H3B 108.2 . . ? C5 C4 C3 111.93(15) . . ? C5 C4 H4A 109.2 . . ? C3 C4 H4A 109.2 . . ? C5 C4 H4B 109.2 . . ? C3 C4 H4B 109.2 . . ? H4A C4 H4B 107.9 . . ? O2 C5 C4 108.25(15) . . ? O2 C5 C8 108.84(14) . . ? C4 C5 C8 111.03(15) . . ? O2 C5 H5 109.6 . . ? C4 C5 H5 109.6 . . ? C8 C5 H5 109.6 . . ? C6 O2 C5 115.68(14) . . ? O3 C6 O2 122.87(19) . . ? O3 C6 C7 125.19(19) . . ? O2 C6 C7 111.93(17) . . ? C6 C7 H7A 109.5 . . ? C6 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? C6 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? C5 C8 C1 112.97(15) . . ? C5 C8 S 113.36(13) . . ? C1 C8 S 114.03(12) . . ? C5 C8 H8 105.1 . . ? C1 C8 H8 105.1 . . ? S C8 H8 105.1 . . ? C8 S C9 104.38(9) . . ? C10 C9 S 108.61(12) . . ? C10 C9 H9A 110.0 . . ? S C9 H9A 110.0 . . ? C10 C9 H9B 110.0 . . ? S C9 H9B 110.0 . . ? H9A C9 H9B 108.3 . . ? C15 C10 C11 119.26(16) . . ? C15 C10 C9 121.10(17) . . ? C11 C10 C9 119.63(17) . . ? C12 C11 C10 120.46(17) . . ? C12 C11 H11 119.8 . . ? C10 C11 H11 119.8 . . ? C12 O4 C16 116.45(14) . . ? O4 C16 H16A 109.5 . . ? O4 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? O4 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? O4 C12 C11 124.80(17) . . ? O4 C12 C13 115.03(15) . . ? C11 C12 C13 120.15(16) . . ? O5 C13 C14 125.35(17) . . ? O5 C13 C12 115.24(15) . . ? C14 C13 C12 119.40(16) . . ? C13 O5 C17 116.58(15) . . ? O5 C17 H17A 109.5 . . ? O5 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? O5 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C13 C14 C15 120.08(17) . . ? C13 C14 H14 120.0 . . ? C15 C14 H14 120.0 . . ? C10 C15 C14 120.62(17) . . ? C10 C15 H15 119.7 . . ? C14 C15 H15 119.7 . . ? 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 C8 C1 C2 O1 125.68(19) . . . . ? C8 C1 C2 C3 -53.1(2) . . . . ? O1 C2 C3 C4 -124.27(19) . . . . ? C1 C2 C3 C4 54.5(2) . . . . ? C2 C3 C4 C5 -54.6(2) . . . . ? C3 C4 C5 O2 -64.74(19) . . . . ? C3 C4 C5 C8 54.7(2) . . . . ? C4 C5 O2 C6 -97.02(17) . . . . ? C8 C5 O2 C6 142.20(15) . . . . ? C5 O2 C6 O3 -5.0(3) . . . . ? C5 O2 C6 C7 174.67(16) . . . . ? O2 C5 C8 C1 65.61(18) . . . . ? C4 C5 C8 C1 -53.4(2) . . . . ? O2 C5 C8 S -66.06(17) . . . . ? C4 C5 C8 S 174.88(12) . . . . ? C2 C1 C8 C5 51.8(2) . . . . ? C2 C1 C8 S -176.90(13) . . . . ? C5 C8 S C9 85.84(14) . . . . ? C1 C8 S C9 -45.31(15) . . . . ? C8 S C9 C10 171.43(13) . . . . ? S C9 C10 C15 108.83(18) . . . . ? S C9 C10 C11 -72.27(19) . . . . ? C15 C10 C11 C12 0.4(3) . . . . ? C9 C10 C11 C12 -178.53(16) . . . . ? C16 O4 C12 C11 1.3(2) . . . . ? C16 O4 C12 C13 179.60(16) . . . . ? C10 C11 C12 O4 176.52(16) . . . . ? C10 C11 C12 C13 -1.7(3) . . . . ? O4 C12 C13 O5 2.2(2) . . . . ? C11 C12 C13 O5 -179.43(16) . . . . ? O4 C12 C13 C14 -176.61(16) . . . . ? C11 C12 C13 C14 1.8(3) . . . . ? C14 C13 O5 C17 -4.7(2) . . . . ? C12 C13 O5 C17 176.58(15) . . . . ? O5 C13 C14 C15 -179.22(16) . . . . ? C12 C13 C14 C15 -0.6(3) . . . . ? C11 C10 C15 C14 0.8(3) . . . . ? C9 C10 C15 C14 179.74(17) . . . . ? C13 C14 C15 C10 -0.8(3) . . . . ? _diffrn_measured_fraction_theta_max 0.960 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.351 _refine_diff_density_min -0.195 _refine_diff_density_rms 0.048