# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Shegming Ma' 'Zhangjie Shi' _publ_contact_author_name 'Dr Shengming Ma ' _publ_contact_author_address ; State Key Laboratory of Organic Chemistry Shanghai Institute of Organic Chemistry 354 Fenglin Lu Shanghai 200032 CHINA ; _publ_contact_author_email 'masm@pub.sioc.ac.cn ' _publ_section_title ; Mechanistic Switch Leading to Highly Efficient Chirality Transfer in Pd(0)-Catalyzed Coupling-Cyclization of Aryl Iodides with 1:1 Acid-Base Salts of 2,3-Allenoic Acids and L-(-)-Cinchonidine or D-(+)-/L-(-)-a-Methylbenzylamine. Enantioselective Synthesis of Highly Optically Active 3-Aryl Polysubstituted Butenolides ; data_shelxs_2 _database_code_CSD 157278 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C13 H13 Br O2' _chemical_formula_weight 281.13 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' '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 P21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 15.468(4) _cell_length_b 5.6049(19) _cell_length_c 15.501(5) _cell_angle_alpha 90.00 _cell_angle_beta 98.61(2) _cell_angle_gamma 90.00 _cell_volume 1328.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 13.96 _cell_measurement_theta_max 24.63 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.405 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 568 _exptl_absorpt_coefficient_mu 3.077 _exptl_absorpt_correction_type Psi-scan _exptl_absorpt_correction_T_min 0.7700 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type Afc7R _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time ? _diffrn_standards_decay_% -8.84 _diffrn_reflns_number 4597 _diffrn_reflns_av_R_equivalents 0.0277 _diffrn_reflns_av_sigmaI/netI 0.0882 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 6 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.66 _diffrn_reflns_theta_max 24.99 _reflns_number_total 3947 _reflns_number_gt 2031 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0561P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0019(13) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.025(18) _refine_ls_number_reflns 3947 _refine_ls_number_parameters 330 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1383 _refine_ls_R_factor_gt 0.0504 _refine_ls_wR_factor_ref 0.1398 _refine_ls_wR_factor_gt 0.1092 _refine_ls_goodness_of_fit_ref 0.998 _refine_ls_restrained_S_all 0.998 _refine_ls_shift/su_max 0.553 _refine_ls_shift/su_mean 0.036 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 0.49425(7) -0.3125(2) 0.18610(6) 0.1277(5) Uani 1 1 d . . . Br2 Br -0.25930(7) -0.2501(2) 0.78904(10) 0.1539(6) Uani 1 1 d . . . O1 O 0.1646(4) 0.0419(12) 0.6392(4) 0.108(2) Uani 1 1 d . . . O2 O 0.3021(4) -0.0640(15) 0.6324(4) 0.109(2) Uani 1 1 d . . . O3 O 0.2742(4) 0.6082(14) 0.7465(4) 0.118(2) Uani 1 1 d . . . O4 O 0.1350(4) 0.7053(16) 0.7484(5) 0.106(2) Uani 