# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2010 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Taguchi, Takeo' _publ_contact_author_email taguchi@toyaku.ac.jp _publ_section_title ; 1,4-Addition of silicon dienoates to \^I+-,\^I^2^-unsaturated aldehydes catalyzed by in situ-generated silicon Lewis acid ; loop_ _publ_author_name H.Yanai A.Takahashi T.Taguchi # Attachment 'CBA04-6d.cif' data_anti-5d _database_code_depnum_ccdc_archive 'CCDC 783222' #TrackingRef 'CBA04-6d.cif' #============================================================================== # anti-5d #============================================================================== _audit_creation_date '17 November 09' _audit_creation_method SHELXL-97 _publ_section_abstract ; In situ-generated silyl methide species (R3Si-CTf2R') nicely catalyzed the reaction of beta-substituted alpha,beta-unsaturated aldehydes with silicon dienoates such as 3-bromo-2-TESO-furan to give the corresponding gamma-adducts with excellent 1,4-selectivity and good anti-selectivity. ; _publ_section_comment ; ; #============================================================================== # TEXT #============================================================================== _publ_section_acknowledgements ; ; _publ_section_references ; Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of G\"ottingen, Germany. A.L.Spek (2004) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. or A.L.Spek, J.Appl.Cryst. 2003, 36, 7-13. ; #============================================================================== # CHEMICAL DATA #============================================================================== _chemical_name_systematic ; (R*)-5-((S*)-1-(1,3-Dioxolan-2-yl)-3-methylbutan-2-yl)-3-bromofuran-2(5H)-one ; _chemical_name_common ;(R*)-5-((S*)-1-(1,3-Dioxolan-2-yl)-3-methylbutan-2-yl)-3- bromofuran-2(5H)-one ; _chemical_melting_point '85.2-86.0 C' _chemical_formula_moiety 'C12 H17 Br O4' _chemical_formula_sum 'C12 H17 Br O4' _chemical_formula_weight 305.17 _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_absolute_configuration . 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' #============================================================================== # CRYSTAL DATA #============================================================================== _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' 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 9.8580(19) _cell_length_b 15.388(3) _cell_length_c 9.3551(18) _cell_angle_alpha 90.00 _cell_angle_beta 116.254(2) _cell_angle_gamma 90.00 _cell_volume 1272.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 90 _cell_measurement_reflns_used 3547 _cell_measurement_theta_min 2.30 _cell_measurement_theta_max 27.61 _exptl_crystal_description Block _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.21 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.593 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 3.230 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.4332 _exptl_absorpt_correction_T_max 0.7057 _exptl_absorpt_process_details ; Crystal