Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Jeremy Scott' _publ_contact_author_address ; Department of Process Research Merck Sharp & Dohme Hertford Road Hoddesdon Hertfordshire EN119BU UNITED KINGDOM ; _publ_contact_author_email 'JEREMY SCOTT@MERCK.COM' _publ_section_title ; The Conformational Bias of Aryl, Arylsulfonyl Geminally Substituted Tertiary Carbon Centers: Applications in Substrate-Based Stereocontrol ; loop_ _publ_author_name 'Jeremy Scott' 'Karel M.J. Brands' 'Sarah E. Brewer' 'Jennifer R. Chilenski' 'Antony J. Davies' ; Ulf-H.Dolling ; 'Andrew D. Gibb' 'David R. Lieberman' 'Peter R. Mullens' 'Allen G. Oliver' # Attachment 'Cyclohexanone2REVISED.cif' data_jrc0831n _database_code_depnum_ccdc_archive 'CCDC 236717' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common jrc0831n _chemical_melting_point ? _chemical_formula_moiety 'C18 H15 Cl F2 O3 S' _chemical_formula_sum 'C18 H15 Cl F2 O3 S' _chemical_formula_weight 384.81 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pca21 _symmetry_space_group_name_Hall p_2c_-2ac loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' 'x+1/2, -y, z' '-x+1/2, y, z+1/2' _cell_length_a 15.450(10) _cell_length_b 10.490(7) _cell_length_c 10.828(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1755(2) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 3268 _cell_measurement_theta_min 2.35 _cell_measurement_theta_max 21.43 _exptl_crystal_description plate _exptl_crystal_colour colorless _exptl_crystal_size_max 0.44 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.456 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 792 _exptl_absorpt_coefficient_mu 0.371 _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 298(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 ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13312 _diffrn_reflns_av_R_equivalents 0.1182 _diffrn_reflns_av_sigmaI/netI 0.0745 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.94 _diffrn_reflns_theta_max 26.47 _reflns_number_total 3373 _reflns_number_gt 2707 _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^)+(0.0618P)^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 -0.01(9) _refine_ls_number_reflns 3373 _refine_ls_number_parameters 226 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0622 _refine_ls_R_factor_gt 0.0515 _refine_ls_wR_factor_ref 0.1225 _refine_ls_wR_factor_gt 0.1173 _refine_ls_goodness_of_fit_ref 0.958 _refine_ls_restrained_S_all 0.958 _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 Cl1 Cl 0.74403(11) 0.13457(13) 0.00974(19) 0.1253(6) Uani 1 1 d . . . C1 C 0.8086(3) 0.2567(4) 0.0673(5) 0.0730(12) Uani 1 1 d . . . C2 C 0.7752(3) 0.3364(4) 0.1558(5) 0.0754(12) Uani 