1 1 d . . . C1 C 0.3716(5) -0.0639(18) 0.3862(7) 0.081(3) Uani 1 1 d . . . C2 C 0.3942(6) -0.2028(17) 0.3203(7) 0.084(3) Uani 1 1 d . . . C3 C 0.4630(6) -0.1250(19) 0.2793(5) 0.083(2) Uani 1 1 d . . . C4 C 0.5076(6) 0.079(2) 0.3035(7) 0.093(3) Uani 1 1 d . . . C5 C 0.4853(5) 0.216(2) 0.3714(6) 0.087(3) Uani 1 1 d . . . C6 C 0.4143(4) 0.1422(17) 0.4123(5) 0.069(2) Uani 1 1 d . . . C7 C 0.3903(5) 0.2930(18) 0.4829(6) 0.086(3) Uani 1 1 d . . . C8 C 0.3143(5) 0.2704(15) 0.5122(5) 0.079(2) Uani 1 1 d . . . C9 C 0.2408(5) 0.2456(18) 0.5433(5) 0.081(2) Uani 1 1 d . . . C10 C 0.2323(7) 0.0690(16) 0.6093(6) 0.084(2) Uani 1 1 d . . . C11 C 0.1577(6) 0.3911(18) 0.5092(6) 0.096(3) Uani 1 1 d . . . H11A H 0.1113 0.2798 0.4883 0.115 Uiso 1 1 calc R . . H11B H 0.1401 0.4770 0.5580 0.115 Uiso 1 1 calc R . . C12 C 0.1649(6) 0.562(2) 0.4400(7) 0.119(4) Uani 1 1 d . . . H12A H 0.1800 0.4766 0.3898 0.143 Uiso 1 1 calc R . . H12B H 0.2121 0.6718 0.4597 0.143 Uiso 1 1 calc R . . C13 C 0.0810(6) 0.705(3) 0.4116(7) 0.138(4) Uani 1 1 d . . . H13A H 0.0352 0.5986 0.3869 0.206 Uiso 1 1 calc R . . H13B H 0.0913 0.8209 0.3687 0.206 Uiso 1 1 calc R . . H13C H 0.0641 0.7842 0.4613 0.206 Uiso 1 1 calc R . . C14 C -0.0129(6) 0.038(2) 0.8359(6) 0.086(3) Uani 1 1 d . . . C15 C -0.0809(9) -0.1119(18) 0.8084(6) 0.096(3) Uani 1 1 d . . . C16 C -0.1633(7) -0.0501(19) 0.8283(6) 0.091(3) Uani 1 1 d . . . C17 C -0.1750(6) 0.145(2) 0.8728(7) 0.099(3) Uani 1 1 d . . . C18 C -0.1065(6) 0.2991(17) 0.9036(5) 0.083(2) Uani 1 1 d . . . C19 C -0.0224(5) 0.2424(18) 0.8830(5) 0.074(2) Uani 1 1 d . . . C20 C 0.0512(6) 0.4030(17) 0.9137(5) 0.083(3) Uani 1 1 d . . . C21 C 0.1258(6) 0.4091(16) 0.8806(5) 0.086(2) Uani 1 1 d . . . C22 C 0.1990(6) 0.4121(19) 0.8462(6) 0.093(3) Uani 1 1 d . . . C23 C 0.2058(7) 0.5783(18) 0.7767(6) 0.090(3) Uani 1 1 d . . . C24 C 0.2773(6) 0.263(2) 0.8795(7) 0.121(4) Uani 1 1 d . . . H24A H 0.2934 0.1740 0.8305 0.145 Uiso 1 1 calc R . . H24B H 0.3254 0.3698 0.8995 0.145 Uiso 1 1 calc R . . C25 C 0.2702(7) 0.093(3) 0.9493(8) 0.164(6) Uani 1 1 d . . . H25A H 0.2244 -0.0210 0.9295 0.197 Uiso 1 1 calc R . . H25B H 0.2535 0.1780 0.9988 0.197 Uiso 1 1 calc R . . C26 C 0.3545(8) -0.039(3) 0.9783(9) 0.207(8) Uani 1 1 d . . . H26A H 0.3748 -0.1091 0.9285 0.310 Uiso 1 1 calc R . . H26B H 0.3445 -0.1631 1.0186 0.310 Uiso 1 1 calc R . . H26C H 0.3977 0.0695 1.0064 0.310 Uiso 1 1 calc R . . H1 H 0.331(9) -0.14(3) 0.426(10) 0.248 Uiso 1 1 d . . . H2 H 0.377(10) -0.34(4) 0.305(10) 0.248 Uiso 1 1 d . . . H3 H 0.538(10) 0.11(3) 0.275(10) 0.248 Uiso 1 1 d . . . H4 H 0.512(10) 0.38(3) 0.384(10) 0.248 Uiso 1 1 d . . . H5 H 0.428(10) 0.38(3) 0.519(10) 0.248 Uiso 1 1 d . . . H13 H 0.286(6) -0.19(2) 0.665(7) 0.15(5) Uiso 1 1 d . . . H14 H 0.042(8) 0.02(2) 0.830(8) 0.175 Uiso 1 1 d . . . H15 H -0.070(6) -0.29(3) 0.774(6) 0.175 Uiso 1 1 d . . . H16 