Faces plugin in Bruker APEX2 software ; _exptl_special_details ; ? ; #============================================================================== # EXPERIMENTAL DATA #============================================================================== _diffrn_ambient_temperature 90 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker TXS fine-focus rotating anode' _diffrn_radiation_monochromator 'Bruker Helios multilayer confocal mirror' _diffrn_measurement_device_type 'Bruker APEXII CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_reflns_number 7094 _diffrn_reflns_av_R_equivalents 0.0245 _diffrn_reflns_av_sigmaI/netI 0.0293 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 19 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.30 _diffrn_reflns_theta_max 27.61 _reflns_number_total 2892 _reflns_number_gt 2505 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker AXS, 2006)' _computing_cell_refinement 'APEX2 (Bruker AXS, 2006)' _computing_data_reduction 'SAINT (Bruker AXS, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSHEL (Bruker AXS,2002)' _computing_publication_material 'XCIF (Bruker AXS, 2001)' _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^)+(0.0377P)^2^+0.4222P] 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 2892 _refine_ls_number_parameters 156 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0338 _refine_ls_R_factor_gt 0.0266 _refine_ls_wR_factor_ref 0.0695 _refine_ls_wR_factor_gt 0.0664 _refine_ls_goodness_of_fit_ref 1.037 _refine_ls_restrained_S_all 1.037 _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 Br1 Br 0.68638(2) -0.077010(12) 1.10976(2) 0.02513(8) Uani 1 1 d . . . C1 C 0.76685(19) 0.03679(11) 0.7531(2) 0.0145(3) Uani 1 1 d . . . H1 H 0.8251 0.0061 0.7037 0.017 Uiso 1 1 calc R . . C2 C 0.8583(2) 0.05034(12) 1.0264(2) 0.0173(4) Uani 1 1 d . . . C3 C 0.6921(2) -0.02869(11) 0.8131(2) 0.0164(4) Uani 1 1 d . . . H3 H 0.6203 -0.0708 0.7495 0.020 Uiso 1 1 calc R . . C4 C 0.58549(19) 0.16186(11) 0.7132(2) 0.0151(3) Uani 1 1 d . . . H4A H 0.5768 0.1299 0.8006 0.018 Uiso 1 1 calc R . . H4B H 0.6539 0.2119 0.7608 0.018 Uiso 1 1 calc R . . C5 C 0.7223(2) 0.15159(11) 0.5353(2) 0.0177(4) Uani 1 1 d . . . H5 H 0.6433 0.1938 0.4663 0.021 Uiso 1 1 calc R . . C6 C 0.7551(2) 0.09139(13) 0.4238(2) 0.0241(4) Uani 1 1 d . . . H6A H 0.7809 0.1263 0.3518 0.036 Uiso 1 1 calc R . . H6B H 0.6652 0.0562 0.3612 0.036 Uiso 1 1 calc R . . H6C H 0.8400 0.0531 0.4871 0.036 Uiso 1 1 calc R . . C7 C 0.2121(2) 0.24481(13) 0.5967(2) 0.0216(4) Uani 1 1 d . . . H7A H 0.1711 0.2971 0.5296 0.026 Uiso 1 1 calc R . . H7B H 0.1657 0.2398 0.6710 0.026 Uiso 1 1 calc R . . C8 C 0.7419(2) -0.01869(11) 0.9687(2) 0.0171(4) Uani 1 1 d . . . C9 C 0.6557(2) 0.10143(11) 0.6325(2) 0.0136(3) Uani 1 1 d . . . H9 H 0.5705 0.0658 0.5539 0.016 Uiso 1 1 calc R . . C10 C 0.1812(2) 0.16312(12) 0.4932(2) 0.0212(4) Uani 1 1 d . . . H10A H 0.1135 0.1227 0.5135 0.025 Uiso 1 1 calc R . . H10B H 0.1342 0.1784 0.3786 0.025 Uiso 1 1 calc R . . C11 C 0.43146(19) 0.19529(11) 0.5993(2) 0.0145(3) Uani 1 1 d . . . H11 H 0.4369 0.2277 0.5093 0.017 Uiso 1 1 calc R . . C12 C 