# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Gang Zhao' _publ_contact_author_email ZHAOG@MAIL.SIOC.AC.CN _publ_section_title ; Highly enantio- and diastereoselective synthesis of ?-trifluoromethyldihydropyrans using a novel bifunctional piperazine-thiourea catalyst ; loop_ _publ_author_name 'Gang Zhao.' 'Yue-Peng Cai.' 'Zhuo Chai.' 'Xiao He.' 'Peng Li.' ; Hai-Feng Wang ; 'Ying-Quan Yang.' 'Sheng-Li Zhao.' 'Chang-Wu Zheng.' 'Shi-Zheng Zhu.' # Attachment 'c.cif' data_c _database_code_depnum_ccdc_archive 'CCDC 738397' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_absolute_configuration rm _chemical_melting_point ? _chemical_formula_moiety 'C40 H30 Br2 F6 N2 O4' _chemical_formula_sum 'C40 H30 Br2 F6 N2 O4' _chemical_formula_weight 876.48 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' N N 0.0061 0.0033 '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' 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 P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 12.306(2) _cell_length_b 11.433(2) _cell_length_c 14.660(3) _cell_angle_alpha 90.00 _cell_angle_beta 112.875(2) _cell_angle_gamma 90.00 _cell_volume 1900.4(6) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 2054 _cell_measurement_theta_min 2.33 _cell_measurement_theta_max 20.18 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.532 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 880 _exptl_absorpt_coefficient_mu 2.206 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5978 _exptl_absorpt_correction_T_max 0.7192 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _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 10058 _diffrn_reflns_av_R_equivalents 0.0297 _diffrn_reflns_av_sigmaI/netI 0.1038 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 1.84 _diffrn_reflns_theta_max 25.50 _reflns_number_total 6887 _reflns_number_gt 4235 _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^)+(0.0089P)^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 0.006(9) _refine_ls_number_reflns 6887 _refine_ls_number_parameters 491 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0945 _refine_ls_R_factor_gt 0.0468 _refine_ls_wR_factor_ref 0.1109 _refine_ls_wR_factor_gt 0.0927 _refine_ls_goodness_of_fit_ref 0.941 _refine_ls_restrained_S_all 0.941 _refine_ls_shift/su_max 0.002 _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 Br1 Br -0.39629(7) 0.66737(5) -0.02720(5) 0.0882(3) Uani 1 1 d . . . Br2 Br 1.54540(6) 0.98448(7) 0.84486(6) 0.0954(3) Uani 1 1 d . . . F1 F -0.1728(4) 0.0229(4) 0.3004(3) 