H -0.219(7) 0.15(3) 0.895(7) 0.175 Uiso 1 1 d . . . H17 H -0.108(7) 0.48(2) 0.936(7) 0.175 Uiso 1 1 d . . . H18 H 0.035(7) 0.54(2) 0.951(6) 0.175 Uiso 1 1 d . . . H26 H 0.148(7) 0.79(2) 0.707(7) 0.14(5) Uiso 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 Br1 0.1277(8) 0.1526(12) 0.1110(7) 0.0014(9) 0.0444(6) 0.0188(8) Br2 0.1182(8) 0.1149(9) 0.2011(12) 0.0431(9) -0.0657(7) -0.0258(8) O1 0.079(4) 0.131(5) 0.125(5) 0.031(4) 0.054(4) 0.014(4) O2 0.077(4) 0.132(6) 0.123(5) 0.055(5) 0.037(4) 0.024(4) O3 0.081(4) 0.148(6) 0.137(5) 0.055(5) 0.058(4) 0.026(4) O4 0.091(4) 0.126(6) 0.112(5) 0.031(5) 0.050(4) 0.026(5) C1 0.056(5) 0.081(6) 0.110(8) 0.014(6) 0.022(5) -0.007(5) C2 0.070(6) 0.081(7) 0.104(7) 0.006(6) 0.021(5) 0.006(5) C3 0.073(6) 0.103(7) 0.076(6) 0.018(5) 0.025(5) 0.013(5) C4 0.066(6) 0.113(8) 0.101(8) 0.036(7) 0.016(5) -0.002(7) C5 0.062(5) 0.115(8) 0.085(5) 0.017(7) 0.016(4) -0.022(6) C6 0.045(4) 0.087(6) 0.072(5) 0.015(5) -0.002(4) -0.004(5) C7 0.070(6) 0.101(8) 0.084(6) 0.015(6) 0.003(5) -0.005(5) C8 0.084(6) 0.073(6) 0.079(5) -0.004(5) 0.009(5) -0.014(5) C9 0.073(5) 0.086(6) 0.089(5) 0.012(6) 0.027(4) 0.010(6) C10 0.097(7) 0.074(6) 0.083(6) 0.001(5) 0.018(6) -0.003(6) C11 0.098(7) 0.089(7) 0.104(7) -0.001(6) 0.025(5) 0.005(6) C12 0.093(7) 0.137(9) 0.133(8) 0.028(8) 0.033(6) -0.002(7) C13 0.112(7) 0.145(10) 0.152(8) 0.046(10) 0.010(6) 0.030(9) C14 0.079(6) 0.095(7) 0.084(6) -0.002(6) 0.015(5) -0.002(7) C15 0.115(8) 0.069(7) 0.098(7) -0.003(5) 0.002(6) 0.012(7) C16 0.092(8) 0.056(6) 0.111(7) 0.020(6) -0.026(6) -0.004(5) C17 0.068(6) 0.090(8) 0.136(8) 0.027(7) 0.007(5) -0.004(7) C18 0.085(6) 0.076(6) 0.090(6) 0.017(5) 0.021(5) 0.013(5) C19 0.082(6) 0.080(6) 0.064(5) -0.017(5) 0.017(4) -0.005(6) C20 0.084(6) 0.094(7) 0.078(6) 0.000(5) 0.038(5) -0.001(6) C21 0.101(7) 0.083(6) 0.074(5) 0.002(5) 0.013(5) 0.000(6) C22 0.073(6) 0.118(8) 0.095(7) 0.014(6) 0.032(5) -0.003(6) C23 0.090(7) 0.091(7) 0.095(7) 0.015(6) 0.033(6) 0.008(6) C24 0.082(6) 0.154(10) 0.131(7) 0.063(9) 0.029(5) 0.000(8) C25 0.112(8) 0.222(15) 0.165(10) 0.108(12) 0.040(8) 0.031(9) C26 0.125(9) 0.271(19) 0.227(14) 0.156(15) 0.038(10) 0.046(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 Br1 C3 1.906(9) . ? Br2 C16 1.888(9) . ? O1 C10 1.216(10) . ? O2 C10 1.317(10) . ? O2 H13 0.93(12) . ? O3 C23 1.232(10) . ? O4 C23 1.325(10) . ? O4 H26 0.84(11) . ? C1 C6 1.362(11) . ? C1 C2 1.371(13) . ? C1 H1 1.03(14) . ? C2 C3 1.389(13) . ? C2 H2 0.8(2) . ? C3 C4 1.360(13) . ? C4 C5 1.386(14) . ? C4 H3 0.71(14) . ? C5 C6 1.409(10) . ? C5 H4 1.03(16) . ? C6 C7 1.474(12) . ? C7 C8 1.328(12) . ? C7 H5 0.90(16) . ? C8 C9 1.307(10) . ? C9 C10 1.444(11) . ? C9 C11 1.547(11) . ? C11 C12 1.454(12) . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? C12 C13 1.532(12) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 C15 1.364(13) . ? C14 C19 1.378(13) . ? C14 H14 0.87(11) . ? C15 C16 1.398(13) . ? C15 H15 1.15(14) . ? C16 C17 1.318(13) . ? C17 C18 1.396(13) . ? C17 H16 0.82(10) . ? C18 C19 1.421(11) . ? C18 H17 1.14(13) . ? C19 C20 1.474(12) . ? C20 C21 1.330(12) . ? C20 H18 1.00(12) . ? C21 C22 1.323(12) . ? C22 C23 1.440(12) . ? C22 C24 1.499(13) . ? C24 C25 1.457(13) . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C25 C26 1.509(15) . ? C25 H25A 0.9700 . ? C25 H25B 0.9700 . ? C26 H26A 0.9600 . ? C26 H26B 0.9600 . ? C26 H26C 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 C10 O2 H13 108(6) . . ? C23 O4 H26 105(7) . . ? C6 C1 C2 122.4(8) . . ? C6 C1 H1 119(9) . . ? C2 C1 H1 118(9) . . ? C1 C2 C3 117.4(9) . . ? C1 C2 H2 129(10) . . ? C3 C2 H2 113(10) . . ? C4 C3 C2 122.0(9) . . ? C4 C3 Br1 119.9(8) . . ? C2 C3 Br1 118.2(9) . . ? C3 C4 C5 120.1(8) . . ? C3 C4 H3 112(10) . . ? C5 C4 H3 127(10) . . ? C4 C5 C6 118.6(10) . . ? C4 C5 H4 121(8) . . ? C6 C5 H4 120(8) . . ? C1 C6 C5 119.5(9) . . ? C1 C6 C7 122.8(7) . . ? C5 C6 C7 117.8(9) . . ? C8 C7 C6 122.3(8) . . ? C8 C7 H5 112(10) . . ? C6 C7 H5 125(10) . . ? C9 C8 C7 178.2(8) . . ? C8 C9 C10 120.8(8) . . ? C8 C9 C11 122.8(8) . . ? C10 C9 C11 116.4(7) . . ? O1 C10 O2 122.9(8) . . ? O1 C10 C9 122.1(9) . . ? O2 C10 C9 115.0(8) . . ? C12 C11 C9 116.6(8) . . ? C12 C11 H11A 108.1 . . ? C9 C11 H11A 108.1 . . ? C12 C11 H11B 108.2 . . ? C9 C11 H11B 108.1 . . ? H11A C11 H11B 107.3 . . ? C11 C12 C13 113.7(8) . . ? C11 C12 H12A 108.8 . . ? C13 C12 H12A 108.8 . . ? C11 C12 H12B 108.8 . . ? C13 C12 H12B 108.8 . . ? H12A C12 H12B 107.7 . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C15 C14 C19 122.6(8) . . ? C15 C14 H14 128(9) . . ? C19 C14 H14 110(9) . . ? C14 C15 C16 117.7(9) . . ? C14 C15 H15 121(5) . . ? C16 C15 H15 121(5) . . ? C17 C16 C15 121.4(9) . . ? C17 C16 Br2 119.8(9) . . ? C15 C16 Br2 118.7(9) . . ? C16 C17 C18 122.4(9) . . ? C16 C17 H16 117(10) . . ? C18 C17 H16 118(10) . . ? C17 C18 C19 117.2(9) . . ? C17 C18 H17 130(6) . . ? C19 C18 H17 112(6) . . ? C14 C19 C18 118.6(8) . . ? C14 C19 C20 122.6(8) . . ? C18 C19 C20 118.7(9) . . ? C21 C20 C19 124.3(8) . . ? C21 C20 H18 121(6) . . ? C19 C20 H18 113(6) . . ? C22 C21 C20 178.7(10) . . ? C21 C22 C23 118.2(9) . . ? C21 C22 C24 123.4(9) . . ? C23 C22 C24 118.3(8) . . ? O3 C23 O4 121.1(9) . . ? O3 C23 C22 122.4(10) . . ? O4 C23 C22 116.5(9) . . ? C25 C24 C22 118.2(8) . . ? C25 C24 H24A 107.8 . . ? C22 C24 H24A 107.8 . . ? C25 C24 H24B 107.7 . . ? C22 C24 H24B 107.8 . . ? H24A C24 H24B 107.1 . . ? C24 C25 C26 112.6(9) . . ? C24 C25 H25A 109.1 . . ? C26 C25 H25A 109.1 . . ? C24 C25 H25B 109.1 . . ? C26 C25 H25B 109.1 . . ? H25A C25 H25B 107.8 . . ? C25 C26 H26A 109.5 . . ? C25 C26 H26B 109.5 . . ? H26A C26 H26B 109.5 . . ? C25 C26 H26C 109.5 . . ? H26A C26 H26C 109.5 . . ? H26B C26 H26C 109.5 . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C6 C1 C2 C3 -0.5(13) . . . . ? C1 C2 C3 C4 0.8(13) . . . . ? C1 C2 C3 Br1 -178.9(7) . . . . ? C2 C3 C4 C5 0.6(14) . . . . ? Br1 C3 C4 C5 -179.8(7) . . . . ? C3 C4 C5 C6 -2.0(13) . . . . ? C2 C1 C6 C5 -0.9(12) . . . . ? C2 C1 C6 C7 179.8(8) . . . . ? C4 C5 C6 C1 2.2(12) . . . . ? C4 C5 C6 C7 -178.5(8) . . . . ? C1 C6 C7 C8 -15.9(12) . . . . ? C5 C6 C7 C8 164.8(8) . . . . ? C6 C7 C8 C9 111(30) . . . . ? C7 C8 C9 C10 -27(31) . . . . ? C7 C8 C9 C11 156(30) . . . . ? C8 C9 C10 O1 -179.8(8) . . . . ? C11 C9 C10 O1 -2.9(12) . . . . ? C8 C9 C10 O2 -1.8(12) . . . . ? C11 C9 C10 O2 175.2(8) . . . . ? C8 C9 C11 C12 -0.4(13) . . . . ? C10 C9 C11 C12 -177.3(9) . . . . ? C9 C11 C12 C13 -178.1(9) . . . . ? C19 C14 C15 C16 1.2(14) . . . . ? C14 C15 C16 C17 -0.8(14) . . . . ? C14 C15 C16 Br2 178.6(7) . . . . ? C15 C16 C17 C18 -0.6(15) . . . . ? Br2 C16 C17 C18 179.9(7) . . . . ? C16 C17 C18 C19 1.7(14) . . . . ? C15 C14 C19 C18 -0.1(13) . . . . ? C15 C14 C19 C20 179.2(9) . . . . ? C17 C18 C19 C14 -1.3(12) . . . . ? C17 C18 C19 C20 179.4(8) . . . . ? C14 C19 C20 C21 19.6(13) . . . . ? C18 C19 C20 C21 -161.1(8) . . . . ? C19 C20 C21 C22 13(45) . . . . ? C20 C21 C22 C23 80(45) . . . . ? C20 C21 C22 C24 -104(44) . . . . ? C21 C22 C23 O3 173.2(9) . . . . ? C24 C22 C23 O3 -3.0(14) . . . . ? C21 C22 C23 O4 -4.4(14) . . . . ? C24 C22 C23 O4 179.3(9) . . . . ? C21 C22 C24 C25 4.4(17) . . . . ? C23 C22 C24 C25 -179.5(10) . . . . ? C22 C24 C25 C26 -178.2(12) . . . . ? _diffrn_measured_fraction_theta_max 0.873 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.873 _refine_diff_density_max 0.288 _refine_diff_density_min -0.332 _refine_diff_density_rms 0.051 data_shelxs _database_code_CSD 157279 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H17 Br O2' _chemical_formula_weight 357.24 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' '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 P21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 5.7446(16) _cell_length_b 8.5350(12) _cell_length_c 16.9094(19) _cell_angle_alpha 90.00 _cell_angle_beta 95.02(2) _cell_angle_gamma 90.00 _cell_volume 825.9(3) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 13.57 _cell_measurement_theta_max 19.50 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.437 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 364 _exptl_absorpt_coefficient_mu 2.493 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.5944 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type AFC7R _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 200 _diffrn_standards_interval_time ? _diffrn_standards_decay_% -0.98 _diffrn_reflns_number 3442 _diffrn_reflns_av_R_equivalents 0.0304 _diffrn_reflns_av_sigmaI/netI 0.0718 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.42 _diffrn_reflns_theta_max 24.99 _reflns_number_total 2899 _reflns_number_gt 