0.8639(2) 0.20452(13) 0.6371(3) 0.0264(4) Uani 1 1 d . . . H12A H 0.9469 0.1650 0.7002 0.040 Uiso 1 1 calc R . . H12B H 0.8427 0.2427 0.7086 0.040 Uiso 1 1 calc R . . H12C H 0.8927 0.2397 0.5676 0.040 Uiso 1 1 calc R . . O1 O 0.93333(16) 0.07685(8) 1.15990(16) 0.0233(3) Uani 1 1 d . . . O2 O 0.87201(15) 0.08226(8) 0.89755(15) 0.0165(3) Uani 1 1 d . . . O3 O 0.32802(14) 0.12519(8) 0.54078(16) 0.0216(3) Uani 1 1 d . . . O4 O 0.37360(14) 0.24953(8) 0.68256(15) 0.0187(3) 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 Br1 0.03395(14) 0.02554(12) 0.02044(11) 0.00619(7) 0.01616(9) 0.00309(8) C1 0.0131(9) 0.0152(8) 0.0131(8) -0.0013(6) 0.0039(7) 0.0008(6) C2 0.0147(9) 0.0184(8) 0.0163(8) 0.0009(7) 0.0046(7) 0.0080(7) C3 0.0152(9) 0.0148(8) 0.0170(8) 0.0011(6) 0.0050(7) 0.0005(7) C4 0.0145(9) 0.0166(8) 0.0140(8) -0.0010(6) 0.0060(7) 0.0009(7) C5 0.0176(9) 0.0185(9) 0.0199(9) 0.0039(7) 0.0111(8) 0.0029(7) C6 0.0287(11) 0.0255(10) 0.0250(10) -0.0008(8) 0.0182(9) -0.0011(8) C7 0.0136(9) 0.0200(9) 0.0305(10) 0.0017(7) 0.0093(8) 0.0012(7) C8 0.0188(9) 0.0164(8) 0.0175(8) 0.0028(6) 0.0092(7) 0.0042(7) C9 0.0130(8) 0.0144(8) 0.0132(8) 0.0004(6) 0.0055(7) 0.0005(6) C10 0.0129(9) 0.0255(10) 0.0220(9) 0.0011(7) 0.0049(7) 0.0010(7) C11 0.0140(9) 0.0147(8) 0.0152(8) -0.0005(6) 0.0068(7) 0.0006(6) C12 0.0279(11) 0.0229(10) 0.0349(11) -0.0046(8) 0.0198(10) -0.0074(8) O1 0.0227(7) 0.0261(7) 0.0147(6) -0.0040(5) 0.0026(5) 0.0052(5) O2 0.0138(6) 0.0183(6) 0.0143(6) -0.0014(5) 0.0034(5) -0.0013(5) O3 0.0128(6) 0.0188(7) 0.0279(7) -0.0044(5) 0.0042(6) -0.0009(5) O4 0.0130(6) 0.0232(7) 0.0202(6) -0.0047(5) 0.0075(5) 0.0025(5) _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 C8 1.8667(18) . ? C1 O2 1.467(2) . ? C1 C3 1.496(2) . ? C1 C9 1.539(2) . ? C1 H1 1.0000 . ? C2 O1 1.207(2) . ? C2 O2 1.363(2) . ? C2 C8 1.479(3) . ? C3 C8 1.324(2) . ? C3 H3 0.9500 . ? C4 C11 1.508(2) . ? C4 C9 1.541(2) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C12 1.530(3) . ? C5 C6 1.532(3) . ? C5 C9 1.544(2) . ? C5 H5 1.0000 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 O4 1.433(2) . ? C7 C10 1.533(3) . ? C7 H7A 0.9900 . ? C7 H7B 0.9900 . ? C9 H9 1.0000 . ? C10 O3 1.437(2) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 O3 1.417(2) . ? C11 O4 1.422(2) . ? C11 H11 1.0000 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? 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 O2 C1 C3 103.89(13) . . ? O2 C1 C9 110.54(13) . . ? C3 C1 C9 113.64(15) . . ? O2 C1 H1 109.5 . . ? C3 C1 H1 109.5 . . ? C9 C1 H1 109.5 . . ? O1 C2 O2 122.56(18) . . ? O1 C2 C8 129.93(18) . . ? O2 C2 C8 107.50(14) . . ? C8 C3 C1 109.27(16) . . ? C8 C3 H3 125.4 . . ? C1 C3 H3 125.4 . . ? C11 C4 C9 112.95(14) . . ? C11 C4 H4A 109.0 . . ? C9 C4 H4A 109.0 . . ? C11 C4 H4B 109.0 . . ? C9 C4 H4B 109.0 . . ? H4A C4 H4B 107.8 . . ? C12 C5 C6 109.67(15) . . ? C12 C5 C9 114.07(15) . . ? C6 C5 C9 111.81(15) . . ? C12 C5 H5 107.0 . . ? C6 C5 H5 107.0 . . ? C9 C5 H5 107.0 . . ? C5 C6 H6A 109.5 . . ? C5 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C5 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? O4 C7 C10 