0.0900(12) Uani 1 1 d . . . F2 F -0.1937(4) -0.1453(3) 0.2328(3) 0.1000(13) Uani 1 1 d . . . F3 F -0.3305(3) -0.0179(4) 0.1773(3) 0.0921(11) Uani 1 1 d . . . F4 F 0.8442(4) 1.0452(4) 0.8020(3) 0.0946(12) Uani 1 1 d . . . F5 F 0.7029(3) 1.1406(3) 0.6958(3) 0.0938(12) Uani 1 1 d . . . F6 F 0.8763(3) 1.2119(3) 0.7508(3) 0.0930(12) Uani 1 1 d . . . O1 O -0.2103(3) -0.0461(3) 0.0547(3) 0.0602(10) Uani 1 1 d . . . H1 H -0.1654 -0.0961 0.0493 0.090 Uiso 1 1 calc R . . O2 O -0.1930(3) 0.1308(3) 0.1302(2) 0.0488(9) Uani 1 1 d . . . O3 O 0.8065(3) 1.1265(3) 0.5584(3) 0.0578(10) Uani 1 1 d . . . H3 H 0.8636 1.1659 0.5617 0.087 Uiso 1 1 calc R . . O4 O 0.9629(3) 1.0352(3) 0.6821(2) 0.0436(8) Uani 1 1 d . . . N1 N 0.0567(4) 0.2905(4) -0.0184(3) 0.0616(13) Uani 1 1 d . . . N2 N 1.0320(4) 0.7885(4) 0.4492(4) 0.0665(14) Uani 1 1 d . . . C1 C 0.5385(4) 0.0811(5) 0.3500(4) 0.0533(15) Uani 1 1 d . . . H1A H 0.5542 0.0694 0.4188 0.080 Uiso 1 1 calc R . . H1B H 0.5696 0.1554 0.3414 0.080 Uiso 1 1 calc R . . H1C H 0.5754 0.0199 0.3274 0.080 Uiso 1 1 calc R . . C2 C 0.4071(5) 0.0786(5) 0.2910(4) 0.0517(14) Uani 1 1 d . . . C3 C 0.3511(5) -0.0233(5) 0.2497(4) 0.0565(14) Uani 1 1 d . . . H3A H 0.3958 -0.0912 0.2597 0.068 Uiso 1 1 calc R . . C4 C 0.2326(5) -0.0301(4) 0.1943(4) 0.0512(13) Uani 1 1 d . . . H4 H 0.1996 -0.1010 0.1660 0.061 Uiso 1 1 calc R . . C5 C 0.1615(4) 0.0672(4) 0.1800(3) 0.0400(12) Uani 1 1 d . . . C6 C 0.2162(5) 0.1719(5) 0.2213(3) 0.0488(12) Uani 1 1 d . . . H6 H 0.1716 0.2398 0.2119 0.059 Uiso 1 1 calc R . . C7 C 0.3349(5) 0.1757(5) 0.2757(4) 0.0546(14) Uani 1 1 d . . . H7 H 0.3687 0.2466 0.3036 0.066 Uiso 1 1 calc R . . C8 C 0.0300(4) 0.0570(4) 0.1245(3) 0.0442(12) Uani 1 1 d . . . H8 H 0.0167 0.0031 0.0693 0.053 Uiso 1 1 calc R . . C9 C -0.0264(4) 0.0026(4) 0.1898(3) 0.0397(11) Uani 1 1 d . . . H9A H -0.0030 -0.0789 0.2014 0.048 Uiso 1 1 calc R . . H9B H 0.0025 0.0422 0.2533 0.048 Uiso 1 1 calc R . . C10 C -0.1579(5) 0.0099(4) 0.1448(4) 0.0456(12) Uani 1 1 d . . . C11 C -0.2141(5) -0.0329(5) 0.2140(5) 0.0623(16) Uani 1 1 d . . . C12 C -0.1341(5) 0.2003(4) 0.0885(3) 0.0433(13) Uani 1 1 d . . . C13 C -0.0341(4) 0.1687(4) 0.0812(3) 0.0374(11) Uani 1 1 d . . . C14 C 0.0142(5) 0.2390(4) 0.0269(4) 0.0466(13) Uani 1 1 d . . . C15 C -0.1987(5) 0.3132(4) 0.0560(3) 0.0433(12) Uani 1 1 d . . . C16 C -0.3176(5) 0.3152(4) 0.0072(4) 0.0503(13) Uani 1 1 d . . . H16 H -0.3588 0.2450 -0.0089 0.060 Uiso 1 1 calc R . . C17 C -0.3794(5) 0.4200(5) -0.0192(4) 0.0635(16) Uani 1 1 d . . . H17 H -0.4608 0.4207 -0.0533 