1 1 d . . . H2 H 0.7191 0.3246 0.1849 0.091 Uiso 1 1 calc R . . C3 C 0.8256(2) 0.4342(3) 0.2012(4) 0.0580(9) Uani 1 1 d . . . H3 H 0.8035 0.4895 0.2605 0.070 Uiso 1 1 calc R . . C4 C 0.9093(2) 0.4497(3) 0.1580(3) 0.0446(8) Uani 1 1 d . . . S1 S 0.97363(4) 0.57511(8) 0.21245(9) 0.0432(2) Uani 1 1 d . . . O1 O 0.93949(15) 0.6123(3) 0.3313(2) 0.0569(6) Uani 1 1 d . . . O2 O 1.06255(13) 0.5385(2) 0.2039(3) 0.0616(6) Uani 1 1 d . . . C5 C 0.9421(2) 0.3678(3) 0.0697(3) 0.0539(9) Uani 1 1 d . . . H5 H 0.9982 0.3783 0.0402 0.065 Uiso 1 1 calc R . . C6 C 0.8906(3) 0.2703(3) 0.0258(4) 0.0650(11) Uani 1 1 d . . . H6 H 0.9124 0.2138 -0.0326 0.078 Uiso 1 1 calc R . . C7 C 0.8017(2) 0.6814(3) 0.0204(3) 0.0493(8) Uani 1 1 d . . . F2 F 0.83188(15) 0.6026(2) -0.0688(2) 0.0734(7) Uani 1 1 d . . . C8 C 0.7137(2) 0.7021(4) 0.0225(4) 0.0641(10) Uani 1 1 d . . . H8 H 0.6783 0.6627 -0.0355 0.077 Uiso 1 1 calc R . . C9 C 0.6788(2) 0.7795(4) 0.1091(4) 0.0678(11) Uani 1 1 d . . . H9 H 0.6195 0.7951 0.1113 0.081 Uiso 1 1 calc R . . C10 C 0.7337(2) 0.8341(3) 0.1935(4) 0.0571(9) Uani 1 1 d . . . F1 F 0.69915(14) 0.9129(2) 0.2800(3) 0.0892(8) Uani 1 1 d . . . C11 C 0.82032(19) 0.8144(3) 0.1923(3) 0.0450(8) Uani 1 1 d . . . H11 H 0.8547 0.8544 0.2511 0.054 Uiso 1 1 calc R . . C12 C 0.85894(18) 0.7355(3) 0.1048(3) 0.0379(7) Uani 1 1 d . . . C13 C 0.95664(18) 0.7101(3) 0.1080(3) 0.0384(7) Uani 1 1 d . . . C14 C 1.0002(2) 0.6822(3) -0.0167(3) 0.0483(8) Uani 1 1 d . . . H14A H 1.0605 0.6601 -0.0033 0.058 Uiso 1 1 calc R . . H14B H 0.9720 0.6101 -0.0558 0.058 Uiso 1 1 calc R . . C15 C 1.0075(2) 0.8202(3) 0.1681(3) 0.0481(8) Uani 1 1 d . . . H15A H 0.9840 0.8378 0.2494 0.058 Uiso 1 1 calc R . . H15B H 1.0676 0.7955 0.1779 0.058 Uiso 1 1 calc R . . C16 C 0.9947(2) 0.7986(4) -0.1019(4) 0.0616(10) Uani 1 1 d . . . H16A H 1.0302 0.7830 -0.1742 0.074 Uiso 1 1 calc R . . H16B H 0.9354 0.8080 -0.1295 0.074 Uiso 1 1 calc R . . C17 C 1.0020(3) 0.9392(4) 0.0891(5) 0.0659(10) Uani 1 1 d . . . H17A H 0.9438 0.9733 0.0953 0.079 Uiso 1 1 calc R . . H17B H 1.0412 1.0025 0.1228 0.079 Uiso 1 1 calc R . . C18 C 1.0230(2) 0.9209(4) -0.0440(4) 0.0632(11) Uani 1 1 d . . . O3 O 1.0590(2) 1.0036(3) -0.1016(4) 0.1016(12) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.1295(11) 0.0883(9) 0.1582(15) -0.0440(11) 0.0113(11) -0.0412(9) C1 0.081(3) 0.050(2) 0.088(3) -0.009(2) 0.010(2) -0.0138(19) C2 0.058(2) 0.069(3) 0.098(3) -0.006(3) 0.023(2) -0.014(2) C3 0.0535(17) 0.056(2) 0.065(2) -0.0036(19) 0.015(2) -0.0006(15) C4 0.0460(16) 0.0414(18) 0.0465(18) 0.0125(16) 0.0077(14) 0.0069(13) S1 0.0395(3) 0.0520(5) 0.0382(4) 0.0082(4) 0.0000(4) 0.0058(3) O1 0.0580(13) 0.0778(17) 0.0351(13) 0.0051(12) 