104.88(14) . . ? O4 C7 H7A 110.8 . . ? C10 C7 H7A 110.8 . . ? O4 C7 H7B 110.8 . . ? C10 C7 H7B 110.8 . . ? H7A C7 H7B 108.8 . . ? C3 C8 C2 109.58(16) . . ? C3 C8 Br1 129.77(15) . . ? C2 C8 Br1 120.66(13) . . ? C1 C9 C4 111.08(14) . . ? C1 C9 C5 113.85(15) . . ? C4 C9 C5 112.77(14) . . ? C1 C9 H9 106.2 . . ? C4 C9 H9 106.2 . . ? C5 C9 H9 106.2 . . ? O3 C10 C7 104.23(14) . . ? O3 C10 H10A 110.9 . . ? C7 C10 H10A 110.9 . . ? O3 C10 H10B 110.9 . . ? C7 C10 H10B 110.9 . . ? H10A C10 H10B 108.9 . . ? O3 C11 O4 105.30(13) . . ? O3 C11 C4 109.92(14) . . ? O4 C11 C4 109.62(13) . . ? O3 C11 H11 110.6 . . ? O4 C11 H11 110.6 . . ? C4 C11 H11 110.6 . . ? C5 C12 H12A 109.5 . . ? C5 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C5 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C2 O2 C1 109.68(14) . . ? C11 O3 C10 105.35(13) . . ? C11 O4 C7 106.18(14) . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 27.61 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.640 _refine_diff_density_min -0.368 _refine_diff_density_rms 0.069 # Attachment 'CBA04-6e.cif' data_anti-5e _database_code_depnum_ccdc_archive 'CCDC 783223' #TrackingRef 'CBA04-6e.cif' #============================================================================== # anti-5e #============================================================================== _audit_creation_date '13 November 09' _audit_creation_method SHELXL-97 _publ_section_abstract ; In situ-generated silyl methide species (R3Si-CTf2R') nicely catalyzed the reaction of beta-substituted alpha,beta-unsaturated aldehydes with silicon dienoates such as 3-bromo-2-TESO-furan to give the corresponding gamma-adducts with excellent 1,4-selectivity and good anti-selectivity. ; _publ_section_comment ; ; #============================================================================== # TEXT #============================================================================== _publ_section_acknowledgements ; ; _publ_section_references ; Sheldrick, G. M. (1997). SHELXL97. Program for the Refinement of Crystal Structures. University of G\"ottingen, Germany. A.L.Spek (2004) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. or A.L.Spek, J.Appl.Cryst. 2003, 36, 7-13. ; #============================================================================== # CHEMICAL DATA #============================================================================== _chemical_name_systematic ; (R*)-3-Bromo-5-((S*)-1-cyclohexyl-2-(1,3-dioxolan-2-yl)ethyl)furan-2(5H)-one ; _chemical_name_common ;(R*)-3-Bromo-5-((S*)-1-cyclohexyl-2-(1,3-dioxolan-2- yl)ethyl)furan-2(5H)-one ; _chemical_melting_point '99.5-101.5 C' _chemical_formula_moiety 'C15 H21 Br O4' _chemical_formula_sum 'C15 H21 Br O4' _chemical_formula_weight 345.23 _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_absolute_configuration . 