1940 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0904P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.002(3) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.014(19) _refine_ls_number_reflns 2899 _refine_ls_number_parameters 255 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1058 _refine_ls_R_factor_gt 0.0572 _refine_ls_wR_factor_ref 0.1605 _refine_ls_wR_factor_gt 0.1384 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.025 _refine_ls_shift/su_max 0.022 _refine_ls_shift/su_mean 0.001 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 Br Br -0.01353(16) 0.43976(12) 0.41877(5) 0.0931(4) Uani 1 1 d . . . O1 O 0.8042(10) 0.2428(7) 0.8531(4) 0.0760(15) Uani 1 1 d . . . O2 O 0.7827(8) 0.3824(6) 0.7400(3) 0.0657(14) Uani 1 1 d . . . C1 C 0.7383(13) 0.3581(10) 0.8177(5) 0.0585(18) Uani 1 1 d . . . C2 C 0.6029(11) 0.4922(8) 0.8442(4) 0.0522(17) Uani 1 1 d . . . C3 C 0.5721(11) 0.5944(8) 0.7840(4) 0.0497(15) Uani 1 1 d . . . C4 C 0.6839(12) 0.5312(8) 0.7136(5) 0.0539(17) Uani 1 1 d . . . C5 C 0.5286(15) 0.4946(10) 0.9265(4) 0.062(2) Uani 1 1 d . . . C6 C 0.3201(18) 0.3901(11) 0.9360(5) 0.070(2) Uani 1 1 d . . . C7 C 0.224(2) 0.4031(17) 1.0154(6) 0.086(3) Uani 1 1 d . . . C8 C 0.4547(11) 0.7467(9) 0.7799(4) 0.0488(16) Uani 1 1 d . . . C9 C 0.2523(13) 0.7734(10) 0.8174(5) 0.0589(18) Uani 1 1 d . . . C10 C 0.1490(14) 0.9211(13) 0.8156(4) 0.069(2) Uani 1 1 d . . . C11 C 0.2409(17) 1.0393(10) 0.7734(5) 0.070(2) Uani 1 1 d . . . C12 C 0.4380(15) 1.0163(10) 0.7354(5) 0.064(2) Uani 1 1 d . . . C13 C 0.5441(13) 0.8704(9) 0.7375(5) 0.0535(18) Uani 1 1 d . . . C14 C 0.5138(12) 0.5088(8) 0.6404(4) 0.0536(17) Uani 1 1 d . . . C15 C 0.5560(16) 0.5714(11) 0.5682(5) 0.073(2) Uani 1 1 d . . . C16 C 0.4011(16) 0.5512(12) 0.5024(5) 0.079(3) Uani 1 1 d . . . C17 C 0.2024(12) 0.4674(10) 0.5087(4) 0.063(2) Uani 1 1 d . . . C18 C 0.1552(15) 0.3994(9) 0.5813(4) 0.065(2) Uani 1 1 d . . . C19 C 0.3129(12) 0.4224(10) 0.6459(4) 0.0565(17) Uani 1 1 d . . . H1 H 0.817(12) 0.582(8) 0.692(4) 0.046(16) Uiso 1 1 d . . . H2 H 0.489(12) 0.600(10) 0.943(4) 0.055 Uiso 1 1 d . . . H3 H 0.659(12) 0.473(9) 0.957(4) 0.055 Uiso 1 1 d . . . H4 H 0.202(11) 0.406(8) 0.893(4) 0.055 Uiso 1 1 d . . . H5 H 0.399(15) 0.311(10) 0.928(4) 0.055 Uiso 1 1 d . . . H6 H 0.146(19) 0.491(15) 1.016(6) 0.09(4) Uiso 1 1 d . . . H7 H 0.340(15) 0.385(11) 1.049(5) 0.08(3) Uiso 1 1 d . . . H8 H 0.094(16) 0.317(12) 1.028(5) 0.09(3) Uiso 1 1 d . . . H9 H 0.174(19) 0.695(12) 0.836(6) 0.107 Uiso 1 1 d . . . H10 H 0.024(16) 0.936(17) 0.845(5) 0.107 Uiso 1 1 d . . . H11 H 0.137(18) 1.146(14) 0.768(6) 0.107 Uiso 1 1 d . . . H12 H 0.521(18) 1.098(14) 0.705(6) 0.107 Uiso 1 1 d . . . H13 H 0.703(19) 0.849(12) 0.711(6) 0.107 Uiso 1 1 d . . . H14 H 0.685(18) 0.650(13) 0.563(6) 0.107 Uiso 1 1 d . . . H15 H 0.406(18) 0.593(13) 0.449(6) 0.107 Uiso 1 1 