0.0005(11) 0.0054(12) O2 0.0454(11) 0.0726(15) 0.0667(16) 0.0176(15) -0.0040(14) 0.0090(10) C5 0.058(2) 0.048(2) 0.056(2) 0.0070(17) 0.0208(17) 0.0071(16) C6 0.090(3) 0.043(2) 0.062(3) -0.0025(19) 0.022(2) 0.0044(19) C7 0.0535(18) 0.0502(19) 0.0441(19) -0.0072(16) -0.0101(15) 0.0020(15) F2 0.0749(13) 0.0855(16) 0.0598(14) -0.0360(12) -0.0152(10) 0.0057(12) C8 0.051(2) 0.072(2) 0.069(2) -0.005(2) -0.0204(19) -0.0039(18) C9 0.0395(18) 0.073(3) 0.091(3) -0.002(2) -0.010(2) 0.0084(17) C10 0.0509(18) 0.052(2) 0.068(3) -0.0058(19) 0.0088(18) 0.0052(15) F1 0.0658(14) 0.0926(18) 0.109(2) -0.0361(16) 0.0245(13) 0.0140(12) C11 0.0454(15) 0.0447(18) 0.0448(19) -0.0023(16) 0.0006(14) -0.0004(13) C12 0.0412(15) 0.0374(16) 0.0351(15) 0.0014(13) -0.0022(13) -0.0001(12) C13 0.0421(15) 0.0406(17) 0.0325(15) 0.0021(14) -0.0003(12) 0.0012(13) C14 0.0496(17) 0.054(2) 0.0414(18) 0.0072(17) 0.0088(14) 0.0039(16) C15 0.0440(16) 0.050(2) 0.050(2) -0.0064(17) -0.0026(13) -0.0066(14) C16 0.070(2) 0.073(3) 0.0421(19) 0.0116(19) 0.0096(17) 0.006(2) C17 0.068(2) 0.046(2) 0.084(3) 0.002(2) 0.005(2) -0.0148(18) C18 0.056(2) 0.059(3) 0.074(3) 0.026(2) -0.0046(19) -0.0023(18) O3 0.116(3) 0.090(2) 0.099(3) 0.054(2) 0.002(2) -0.025(2) _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 Cl1 C1 1.740(4) . ? C1 C6 1.352(6) . ? C1 C2 1.373(6) . ? C2 C3 1.378(5) . ? C2 H2 0.9300 . ? C3 C4 1.385(4) . ? C3 H3 0.9300 . ? C4 C5 1.381(5) . ? C4 S1 1.751(4) . ? S1 O2 1.430(2) . ? S1 O1 1.445(3) . ? S1 C13 1.831(3) . ? C5 C6 1.381(5) . ? C5 H5 0.9300 . ? C6 H6 0.9300 . ? C7 F2 1.355(4) . ? C7 C8 1.377(5) . ? C7 C12 1.392(4) . ? C8 C9 1.352(6) . ? C8 H8 0.9300 . ? C9 C10 1.373(6) . ? C9 H9 0.9300 . ? C10 C11 1.355(4) . ? C10 F1 1.357(4) . ? C11 C12 1.392(4) . ? C11 H11 0.9300 . ? C12 C13 1.533(4) . ? C13 C14 1.537(5) . ? C13 C15 1.541(4) . ? C14 C16 1.533(5) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 C17 1.516(6) . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? C16 C18 1.493(6) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 C18 1.490(7) . ? C17 H17A 0.9700 . ? C17 H17B 0.9700 . ? C18 O3 1.204(5) . ? 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 C6 C1 C2 121.4(4) . . ? C6 C1 Cl1 119.7(3) . . ? C2 C1 Cl1 118.9(3) . . ? C1 C2 C3 119.3(4) . . ? C1 C2 H2 120.3 . . ? C3 C2 H2 120.3 . . ? C2 C3 C4 119.6(4) . . ? C2 C3 H3 120.2 . . ? C4 C3 H3 120.2 . . ? C5 C4 C3 120.2(3) . . ? C5 C4 S1 119.5(3) . . ? C3 C4 S1 120.3(3) . . ? O2 S1 O1 118.76(16) . . ? O2 S1 C4 108.75(16) . . ? O1 S1 C4 107.22(16) . . ? O2 S1 C13 107.78(14) . . ? O1 S1 C13 106.79(15) . . ? C4 S1 C13 106.97(15) . . ? C6 C5 C4 119.2(3) . . ? C6 C5 H5 120.4 . . ? C4 C5 H5 120.4 . . ? C1 C6 C5 