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' #============================================================================== # CRYSTAL DATA #============================================================================== _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M 'C2/c ' _symmetry_space_group_name_Hall '-C 2yc' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 24.402(3) _cell_length_b 6.4509(7) _cell_length_c 20.012(2) _cell_angle_alpha 90.00 _cell_angle_beta 107.1560(10) _cell_angle_gamma 90.00 _cell_volume 3010.0(5) _cell_formula_units_Z 8 _cell_measurement_temperature 90 _cell_measurement_reflns_used 6105 _cell_measurement_theta_min 2.32 _cell_measurement_theta_max 27.62 _exptl_crystal_description Block _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.18 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.524 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1424 _exptl_absorpt_coefficient_mu 2.742 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.5281 _exptl_absorpt_correction_T_max 0.6440 _exptl_absorpt_process_details ; Crystal Faces plugin in Bruker APEX2 software ; _exptl_special_details ; ? ; #============================================================================== # EXPERIMENTAL DATA #============================================================================== _diffrn_ambient_temperature 90 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker TXS fine-focus rotating anode' _diffrn_radiation_monochromator 'Bruker Helios multilayer confocal mirror' _diffrn_measurement_device_type 'Bruker APEXII CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 8.333 _diffrn_reflns_number 16573 _diffrn_reflns_av_R_equivalents 0.0322 _diffrn_reflns_av_sigmaI/netI 0.0264 _diffrn_reflns_limit_h_min -31 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 1.75 _diffrn_reflns_theta_max 27.66 _reflns_number_total 3496 _reflns_number_gt 2846 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker AXS, 2006)' _computing_cell_refinement 'APEX2 (Bruker AXS, 2006)' _computing_data_reduction 'SAINT (Bruker AXS, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XSHEL (Bruker AXS,2002)' _computing_publication_material 'XCIF (Bruker AXS, 2001)' _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^)+(0.0297P)^2^+4.6826P] 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 3496 _refine_ls_number_parameters 181 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.0383 _refine_ls_R_factor_gt 0.0277 _refine_ls_wR_factor_ref 0.0700 _refine_ls_wR_factor_gt 0.0658 _refine_ls_goodness_of_fit_ref 1.068 _refine_ls_restrained_S_all 1.090 _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 Br1 Br 0.292467(8) 0.74596(3) 1.224135(10) 0.01896(7) Uani 1 1 d . A 1 O1 O 0.23069(6) 1.0045(2) 1.08058(8) 0.0203(3) Uani 1 1 d . A 1 O2 O 0.19418(6) 0.7149(2) 1.02180(7) 0.0152(3) Uani 1 1 d . A 1 O3 O 0.10229(7) 0.2933(2) 1.14846(8) 0.0230(3) Uani 1 1 d . A 1 O4 O 0.03098(6) 0.2491(2) 1.04676(8) 0.0217(3) Uani 1 1 d . A 1 C1 C 0.13437(8) 0.4047(3) 1.02013(10) 0.0128(4) Uani 1 1 d . A 1 H1 H 0.1383 0.2672 1.0419 0.015 Uiso 1 1 calc R A 1 C2 C 0.09752(8) 0.5335(3) 1.05523(10) 0.0148(4) Uani 1 1 d . A 1 H2A H 0.1222 0.6270 1.0889 0.018 Uiso 1 1 calc R A 1 H2B H 0.0708 0.6171 1.0200 0.018 Uiso 1 1 calc R A 1 C3 C 0.19539(8) 0.4925(3) 1.03624(10) 0.0131(4) Uani 1 1 d . A 1 H3 H 0.2156 0.4211 1.0073 0.016 Uiso 1 1 calc R A 1 C4 C 