0.076 Uiso 1 1 calc R . . C18 C -0.3154(5) 0.5238(5) 0.0071(4) 0.0527(14) Uani 1 1 d . . . C19 C -0.1961(5) 0.5235(4) 0.0565(4) 0.0497(13) Uani 1 1 d . . . H19 H -0.1548 0.5936 0.0735 0.060 Uiso 1 1 calc R . . C20 C -0.1374(5) 0.4185(4) 0.0812(4) 0.0463(13) Uani 1 1 d . . . H20 H -0.0559 0.4179 0.1150 0.056 Uiso 1 1 calc R . . C21 C 0.6148(7) 0.4116(5) 0.4799(5) 0.087(2) Uani 1 1 d . . . H21A H 0.5809 0.4021 0.5284 0.131 Uiso 1 1 calc R . . H21B H 0.6757 0.3544 0.4909 0.131 Uiso 1 1 calc R . . H21C H 0.5547 0.4013 0.4149 0.131 Uiso 1 1 calc R . . C22 C 0.6660(6) 0.5310(5) 0.4885(4) 0.0546(15) Uani 1 1 d . . . C23 C 0.5981(5) 0.6244(5) 0.4431(5) 0.0645(17) Uani 1 1 d . . . H23 H 0.5184 0.6131 0.4049 0.077 Uiso 1 1 calc R . . C24 C 0.6453(5) 0.7363(5) 0.4526(4) 0.0592(15) Uani 1 1 d . . . H24 H 0.5971 0.7984 0.4196 0.071 Uiso 1 1 calc R . . C25 C 0.7630(5) 0.7568(4) 0.5103(4) 0.0426(13) Uani 1 1 d . . . C26 C 0.8325(5) 0.6626(5) 0.5562(3) 0.0536(14) Uani 1 1 d . . . H26 H 0.9123 0.6731 0.5944 0.064 Uiso 1 1 calc R . . C27 C 0.7824(5) 0.5519(5) 0.5450(4) 0.0524(14) Uani 1 1 d . . . H27 H 0.8301 0.4893 0.5774 0.063 Uiso 1 1 calc R . . C28 C 0.8088(4) 0.8827(4) 0.5275(4) 0.0410(12) Uani 1 1 d . . . H28 H 0.7701 0.9264 0.4658 0.049 Uiso 1 1 calc R . . C29 C 0.7753(5) 0.9391(4) 0.6073(4) 0.0468(13) Uani 1 1 d . . . H29A H 0.6908 0.9519 0.5818 0.056 Uiso 1 1 calc R . . H29B H 0.7965 0.8875 0.6640 0.056 Uiso 1 1 calc R . . C30 C 0.8382(4) 1.0532(4) 0.6381(4) 0.0449(13) Uani 1 1 d . . . C31 C 0.8158(6) 1.1137(6) 0.7238(5) 0.0651(17) Uani 1 1 d . . . C32 C 1.0093(4) 0.9609(4) 0.6337(3) 0.0383(11) Uani 1 1 d . . . C33 C 0.9397(4) 0.8936(4) 0.5578(3) 0.0405(12) Uani 1 1 d . . . C34 C 0.9940(5) 0.8344(4) 0.4994(4) 0.0479(13) Uani 1 1 d . . . C35 C 1.1388(4) 0.9662(4) 0.6768(3) 0.0394(11) Uani 1 1 d . . . C36 C 1.1954(5) 1.0732(4) 0.7040(4) 0.0484(14) Uani 1 1 d . . . H36 H 1.1508 1.1414 0.6908 0.058 Uiso 1 1 calc R . . C37 C 1.3153(5) 1.0802(5) 0.7497(4) 0.0530(14) Uani 1 1 d . . . H37 H 1.3523 1.1527 0.7644 0.064 Uiso 1 1 calc R . . C38 C 1.3805(4) 0.9790(5) 0.7738(4) 0.0526(13) Uani 1 1 d . . . C39 C 1.3267(5) 0.8714(5) 0.7488(4) 0.0582(15) Uani 1 1 d . . . H39 H 1.3719 0.8035 0.7646 0.070 Uiso 1 1 calc R . . C40 C 1.2062(5) 0.8643(4) 0.7005(4) 0.0504(14) Uani 1 1 d . . . H40 H 1.1698 0.7918 0.6836 0.060 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 Br1 0.1075(6) 0.0584(4) 0.1077(5) 0.0200(4) 0.0514(5) 0.0375(4) Br2 0.0393(3) 0.1110(6) 0.1153(6) -0.0065(5) 0.0074(3) 0.0055(4) F1 0.099(3) 