120.2(4) . . ? C1 C6 H6 119.9 . . ? C5 C6 H6 119.9 . . ? F2 C7 C8 116.6(3) . . ? F2 C7 C12 119.9(3) . . ? C8 C7 C12 123.5(3) . . ? C9 C8 C7 120.0(3) . . ? C9 C8 H8 120.0 . . ? C7 C8 H8 120.0 . . ? C8 C9 C10 117.8(3) . . ? C8 C9 H9 121.1 . . ? C10 C9 H9 121.1 . . ? C11 C10 F1 119.2(3) . . ? C11 C10 C9 122.7(4) . . ? F1 C10 C9 118.1(3) . . ? C10 C11 C12 121.4(3) . . ? C10 C11 H11 119.3 . . ? C12 C11 H11 119.3 . . ? C7 C12 C11 114.6(3) . . ? C7 C12 C13 124.7(3) . . ? C11 C12 C13 120.6(3) . . ? C12 C13 C14 116.4(3) . . ? C12 C13 C15 112.4(2) . . ? C14 C13 C15 106.9(3) . . ? C12 C13 S1 106.9(2) . . ? C14 C13 S1 109.4(2) . . ? C15 C13 S1 104.2(2) . . ? C16 C14 C13 110.6(3) . . ? C16 C14 H14A 109.5 . . ? C13 C14 H14A 109.5 . . ? C16 C14 H14B 109.5 . . ? C13 C14 H14B 109.5 . . ? H14A C14 H14B 108.1 . . ? C17 C15 C13 110.5(3) . . ? C17 C15 H15A 109.5 . . ? C13 C15 H15A 109.5 . . ? C17 C15 H15B 109.5 . . ? C13 C15 H15B 109.5 . . ? H15A C15 H15B 108.1 . . ? C18 C16 C14 114.6(3) . . ? C18 C16 H16A 108.6 . . ? C14 C16 H16A 108.6 . . ? C18 C16 H16B 108.6 . . ? C14 C16 H16B 108.6 . . ? H16A C16 H16B 107.6 . . ? C18 C17 C15 115.3(4) . . ? C18 C17 H17A 108.4 . . ? C15 C17 H17A 108.4 . . ? C18 C17 H17B 108.4 . . ? C15 C17 H17B 108.4 . . ? H17A C17 H17B 107.5 . . ? O3 C18 C17 120.6(4) . . ? O3 C18 C16 122.4(5) . . ? C17 C18 C16 116.9(3) . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 26.47 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.303 _refine_diff_density_min -0.172 _refine_diff_density_rms 0.057 # Attachment 'Alcohol4MOD.cif' data_jrc2573n _database_code_depnum_ccdc_archive 'CCDC 600829' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common jrc2573n _chemical_melting_point ? _chemical_formula_moiety 'C18 H17 Cl F2 O3 S' _chemical_formula_sum 'C18 H17 Cl F2 O3 S' _chemical_formula_weight 386.83 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21/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 6.9274(5) _cell_length_b 8.4158(6) _cell_length_c 29.301(2) _cell_angle_alpha 90.00 _cell_angle_beta 92.7430(10) _cell_angle_gamma 90.00 _cell_volume 1706.3(2) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 8694 _cell_measurement_theta_min 2.52 _cell_measurement_theta_max 26.41 _exptl_crystal_description polyhedron _exptl_crystal_colour colorless _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.225 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.506 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 800 _exptl_absorpt_coefficient_mu 0.382 _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 223(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 ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17593 _diffrn_reflns_av_R_equivalents 