d . . . H16 H 0.015(17) 0.340(14) 0.583(5) 0.107 Uiso 1 1 d . . . H17 H 0.280(17) 0.392(12) 0.694(6) 0.107 Uiso 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 Br 0.0866(6) 0.1268(9) 0.0641(5) -0.0192(6) -0.0031(3) 0.0326(6) O1 0.078(3) 0.062(3) 0.086(4) 0.003(3) -0.007(3) 0.015(3) O2 0.057(3) 0.061(3) 0.080(4) -0.004(2) 0.009(2) 0.018(2) C1 0.053(4) 0.060(5) 0.063(4) 0.000(4) 0.002(3) 0.003(4) C2 0.049(3) 0.054(5) 0.052(4) -0.002(3) 0.000(3) -0.002(3) C3 0.045(3) 0.049(4) 0.055(4) -0.008(3) 0.005(3) 0.004(3) C4 0.045(4) 0.047(4) 0.071(5) -0.001(3) 0.013(3) 0.007(3) C5 0.064(5) 0.065(6) 0.055(4) -0.001(4) -0.005(4) 0.009(4) C6 0.083(6) 0.078(7) 0.048(4) -0.001(4) 0.006(4) -0.002(5) C7 0.103(8) 0.094(9) 0.065(5) 0.005(5) 0.018(6) -0.003(8) C8 0.048(3) 0.057(4) 0.042(3) -0.006(3) 0.005(3) 0.000(3) C9 0.054(4) 0.057(5) 0.067(5) 0.000(4) 0.012(3) 0.004(4) C10 0.069(4) 0.085(6) 0.055(4) -0.006(5) 0.015(3) 0.024(5) C11 0.090(6) 0.057(5) 0.063(5) -0.006(4) 0.002(4) 0.024(5) C12 0.072(5) 0.055(5) 0.067(5) -0.001(4) 0.008(4) 0.004(4) C13 0.055(4) 0.056(5) 0.050(4) -0.002(3) 0.008(3) 0.001(4) C14 0.057(4) 0.047(4) 0.058(4) 0.001(3) 0.015(3) 0.011(3) C15 0.076(6) 0.073(6) 0.072(6) 0.008(4) 0.014(4) -0.002(5) C16 0.089(6) 0.098(7) 0.053(4) 0.017(4) 0.021(4) 0.017(5) C17 0.061(4) 0.066(6) 0.063(4) -0.007(4) 0.015(3) 0.014(4) C18 0.083(5) 0.051(5) 0.061(4) -0.004(3) 0.005(4) -0.001(4) C19 0.061(4) 0.055(4) 0.054(3) 0.006(4) 0.012(3) 0.000(4) _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 Br C17 1.891(7) . ? O1 C1 1.196(9) . ? O2 C1 1.376(9) . ? O2 C4 1.445(8) . ? C1 C2 1.475(10) . ? C2 C3 1.341(10) . ? C2 C5 1.493(10) . ? C3 C8 1.463(10) . ? C3 C4 1.501(10) . ? C4 C14 1.521(11) . ? C4 H1 0.98(7) . ? C5 C6 1.513(12) . ? C5 H2 0.98(8) . ? C5 H3 0.89(7) . ? C6 C7 1.501(13) . ? C6 H4 0.96(7) . ? C6 H5 0.83(8) . ? C7 H6 0.87(12) . ? C7 H7 0.85(9) . ? C7 H8 1.08(10) . ? C8 C9 1.391(10) . ? C8 C13 1.399(10) . ? C9 C10 1.393(13) . ? C9 H9 0.88(11) . ? C10 C11 1.367(14) . ? C10 H10 0.92(10) . ? C11 C12 1.365(13) . ? C11 H11 1.09(12) . ? C12 C13 1.386(11) . ? C12 H12 1.01(12) . ? C13 H13 1.07(11) . ? C14 C15 1.373(11) . ? C14 C19 1.380(10) . ? C15 C16 1.373(13) . ? C15 H14 1.01(11) . ? C16 C17 1.359(12) . ? C16 H15 0.98(11) . ? C17 C18 1.405(11) . ? C18 C19 1.371(10) . ? C18 H16 0.95(10) . ? C19 H17 0.88(10) . ? 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 O2 C4 109.1(6) . . ? O1 C1 O2 121.7(7) . . ? O1 C1 C2 129.7(7) . . ? O2 C1 C2 108.6(7) . . ? C3 C2 C1 108.2(6) . . ? C3 C2 C5 132.1(7) . . ? C1 C2 C5 119.7(6) . . ? C2 C3 C8 130.0(6) . . ? C2 C3 C4 109.3(6) . . ? C8 C3 C4 120.6(6) . . ? O2 C4 C3 104.8(6) . . ? O2 C4 C14 110.4(6) . . ? C3 C4 C14 113.7(5) . . ? O2 C4 H1 102(4) . . ? C3 C4 H1 122(4) . . ? C14 C4 H1 103(4) . . ? C2 C5 C6 112.6(6) . . ? C2 C5 H2 112(4) . . ? C6 C5 H2 108(4) . . ? C2 C5 H3 