0.115(3) 0.070(2) 0.011(2) 0.048(2) -0.008(3) F2 0.105(3) 0.064(2) 0.139(3) 0.040(2) 0.056(3) -0.006(2) F3 0.054(2) 0.108(3) 0.122(3) 0.024(3) 0.043(2) -0.004(2) F4 0.115(3) 0.113(3) 0.074(2) -0.003(2) 0.056(2) 0.013(3) F5 0.053(2) 0.104(3) 0.133(3) -0.032(3) 0.045(2) 0.009(2) F6 0.078(3) 0.077(2) 0.135(3) -0.058(2) 0.052(2) -0.014(2) O1 0.044(2) 0.053(2) 0.071(2) -0.0120(19) 0.0080(19) 0.0000(18) O2 0.053(2) 0.036(2) 0.066(2) 0.0063(16) 0.0316(19) 0.0050(17) O3 0.049(2) 0.046(2) 0.068(2) 0.0113(18) 0.012(2) -0.0028(18) O4 0.036(2) 0.0470(19) 0.0465(19) -0.0086(15) 0.0139(17) 0.0051(16) N1 0.070(4) 0.051(3) 0.072(3) 0.016(2) 0.037(3) 0.010(3) N2 0.060(3) 0.069(3) 0.075(3) -0.022(3) 0.031(3) 0.005(3) C1 0.024(3) 0.068(4) 0.061(3) 0.012(3) 0.009(3) -0.007(3) C2 0.043(3) 0.057(4) 0.054(3) 0.003(3) 0.018(3) -0.006(3) C3 0.052(3) 0.053(3) 0.061(3) 0.012(3) 0.018(3) 0.018(3) C4 0.063(4) 0.036(3) 0.051(3) 0.000(3) 0.019(3) 0.000(3) C5 0.045(3) 0.037(3) 0.037(3) 0.001(2) 0.014(2) 0.004(3) C6 0.046(3) 0.044(3) 0.052(3) -0.010(3) 0.013(3) 0.000(3) C7 0.046(4) 0.049(3) 0.064(3) 0.002(3) 0.015(3) -0.006(3) C8 0.042(3) 0.039(3) 0.046(3) 0.000(2) 0.011(2) 0.003(3) C9 0.044(3) 0.031(2) 0.043(3) 0.001(2) 0.016(2) -0.006(2) C10 0.045(3) 0.039(3) 0.050(3) 0.001(2) 0.015(3) 0.001(2) C11 0.052(4) 0.061(4) 0.073(4) 0.021(3) 0.023(3) -0.002(3) C12 0.051(4) 0.031(3) 0.045(3) 0.002(2) 0.015(3) 0.000(2) C13 0.037(3) 0.034(2) 0.042(3) 0.001(2) 0.015(2) -0.003(3) C14 0.048(4) 0.041(3) 0.053(3) 0.006(3) 0.022(3) 0.010(3) C15 0.053(4) 0.034(3) 0.048(3) 0.006(2) 0.024(3) 0.009(3) C16 0.045(4) 0.040(3) 0.063(3) -0.003(3) 0.018(3) -0.001(3) C17 0.051(4) 0.069(4) 0.066(4) 0.013(3) 0.018(3) 0.019(3) C18 0.057(4) 0.046(3) 0.063(4) 0.008(3) 0.032(3) 0.018(3) C19 0.057(4) 0.038(3) 0.063(3) 0.000(3) 0.033(3) 0.000(3) C20 0.045(3) 0.043(3) 0.052(3) -0.005(2) 0.021(3) 0.001(3) C21 0.101(6) 0.058(4) 0.115(6) -0.023(4) 0.056(5) -0.026(4) C22 0.065(4) 0.044(3) 0.062(3) -0.015(3) 0.033(3) -0.017(3) C23 0.042(4) 0.061(4) 0.085(4) -0.016(3) 0.019(3) -0.014(3) C24 0.048(4) 0.051(4) 0.067(4) -0.001(3) 0.009(3) 0.004(3) C25 0.043(3) 0.042(3) 0.044(3) -0.003(2) 0.018(3) 0.000(3) C26 0.049(4) 0.047(3) 0.056(3) 0.005(3) 0.011(3) -0.005(3) C27 0.067(4) 0.037(3) 0.052(3) 0.002(3) 0.021(3) 0.001(3) C28 0.038(3) 0.033(3) 0.054(3) 0.006(2) 0.019(3) 0.004(2) C29 0.049(3) 0.037(3) 0.059(3) -0.002(2) 0.026(3) -0.005(2) C30 0.037(3) 0.041(3) 0.050(3) 0.001(3) 0.010(3) 0.002(2) C31 0.056(4) 0.060(4) 0.087(5) -0.013(4) 0.035(4) 0.011(3) C32 0.042(3) 0.031(3) 