0.0271 _diffrn_reflns_av_sigmaI/netI 0.0228 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 36 _diffrn_reflns_theta_min 1.39 _diffrn_reflns_theta_max 26.41 _reflns_number_total 3513 _reflns_number_gt 3012 _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^)+(0.0545P)^2^+0.5977P] 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 3513 _refine_ls_number_parameters 227 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0472 _refine_ls_R_factor_gt 0.0401 _refine_ls_wR_factor_ref 0.1054 _refine_ls_wR_factor_gt 0.1009 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_restrained_S_all 1.041 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.2244(3) 0.2046(2) 0.41122(6) 0.0427(4) Uani 1 1 d . . . H1 H 0.3417 0.2312 0.4268 0.051 Uiso 1 1 calc R . . C2 C 0.0875(3) 0.1158(3) 0.43261(7) 0.0481(5) Uani 1 1 d . . . H2 H 0.1105 0.0810 0.4629 0.058 Uiso 1 1 calc R . . C3 C -0.0840(3) 0.0788(2) 0.40885(7) 0.0412(4) Uani 1 1 d . . . C4 C -0.1212(3) 0.1269(2) 0.36431(7) 0.0384(4) Uani 1 1 d . . . H4 H -0.2386 0.1002 0.3488 0.046 Uiso 1 1 calc R . . C5 C 0.0158(2) 0.2148(2) 0.34272(6) 0.0352(4) Uani 1 1 d . . . H5 H -0.0066 0.2477 0.3123 0.042 Uiso 1 1 calc R . . C6 C 0.1872(2) 0.2541(2) 0.36660(6) 0.0324(4) Uani 1 1 d . . . C7 C 0.0864(2) 0.6155(2) 0.41368(6) 0.0350(4) Uani 1 1 d . . . C8 C 0.0698(3) 0.6444(2) 0.45949(6) 0.0423(4) Uani 1 1 d . . . H8 H -0.0527 0.6452 0.4720 0.051 Uiso 1 1 calc R . . C9 C 0.2328(3) 0.6724(2) 0.48714(6) 0.0439(5) Uani 1 1 d . . . H9 H 0.2251 0.6923 0.5186 0.053 Uiso 1 1 calc R . . C10 C 0.4073(3) 0.6701(2) 0.46666(6) 0.0392(4) Uani 1 1 d . . . C11 C 0.4244(2) 0.6422(2) 0.42100(6) 0.0345(4) Uani 1 1 d . . . H11 H 0.5476 0.6421 0.4089 0.041 Uiso 1 1 calc R . . C12 C 0.2614(2) 0.6138(2) 0.39212(5) 0.0294(3) Uani 1 1 d . . . C13 C 0.2871(2) 0.5756(2) 0.34180(5) 0.0300(4) Uani 1 1 d . . . C14 C 0.4569(2) 0.6682(2) 0.32148(6) 0.0354(4) Uani 1 1 d . . . H14A H 0.5734 0.6555 0.3415 0.042 Uiso 1 1 calc R . . H14B H 0.4837 0.6242 0.2915 0.042 Uiso 1 1 calc R . . C15 C 0.4088(3) 0.8442(2) 0.31657(6) 0.0390(4) Uani 1 1 d . . . H15A H 0.3913 0.8897 0.3469 0.047 Uiso 1 1 calc R . . H15B H 0.5171 0.8994 0.3032 0.047 Uiso 1 1 calc R . . C16 C 0.2264(3) 0.8709(2) 0.28663(6) 0.0393(4) Uani 1 1 d . . . H16 H 0.1934 0.9854 0.2866 0.047 Uiso 1 1 calc R . . C17 C 0.0584(2) 0.7759(2) 0.30430(6) 0.0362(4) Uani 1 1 d . . . H17A H -0.0549 0.7884 0.2833 0.043 Uiso 1 1 calc R . . H17B H 0.0253 0.8174 0.3342 0.043 Uiso 1 1 calc R . . C18 C 0.1088(2) 0.5999(2) 0.30878(6) 0.0327(4) Uani 1 1 d . . . H18A H 0.1358 0.5569 0.2787 0.039 Uiso 1 1 calc R . . H18B H -0.0017 0.5419 0.3202 0.039 Uiso 1 1 calc R . . Cl1 Cl -0.25920(9) -0.02856(7) 0.43586(2) 0.06376(19) Uani 1 1 d . . . F1 F -0.08208(14) 0.58525(17) 0.38958(4) 0.0535(3) Uani 1 1 d . . . F2 F 0.57147(17) 0.69454(18) 0.49295(4) 0.0596(4) Uani 1 1 d . . . O1 O 0.54191(18) 0.35195(17) 0.36609(5) 0.0486(4) Uani 1 1 d . . . O2 O 0.35972(19) 0.31983(17) 0.29202(4) 0.0471(3) Uani 1 1 d . . . O3 O 0.25001(19) 0.8192(2) 0.24076(4) 0.0482(4) Uani 1 1 d . . . H3 H 0.3638 0.8329 0.2340 0.072 Uiso 1 1 calc R . . S1 S 0.36304(6) 0.36678(6) 0.339586(15) 0.03587(14) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0421(10) 0.0473(11) 0.0377(10) -0.0044(8) -0.0090(8) 0.0009(9) C2 0.0615(13) 0.0489(12) 0.0334(10) 0.0039(9) -0.0035(9) -0.0008(10) C3 0.0461(10) 0.0317(9) 0.0461(11) -0.0014(8) 0.0057(8) 0.0010(8) C4 0.0353(9) 0.0318(9) 0.0472(11) -0.0047(8) -0.0070(8) 0.0045(7) C5 0.0387(9) 0.0313(9) 0.0347(9) -0.0027(7) -0.0066(7) 0.0049(7) C6 0.0328(8) 0.0320(9) 0.0321(8) -0.0061(7) -0.0024(7) 0.0064(7) C7 0.0270(8) 0.0410(10) 0.0373(9) -0.0024(8) 0.0040(7) -0.0019(7) C8 0.0416(10) 0.0462(11) 0.0404(10) 0.0001(8) 0.0148(8) 0.0012(8) C9 0.0596(12) 0.0452(11) 0.0279(9) -0.0022(8) 0.0108(8) -0.0030(9) C10 0.0415(10) 0.0440(11) 0.0314(9) -0.0001(8) -0.0039(7) -0.0094(8) C11 0.0310(8) 0.0416(10) 0.0311(9) 0.0000(7) 0.0017(7) -0.0052(7) C12 0.0285(8) 0.0302(9) 0.0296(8) -0.0025(7) 0.0023(6) -0.0009(6) C13 0.0236(7) 0.0351(9) 0.0313(8) -0.0044(7) 0.0005(6) 0.0008(7) C14 0.0264(8) 0.0525(11) 0.0272(8) -0.0035(8) 0.0019(6) -0.0052(7) C15 0.0392(9) 0.0482(11) 0.0294(9) -0.0036(8) 0.0006(7) -0.0128(8) C16 0.0430(10) 0.0415(10) 0.0334(9) -0.0013(8) 0.0008(7) -0.0021(8) C17 0.0328(8) 0.0422(10) 0.0336(9) -0.0006(8) 0.0009(7) 0.0029(7) C18 0.0278(8) 0.0386(10) 0.0314(8) -0.0056(7) -0.0015(6) -0.0010(7) Cl1 0.0675(4) 0.0529(3) 0.0719(4) 0.0072(3) 0.0145(3) -0.0148(3) F1 0.0252(5) 0.0862(9) 0.0493(7) -0.0087(6) 0.0051(4) -0.0066(5) F2 0.0553(7) 0.0908(10) 0.0317(6) -0.0024(6) -0.0093(5) -0.0193(7) O1 0.0282(6) 0.0512(8) 0.0658(9) -0.0051(7) -0.0039(6) 0.0096(6) O2 0.0479(8) 0.0505(8) 0.0438(8) -0.0135(6) 0.0129(6) 0.0027(6) O3 0.0401(7) 0.0757(10) 0.0285(6) -0.0018(6) 0.0002(5) -0.0071(7) S1 0.0282(2) 0.0403(3) 0.0393(3) -0.00769(19) 0.00286(17) 0.00545(17) _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 1.382(3) . ? C1 C6 1.385(3) . ? C1 H1 0.9400 . ? C2 C3 1.383(3) . ? C2 H2 0.9400 . ? C3 C4 1.379(3) . ? C3 Cl1 1.734(2) . ? C4 C5 1.381(3) . ? C4 H4 0.9400 . ? C5 C6 1.388(2) . ? C5 H5 0.9400 . ? C6 S1 1.7614(18) . ? C7 F1 1.3586(19) . ? C7 C8 1.375(2) . ? C7 C12 1.394(2) . ? C8 C9 1.378(3) . ? C8 H8 0.9400 . ? C9 C10 1.375(3) . ? C9 H9 0.9400 . ? C10 F2 1.359(2) . ? C10 C11 1.369(2) . ? C11 C12 1.399(2) . ? C11 H11 0.9400 . ? C12 C13 1.528(2) . ? C13 C18 1.546(2) . ? C13 C14 1.554(2) . ? C13 S1 1.8366(18) . ? C14 C15 1.523(3) . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C15 C16 1.520(2) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C16 O3 1.430(2) . ? C16 C17 1.523(3) . ? C16 H16 0.9900 . ? C17 C18 1.526(3) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C18 H18A 0.9800 . ? C18 H18B 0.9800 . ? O1 S1 1.4359(13) . ? O2 S1 1.4477(13) . ? O3 H3 0.8300 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 C1 C6 119.36(17) . . ? C2 C1 H1 120.3 . . ? C6 C1 H1 120.3 . . ? C1 C2 C3 119.02(18) . . ? C1 C2 H2 120.5 . . ? C3 C2 H2 120.5 . . ? C4 C3 C2 121.82(18) . . ? C4 C3 Cl1 118.80(15) . . ? C2 C3 Cl1 119.37(15) . . ? C3 C4 C5 119.33(17) . . ? C3 C4 H4 120.3 . . ? C5 C4 H4 120.3 . . ? C4 C5 C6 119.11(16) . . ? C4 C5 H5 120.4 . . ? C6 C5 H5 120.4 . . ? C1 C6 C5 121.36(17) . . ? C1 C6 S1 118.99(13) . . ? C5 C6 S1 119.65(13) . . ? F1 C7 C8 115.54(15) . . ? F1 C7 C12 120.45(15) . . ? C8 C7 C12 124.00(16) . . ? C7 C8 C9 120.02(16) . . ? C7 C8 H8 120.0 . . ? C9 C8 H8 120.0 . . ? C10 C9 C8 116.96(16) . . ? C10 C9 H9 121.5 . . ? C8 C9 H9 121.5 . . ? F2 C10 C11 118.07(16) . . ? F2 C10 C9 118.67(16) . . ? C11 C10 C9 123.25(17) . . ? C10 C11 C12 121.01(16) . . ? C10 C11 H11 119.5 . . ? C12 C11 H11 119.5 . . ? C7 C12 C11 114.75(15) . . ? C7 C12 C13 125.68(15) . . ? C11 C12 C13 119.48(14) . . ? C12 C13 C18 116.74(13) . . ? C12 C13 C14 112.92(13) . . ? C18 C13 C14 106.93(13) . . ? C12 C13 S1 106.37(11) . . ? C18 C13 S1 109.03(11) . . ? C14 C13 S1 104.07(11) . . ? C15 C14 C13 110.95(14) . . ? C15 C14 H14A 109.4 . . ? C13 C14 H14A 109.4 . . ? C15 C14 H14B 109.4 . . ? C13 C14 H14B 109.4 . . ? H14A C14 H14B 108.0 . . ? C16 C15 C14 111.75(15) . . ? C16 C15 H15A 109.3 . . ? C14 C15 H15A 109.3 . . ? C16 C15 H15B 109.3 . . ? C14 C15 H15B 109.3 . . ? H15A C15 H15B 107.9 . . ? O3 C16 C15 111.61(15) . . ? O3 C16 C17 106.44(14) . . ? C15 C16 C17 110.72(15) . . ? O3 C16 H16 109.3 . . ? C15 C16 H16 109.3 . . ? C17 C16 H16 109.3 . . ? C16 C17 C18 111.32(14) . . ? C16 C17 H17A 109.4 . . ? C18 C17 H17A 109.4 . . ? C16 C17 H17B 109.4 . . ? C18 C17 H17B 109.4 . . ? H17A C17 H17B 108.0 . . ? C17 C18 C13 110.78(14) . . ? C17 C18 H18A 109.5 . . ? C13 C18 H18A 109.5 . . ? C17 C18 H18B 109.5 . . ? C13 C18 H18B 109.5 . . ? H18A C18 H18B 108.1 . . ? C16 O3 H3 109.5 . . ? O1 S1 O2 118.06(8) . . ? O1 S1 C6 107.93(8) . . ? O2 S1 C6 107.83(8) . . ? O1 S1 C13 107.78(8) . . ? O2 S1 C13 107.68(8) . . ? C6 S1 C13 107.09(8) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 26.41 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.413 _refine_diff_density_min -0.208 _refine_diff_density_rms 0.053