104(4) . . ? C6 C5 H3 117(5) . . ? H2 C5 H3 103(7) . . ? C7 C6 C5 114.1(8) . . ? C7 C6 H4 112(4) . . ? C5 C6 H4 110(4) . . ? C7 C6 H5 118(6) . . ? C5 C6 H5 91(6) . . ? H4 C6 H5 110(7) . . ? C6 C7 H6 108(7) . . ? C6 C7 H7 105(6) . . ? H6 C7 H7 121(10) . . ? C6 C7 H8 116(5) . . ? H6 C7 H8 103(8) . . ? H7 C7 H8 105(8) . . ? C9 C8 C13 118.0(7) . . ? C9 C8 C3 121.6(7) . . ? C13 C8 C3 120.4(6) . . ? C8 C9 C10 120.6(8) . . ? C8 C9 H9 121(7) . . ? C10 C9 H9 117(7) . . ? C11 C10 C9 119.8(7) . . ? C11 C10 H10 122(9) . . ? C9 C10 H10 118(9) . . ? C12 C11 C10 120.9(8) . . ? C12 C11 H11 123(6) . . ? C10 C11 H11 115(6) . . ? C11 C12 C13 119.9(8) . . ? C11 C12 H12 126(6) . . ? C13 C12 H12 114(6) . . ? C12 C13 C8 120.7(7) . . ? C12 C13 H13 122(6) . . ? C8 C13 H13 117(5) . . ? C15 C14 C19 118.8(7) . . ? C15 C14 C4 121.6(7) . . ? C19 C14 C4 119.6(6) . . ? C14 C15 C16 121.3(8) . . ? C14 C15 H14 121(6) . . ? C16 C15 H14 116(6) . . ? C17 C16 C15 119.4(8) . . ? C17 C16 H15 111(6) . . ? C15 C16 H15 129(6) . . ? C16 C17 C18 120.9(7) . . ? C16 C17 Br 119.9(6) . . ? C18 C17 Br 119.2(6) . . ? C19 C18 C17 118.2(7) . . ? C19 C18 H16 124(6) . . ? C17 C18 H16 118(6) . . ? C18 C19 C14 121.4(7) . . ? C18 C19 H17 120(7) . . ? C14 C19 H17 118(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 C4 O2 C1 O1 -179.5(7) . . . . ? C4 O2 C1 C2 1.0(7) . . . . ? O1 C1 C2 C3 179.4(8) . . . . ? O2 C1 C2 C3 -1.1(8) . . . . ? O1 C1 C2 C5 -0.2(12) . . . . ? O2 C1 C2 C5 179.3(6) . . . . ? C1 C2 C3 C8 -178.6(6) . . . . ? C5 C2 C3 C8 0.9(13) . . . . ? C1 C2 C3 C4 0.8(8) . . . . ? C5 C2 C3 C4 -179.7(7) . . . . ? C1 O2 C4 C3 -0.5(7) . . . . ? C1 O2 C4 C14 -123.2(6) . . . . ? C2 C3 C4 O2 -0.2(7) . . . . ? C8 C3 C4 O2 179.3(5) . . . . ? C2 C3 C4 C14 120.3(7) . . . . ? C8 C3 C4 C14 -60.2(8) . . . . ? C3 C2 C5 C6 102.9(10) . . . . ? C1 C2 C5 C6 -77.6(9) . . . . ? C2 C5 C6 C7 -173.5(9) . . . . ? C2 C3 C8 C9 -37.6(11) . . . . ? C4 C3 C8 C9 143.1(7) . . . . ? C2 C3 C8 C13 142.6(8) . . . . ? C4 C3 C8 C13 -36.7(9) . . . . ? C13 C8 C9 C10 -2.9(11) . . . . ? C3 C8 C9 C10 177.3(7) . . . . ? C8 C9 C10 C11 3.0(12) . . . . ? C9 C10 C11 C12 -2.5(13) . . . . ? C10 C11 C12 C13 1.8(13) . . . . ? C11 C12 C13 C8 -1.7(13) . . . . ? C9 C8 C13 C12 2.2(11) . . . . ? C3 C8 C13 C12 -178.0(7) . . . . ? O2 C4 C14 C15 -115.1(8) . . . . ? C3 C4 C14 C15 127.5(8) . . . . ? O2 C4 C14 C19 64.3(8) . . . . ? C3 C4 C14 C19 -53.1(9) . . . . ? C19 C14 C15 C16 0.9(12) . . . . ? C4 C14 C15 C16 -179.7(7) . . . . ? C14 C15 C16 C17 -0.1(13) . . . . ? C15 C16 C17 C18 -1.0(12) . . . . ? C15 C16 C17 Br 179.6(7) . . . . ? C16 C17 C18 C19 1.3(11) . . . . ? Br C17 C18 C19 -179.3(6) . . . . ? C17 C18 C19 C14 -0.5(11) . . . . ? C15 C14 C19 C18 -0.5(11) . . . . ? C4 C14 C19 C18 -179.9(7) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.381 _refine_diff_density_min -0.621 _refine_diff_density_rms 0.079