0.07124(9) 0.5167(3) 0.81864(10) 0.0198(4) Uani 1 1 d . A 1 H4A H 0.0313 0.4925 0.8153 0.024 Uiso 1 1 calc R A 1 H4B H 0.0732 0.6369 0.7903 0.024 Uiso 1 1 calc R A 1 C5 C 0.24669(8) 0.6647(3) 1.13569(10) 0.0142(4) Uani 1 1 d . A 1 C6 C 0.10492(8) 0.3703(3) 0.94130(10) 0.0140(4) Uani 1 1 d . A 1 H6 H 0.0646 0.3383 0.9363 0.017 Uiso 1 1 calc R A 1 C7 C 0.23023(8) 0.4765(3) 1.11167(10) 0.0144(4) Uani 1 1 d . A 1 H7 H 0.2388 0.3544 1.1373 0.017 Uiso 1 1 calc R A 1 C8 C 0.12951(9) 0.1825(3) 0.91286(11) 0.0196(4) Uani 1 1 d . A 1 H8A H 0.1695 0.2082 0.9167 0.023 Uiso 1 1 calc R A 1 H8B H 0.1277 0.0616 0.9410 0.023 Uiso 1 1 calc R A 1 C9 C 0.10504(9) 0.5599(3) 0.89491(10) 0.0170(4) Uani 1 1 d . A 1 H9A H 0.0882 0.6772 0.9119 0.020 Uiso 1 1 calc R A 1 H9B H 0.1443 0.5955 0.8977 0.020 Uiso 1 1 calc R A 1 C10 C 0.06425(9) 0.4017(3) 1.09199(10) 0.0180(4) Uani 1 1 d . A 1 H10 H 0.0390 0.4904 1.1097 0.022 Uiso 1 1 calc R A 1 C11 C 0.22470(8) 0.8196(3) 1.07946(10) 0.0151(4) Uani 1 1 d . A 1 C12 C 0.09514(10) 0.3277(4) 0.79036(11) 0.0215(4) Uani 1 1 d . A 1 H12A H 0.0714 0.2983 0.7432 0.026 Uiso 1 1 calc R A 1 H12B H 0.1336 0.3578 0.7886 0.026 Uiso 1 1 calc R A 1 C13 C 0.09655(10) 0.1385(3) 0.83650(11) 0.0223(5) Uani 1 1 d . A 1 H13A H 0.1146 0.0240 0.8196 0.027 Uiso 1 1 calc R A 1 H13B H 0.0576 0.0980 0.8334 0.027 Uiso 1 1 calc R A 1 C14 C 0.02972(13) 0.0754(4) 1.08868(15) 0.0442(7) Uani 1 1 d U A 1 H14A H 0.0345 -0.0509 1.0647 0.050 Uiso 1 1 calc R A 1 H14B H -0.0067 0.0684 1.0990 0.050 Uiso 1 1 calc R A 1 C15 C 0.07632(15) 0.0985(5) 1.15257(15) 0.0549(9) Uani 1 1 d U A 1 H15A H 0.0619 0.0947 1.1928 0.050 Uiso 1 1 calc R A 1 H15B H 0.1040 -0.0125 1.1570 0.050 Uiso 1 1 calc R A 1 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 0.02036(12) 0.02018(12) 0.01410(11) -0.00424(8) 0.00161(8) -0.00391(8) O1 0.0214(7) 0.0132(7) 0.0251(8) -0.0004(6) 0.0051(6) -0.0016(6) O2 0.0162(7) 0.0122(7) 0.0153(7) 0.0011(5) 0.0015(5) -0.0021(5) O3 0.0284(8) 0.0226(8) 0.0142(7) 0.0040(6) 0.0004(6) -0.0044(6) O4 0.0191(7) 0.0228(8) 0.0201(7) 0.0019(6) 0.0010(6) -0.0071(6) C1 0.0126(9) 0.0114(9) 0.0135(9) 0.0012(7) 0.0025(7) -0.0003(7) C2 0.0131(9) 0.0152(9) 0.0148(9) -0.0012(8) 0.0020(7) 0.0009(7) C3 0.0142(9) 0.0093(9) 0.0156(9) 0.0003(7) 0.0038(8) 0.0002(7) C4 0.0251(11) 0.0178(10) 0.0141(10) 0.0013(8) 0.0023(8) 0.0004(9) C5 0.0112(9) 0.0168(9) 0.0133(9) -0.0013(8) 0.0014(7) -0.0008(8) C6 0.0129(9) 0.0147(10) 0.0133(9) -0.0010(7) 0.0022(7) -0.0013(7) C7 0.0118(9) 0.0164(10) 0.0145(9) 0.0017(8) 0.0032(7) 0.0014(7) C8 0.0240(11) 0.0157(9) 0.0164(10) -0.0020(8) 0.0020(8) 0.0012(8) C9 0.0199(10) 0.0143(10) 0.0150(10) -0.0004(8) 0.0024(8) -0.0007(8) C10 0.0162(10) 0.0209(10) 0.0170(10) -0.0011(8) 0.0050(8) 0.0000(8) C11 0.0118(9) 0.0166(10) 0.0173(10) -0.0016(8) 0.0048(8) -0.0009(7) C12 0.0257(11) 0.0219(11) 0.0161(10) -0.0031(9) 0.0050(9) -0.0023(9) C13 0.0290(12) 0.0184(11) 0.0181(10) -0.0061(8) 0.0048(9) -0.0007(9) C14 0.0476(16) 0.0313(14) 0.0418(15) 0.0155(12) -0.0049(12) -0.0129(12) C15 0.081(2) 0.0360(15) 0.0314(14) 0.0100(12) -0.0084(14) -0.0288(15) _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 