0.043(3) 0.003(2) 0.017(2) 0.001(2) C33 0.036(3) 0.038(3) 0.050(3) -0.001(2) 0.019(3) 0.004(2) C34 0.041(3) 0.042(3) 0.054(3) -0.009(3) 0.011(3) -0.008(3) C35 0.034(3) 0.043(3) 0.043(3) 0.002(2) 0.016(2) 0.002(3) C36 0.043(4) 0.046(3) 0.057(3) 0.002(3) 0.019(3) 0.003(3) C37 0.044(4) 0.050(3) 0.057(3) 0.000(3) 0.011(3) -0.006(3) C38 0.036(3) 0.067(4) 0.049(3) 0.004(3) 0.010(2) 0.003(3) C39 0.048(4) 0.063(4) 0.058(4) 0.003(3) 0.014(3) 0.015(3) C40 0.054(4) 0.042(3) 0.055(3) 0.005(3) 0.021(3) 0.002(3) _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 C18 1.884(5) . ? Br2 C38 1.888(5) . ? F1 C11 1.330(7) . ? F2 C11 1.318(7) . ? F3 C11 1.331(6) . ? F4 C31 1.319(7) . ? F5 C31 1.323(7) . ? F6 C31 1.320(7) . ? O1 C10 1.381(5) . ? O1 H1 0.8200 . ? O2 C12 1.370(6) . ? O2 C10 1.439(6) . ? O3 C30 1.366(5) . ? O3 H3 0.8200 . ? O4 C32 1.366(5) . ? O4 C30 1.430(5) . ? N1 C14 1.154(6) . ? N2 C34 1.141(6) . ? C1 C2 1.509(7) . ? C1 H1A 0.9600 . ? C1 H1B 0.9600 . ? C1 H1C 0.9600 . ? C2 C3 1.369(7) . ? C2 C7 1.384(7) . ? C3 C4 1.368(7) . ? C3 H3A 0.9300 . ? C4 C5 1.379(7) . ? C4 H4 0.9300 . ? C5 C6 1.392(7) . ? C5 C8 1.507(7) . ? C6 C7 1.365(7) . ? C6 H6 0.9300 . ? C7 H7 0.9300 . ? C8 C13 1.506(7) . ? C8 C9 1.516(6) . ? C8 H8 0.9800 . ? C9 C10 1.495(6) . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C10 C11 1.513(7) . ? C12 C13 1.327(7) . ? C12 C15 1.493(7) . ? C13 C14 1.414(7) . ? C15 C16 1.357(7) . ? C15 C20 1.392(7) . ? C16 C17 1.390(7) . ? C16 H16 0.9300 . ? C17 C18 1.393(8) . ? C17 H17 0.9300 . ? C18 C19 1.361(7) . ? C19 C20 1.375(7) . ? C19 H19 0.9300 . ? C20 H20 0.9300 . ? C21 C22 1.488(8) . ? C21 H21A 0.9600 . ? C21 H21B 0.9600 . ? C21 H21C 0.9600 . ? C22 C23 1.359(8) . ? C22 C27 1.369(8) . ? C23 C24 1.390(8) . ? C23 H23 0.9300 . ? C24 C25 1.384(7) . ? C24 H24 0.9300 . ? C25 C26 1.377(7) . ? C25 C28 1.531(6) . ? C26 C27 1.389(7) . ? C26 H26 0.9300 . ? C27 H27 0.9300 . ? C28 C33 1.500(7) . ? C28 C29 1.526(6) . ? C28 H28 0.9800 . ? C29 C30 1.494(6) . ? C29 H29A 0.9700 . ? C29 H29B 0.9700 . ? C30 C31 1.548(8) . ? C32 C33 1.350(6) . ? C32 C35 1.469(6) . ? C33 C34 1.443(7) . ? C35 C36 1.387(7) . ? C35 C40 1.393(7) . ? C36 C37 1.365(8) . ? C36 H36 0.9300 . ? C37 C38 1.374(7) . ? C37 H37 0.9300 . ? C38 C39 1.378(8) . ? C39 C40 1.375(8) . ? C39 H39 0.9300 . ? C40 H40 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 C10 O1 H1 109.5 . . ? C12 O2 C10 116.4(4) . . ? C30 O3 H3 109.5 . . ? C32 O4 C30 116.6(4) . . ? C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? C3 C2 C7 115.4(5) . . ? C3 C2 C1 120.8(5) . . ? C7 C2 C1 123.7(5) . . ? C4 C3 C2 123.2(5) . . ? C4 C3 H3A 118.4 . . ? C2 C3 H3A 118.4 . . ? C3 C4 C5 120.7(5) . . ? C3 C4 H4 119.6 . . ? C5 C4 H4 119.6 . . ? C4 C5 C6 117.2(5) . . ? C4 C5 C8 120.3(4) . . ? C6 C5 C8 122.5(4) . . ? C7 C6 C5 120.5(5) . . ? C7 C6 H6 119.7 . . ? C5 C6 H6 119.7 . . ? C6 C7 C2 122.9(5) . . ? C6 C7 H7 118.6 . . ? C2 C7 H7 118.6 . . ? C13 C8 C5 116.0(4) . . ? C13 C8 C9 108.7(4) . . ? C5 C8 C9 110.5(4) . . ? C13 C8 H8 107.1 . . ? C5 C8 H8 107.1 . . ? C9 C8 H8 107.1 . . ? C10 C9 C8 112.5(4) . . ? C10 C9 H9A 109.1 . . ? C8 C9 H9A 109.1 . . ? C10 C9 H9B 109.1 . . ? C8 C9 H9B 109.1 . . ? H9A C9 H9B 107.8 . . ? O1 C10 O2 107.5(4) . . ? O1 C10 C9 114.7(4) . . ? O2 C10 C9 109.3(4) . . ? O1 C10 C11 109.0(4) . . ? O2 C10 C11 102.8(4) . . ? C9 C10 C11 112.6(4) . . ? F2 C11 F1 107.3(5) . . ? F2 C11 F3 107.4(5) . . ? F1 C11 F3 106.0(5) . . ? F2 C11 C10 110.9(5) . . ? F1 C11 C10 112.2(5) . . ? F3 C11 C10 112.7(5) . . ? C13 C12 O2 123.1(4) . . ? C13 C12 C15 127.2(5) . . ? O2 C12 C15 109.7(4) . . ? C12 C13 C14 119.8(5) . . ? C12 C13 C8 123.2(4) . . ? C14 C13 C8 117.0(4) . . ? N1 C14 C13 175.9(5) . . ? C16 C15 C20 119.1(5) . . ? C16 C15 C12 120.9(5) . . ? C20 C15 C12 119.8(5) . . ? C15 C16 C17 121.5(5) . . ? C15 C16 H16 119.3 . . ? C17 C16 H16 119.3 . . ? C16 C17 C18 117.9(5) . . ? C16 C17 H17 121.0 . . ? C18 C17 H17 121.0 . . ? C19 C18 C17 121.5(5) . . ? C19 C18 Br1 119.5(4) . . ? C17 C18 Br1 119.0(4) . . ? C18 C19 C20 119.3(5) . . ? C18 C19 H19 120.3 . . ? C20 C19 H19 120.3 . . ? C19 C20 C15 120.7(5) . . ? C19 C20 H20 119.7 . . ? C15 C20 H20 119.7 . . ? C22 C21 H21A 109.5 . . ? C22 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C22 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C23 C22 C27 117.3(5) . . ? C23 C22 C21 121.3(6) . . ? C27 C22 C21 121.4(6) . . ? C22 C23 C24 121.4(6) . . ? C22 C23 H23 119.3 . . ? C24 C23 H23 119.3 . . ? C25 C24 C23 120.9(5) . . ? C25 C24 H24 119.6 . . ? C23 C24 H24 119.6 . . ? C26 C25 C24 118.1(5) . . ? C26 C25 C28 122.4(5) . . ? C24 C25 C28 119.4(5) . . ? C25 C26 C27 119.5(5) . . ? C25 C26 H26 120.3 . . ? C27 C26 H26 120.3 . . ? C22 C27 C26 122.8(5) . . ? C22 C27 H27 118.6 . . ? C26 C27 H27 118.6 . . ? C33 C28 C29 108.5(4) . . ? C33 C28 C25 114.3(4) . . ? C29 C28 C25 109.4(4) . . ? C33 C28 H28 108.2 . . ? C29 C28 H28 108.2 . . ? C25 C28 H28 108.2 . . ? C30 C29 C28 109.8(4) . . ? C30 C29 H29A 109.7 . . ? C28 C29 H29A 109.7 . . ? C30 C29 H29B 109.7 . . ? C28 C29 H29B 109.7 . . ? H29A C29 H29B 108.2 . . ? O3 C30 O4 