C5 1.8679(19) . ? O1 C11 1.201(3) . ? O2 C11 1.355(2) . ? O2 C3 1.463(2) . ? O3 C10 1.417(2) . ? O3 C15 1.421(3) . ? O4 C14 1.406(3) . ? O4 C10 1.419(2) . ? C1 C3 1.536(3) . ? C1 C2 1.538(3) . ? C1 C6 1.545(3) . ? C1 H1 0.9800 . ? C2 C10 1.509(3) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 C7 1.502(3) . ? C3 H3 0.9800 . ? C4 C12 1.530(3) . ? C4 C9 1.531(3) . ? C4 H4A 0.9700 . ? C4 H4B 0.9700 . ? C5 C7 1.324(3) . ? C5 C11 1.482(3) . ? C6 C8 1.534(3) . ? C6 C9 1.536(3) . ? C6 H6 0.9800 . ? C7 H7 0.9300 . ? C8 C13 1.529(3) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 H10 0.9800 . ? C12 C13 1.525(3) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C13 H13A 0.9700 . ? C13 H13B 0.9700 . ? C14 C15 1.447(4) . ? C14 H14A 0.9700 . ? C14 H14B 0.9700 . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? 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 C11 O2 C3 110.29(15) . . ? C10 O3 C15 106.50(18) . . ? C14 O4 C10 106.35(17) . . ? C3 C1 C2 111.48(16) . . ? C3 C1 C6 113.43(15) . . ? C2 C1 C6 112.68(16) . . ? C3 C1 H1 106.2 . . ? C2 C1 H1 106.2 . . ? C6 C1 H1 106.2 . . ? C10 C2 C1 112.92(17) . . ? C10 C2 H2A 109.0 . . ? C1 C2 H2A 109.0 . . ? C10 C2 H2B 109.0 . . ? C1 C2 H2B 109.0 . . ? H2A C2 H2B 107.8 . . ? O2 C3 C7 103.80(15) . . ? O2 C3 C1 111.01(15) . . ? C7 C3 C1 114.33(16) . . ? O2 C3 H3 109.2 . . ? C7 C3 H3 109.2 . . ? C1 C3 H3 109.2 . . ? C12 C4 C9 111.21(17) . . ? C12 C4 H4A 109.4 . . ? C9 C4 H4A 109.4 . . ? C12 C4 H4B 109.4 . . ? C9 C4 H4B 109.4 . . ? H4A C4 H4B 108.0 . . ? C7 C5 C11 109.85(17) . . ? C7 C5 Br1 129.34(16) . . ? C11 C5 Br1 120.78(15) . . ? C8 C6 C9 109.50(16) . . ? C8 C6 C1 112.17(16) . . ? C9 C6 C1 114.80(16) . . ? C8 C6 H6 106.6 . . ? C9 C6 H6 106.6 . . ? C1 C6 H6 106.6 . . ? C5 C7 C3 108.86(17) . . ? C5 C7 H7 125.6 . . ? C3 C7 H7 125.6 . . ? C13 C8 C6 111.67(17) . . ? C13 C8 H8A 109.3 . . ? C6 C8 H8A 109.3 . . ? C13 C8 H8B 109.3 . . ? C6 C8 H8B 109.3 . . ? H8A C8 H8B 107.9 . . ? C4 C9 C6 111.15(16) . . ? C4 C9 H9A 109.4 . . ? C6 C9 H9A 109.4 . . ? C4 C9 H9B 109.4 . . ? C6 C9 H9B 109.4 . . ? H9A C9 H9B 108.0 . . ? O3 C10 O4 106.46(16) . . ? O3 C10 C2 110.29(16) . . ? O4 C10 C2 111.64(16) . . ? O3 C10 H10 109.5 . . ? O4 C10 H10 109.5 . . ? C2 C10 H10 109.5 . . ? O1 C11 O2 122.97(19) . . ? O1 C11 C5 129.83(19) . . ? O2 C11 C5 107.20(17) . . ? C13 C12 C4 110.90(17) . . ? C13 C12 H12A 109.5 . . ? C4 C12 H12A 109.5 . . ? C13 C12 H12B 109.5 . . ? C4 C12 H12B 109.5 . . ? H12A C12 H12B 108.0 . . ? C12 C13 C8 111.60(18) . . ? C12 C13 H13A 109.3 . . ? C8 C13 H13A 109.3 . . ? C12 C13 H13B 109.3 . . ? C8 C13 H13B 109.3 . . ? H13A C13 H13B 108.0 . . ? O4 C14 C15 107.2(2) . . ? O4 C14 H14A 110.3 . . ? C15 C14 H14A 110.3 . . ? O4 C14 H14B 110.3 . . ? C15 C14 H14B 110.3 . . ? H14A C14 H14B 108.5 . . ? O3 C15 C14 106.7(2) . . ? O3 C15 H15A 110.4 . . ? C14 C15 H15A 110.4 . . ? O3 C15 H15B 110.4 . . ? C14 C15 H15B 110.4 . . ? H15A C15 H15B 108.6 . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 27.66 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.600 _refine_diff_density_min -0.409 _refine_diff_density_rms 0.068