111.9(4) . . ? O3 C30 C29 109.5(4) . . ? O4 C30 C29 110.5(4) . . ? O3 C30 C31 109.8(4) . . ? O4 C30 C31 101.4(4) . . ? C29 C30 C31 113.6(5) . . ? F4 C31 F6 108.4(6) . . ? F4 C31 F5 107.4(6) . . ? F6 C31 F5 107.2(5) . . ? F4 C31 C30 111.7(5) . . ? F6 C31 C30 111.5(5) . . ? F5 C31 C30 110.4(5) . . ? C33 C32 O4 121.5(4) . . ? C33 C32 C35 127.8(4) . . ? O4 C32 C35 110.7(4) . . ? C32 C33 C34 117.7(5) . . ? C32 C33 C28 123.8(4) . . ? C34 C33 C28 118.5(4) . . ? N2 C34 C33 176.7(6) . . ? C36 C35 C40 118.8(4) . . ? C36 C35 C32 120.0(4) . . ? C40 C35 C32 120.9(5) . . ? C37 C36 C35 121.3(5) . . ? C37 C36 H36 119.4 . . ? C35 C36 H36 119.4 . . ? C36 C37 C38 119.2(5) . . ? C36 C37 H37 120.4 . . ? C38 C37 H37 120.4 . . ? C37 C38 C39 120.8(5) . . ? C37 C38 Br2 120.6(4) . . ? C39 C38 Br2 118.6(4) . . ? C40 C39 C38 120.0(5) . . ? C40 C39 H39 120.0 . . ? C38 C39 H39 120.0 . . ? C39 C40 C35 119.9(5) . . ? C39 C40 H40 120.1 . . ? C35 C40 H40 120.1 . . ? 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 C7 C2 C3 C4 1.9(8) . . . . ? C1 C2 C3 C4 -179.0(5) . . . . ? C2 C3 C4 C5 -2.3(8) . . . . ? C3 C4 C5 C6 2.0(7) . . . . ? C3 C4 C5 C8 -176.0(4) . . . . ? C4 C5 C6 C7 -1.6(7) . . . . ? C8 C5 C6 C7 176.3(4) . . . . ? C5 C6 C7 C2 1.4(8) . . . . ? C3 C2 C7 C6 -1.4(8) . . . . ? C1 C2 C7 C6 179.5(5) . . . . ? C4 C5 C8 C13 -158.9(4) . . . . ? C6 C5 C8 C13 23.2(7) . . . . ? C4 C5 C8 C9 76.8(5) . . . . ? C6 C5 C8 C9 -101.1(5) . . . . ? C13 C8 C9 C10 41.5(5) . . . . ? C5 C8 C9 C10 169.9(4) . . . . ? C12 O2 C10 O1 -79.2(5) . . . . ? C12 O2 C10 C9 46.0(5) . . . . ? C12 O2 C10 C11 165.8(4) . . . . ? C8 C9 C10 O1 60.3(5) . . . . ? C8 C9 C10 O2 -60.5(5) . . . . ? C8 C9 C10 C11 -174.1(4) . . . . ? O1 C10 C11 F2 64.0(6) . . . . ? O2 C10 C11 F2 177.9(5) . . . . ? C9 C10 C11 F2 -64.7(6) . . . . ? O1 C10 C11 F1 -176.1(4) . . . . ? O2 C10 C11 F1 -62.2(6) . . . . ? C9 C10 C11 F1 55.3(6) . . . . ? O1 C10 C11 F3 -56.5(6) . . . . ? O2 C10 C11 F3 57.5(6) . . . . ? C9 C10 C11 F3 174.9(5) . . . . ? C10 O2 C12 C13 -14.6(7) . . . . ? C10 O2 C12 C15 166.4(4) . . . . ? O2 C12 C13 C14 172.6(4) . . . . ? C15 C12 C13 C14 -8.5(8) . . . . ? O2 C12 C13 C8 -4.6(7) . . . . ? C15 C12 C13 C8 174.3(5) . . . . ? C5 C8 C13 C12 -134.9(5) . . . . ? C9 C8 C13 C12 -9.7(6) . . . . ? C5 C8 C13 C14 47.8(6) . . . . ? C9 C8 C13 C14 173.1(4) . . . . ? C12 C13 C14 N1 -153(8) . . . . ? C8 C13 C14 N1 25(8) . . . . ? C13 C12 C15 C16 136.6(6) . . . . ? O2 C12 C15 C16 -44.4(6) . . . . ? C13 C12 C15 C20 -47.4(7) . . . . ? O2 C12 C15 C20 131.6(5) . . . . ? C20 C15 C16 C17 0.8(8) . . . . ? C12 C15 C16 C17 176.8(5) . . . . ? C15 C16 C17 C18 -0.8(8) . . . . ? C16 C17 C18 C19 0.3(8) . . . . ? C16 C17 C18 Br1 -179.8(4) . . . . ? C17 C18 C19 C20 0.0(8) . . . . ? Br1 C18 C19 C20 -179.8(4) . . . . ? C18 C19 C20 C15 0.1(7) . . . . ? C16 C15 C20 C19 -0.5(7) . . . . ? C12 C15 C20 C19 -176.5(4) . . . . ? C27 C22 C23 C24 0.9(9) . . . . ? C21 C22 C23 C24 178.7(6) . . . . ? C22 C23 C24 C25 -1.3(10) . . . . ? C23 C24 C25 C26 1.5(9) . . . . ? C23 C24 C25 C28 -173.8(5) . . . . ? C24 C25 C26 C27 -1.4(7) . . . . ? C28 C25 C26 C27 173.8(5) . . . . ? C23 C22 C27 C26 -0.8(8) . . . . ? C21 C22 C27 C26 -178.7(5) . . . . ? C25 C26 C27 C22 1.1(8) . . . . ? C26 C25 C28 C33 26.0(7) . . . . ? C24 C25 C28 C33 -158.9(5) . . . . ? C26 C25 C28 C29 -95.8(5) . . . . ? C24 C25 C28 C29 79.3(6) . . . . ? C33 C28 C29 C30 44.2(5) . . . . ? C25 C28 C29 C30 169.5(4) . . . . ? C32 O4 C30 O3 -76.6(5) . . . . ? C32 O4 C30 C29 45.7(5) . . . . ? C32 O4 C30 C31 166.5(4) . . . . ? C28 C29 C30 O3 60.5(5) . . . . ? C28 C29 C30 O4 -63.2(5) . . . . ? C28 C29 C30 C31 -176.4(4) . . . . ? O3 C30 C31 F4 179.3(5) . . . . ? O4 C30 C31 F4 -62.2(6) . . . . ? C29 C30 C31 F4 56.3(7) . . . . ? O3 C30 C31 F6 -59.2(6) . . . . ? O4 C30 C31 F6 59.3(6) . . . . ? C29 C30 C31 F6 177.8(5) . . . . ? O3 C30 C31 F5 59.9(6) . . . . ? O4 C30 C31 F5 178.4(5) . . . . ? C29 C30 C31 F5 -63.1(6) . . . . ? C30 O4 C32 C33 -10.4(6) . . . . ? C30 O4 C32 C35 170.2(4) . . . . ? O4 C32 C33 C34 168.7(4) . . . . ? C35 C32 C33 C34 -12.1(7) . . . . ? O4 C32 C33 C28 -7.5(7) . . . . ? C35 C32 C33 C28 171.7(4) . . . . ? C29 C28 C33 C32 -10.9(6) . . . . ? C25 C28 C33 C32 -133.1(5) . . . . ? C29 C28 C33 C34 172.9(4) . . . . ? C25 C28 C33 C34 50.6(6) . . . . ? C32 C33 C34 N2 -144(9) . . . . ? C28 C33 C34 N2 33(9) . . . . ? C33 C32 C35 C36 139.5(5) . . . . ? O4 C32 C35 C36 -41.3(6) . . . . ? C33 C32 C35 C40 -47.2(7) . . . . ? O4 C32 C35 C40 132.1(4) . . . . ? C40 C35 C36 C37 2.5(7) . . . . ? C32 C35 C36 C37 176.0(5) . . . . ? C35 C36 C37 C38 -3.4(8) . . . . ? C36 C37 C38 C39 2.6(8) . . . . ? C36 C37 C38 Br2 -175.7(4) . . . . ? C37 C38 C39 C40 -0.9(8) . . . . ? Br2 C38 C39 C40 177.4(4) . . . . ? C38 C39 C40 C35 0.0(8) . . . . ? C36 C35 C40 C39 -0.8(7) . . . . ? C32 C35 C40 C39 -174.2(5) . . . . ? 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 O3 H3 N2 0.82 1.95 2.751(6) 165.2 2_756 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.50 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.420 _refine_diff_density_min -0.307 _refine_diff_density_rms 0.051