# 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 'Xiaoming Feng' _publ_contact_author_email XMFENG@SCU.EDU.CN _publ_section_title ; Highly Enantioselective Aza-ene-type Reaction Catalyzed by Chiral N,N'-Dioxide-Nickel(II) Complex: Enamides and Enecarbamates as Nucleophiles ; loop_ _publ_author_name 'Xiaoming Feng' 'Lili Lin' 'Xiaohua Liu' 'Yang Yang' 'Jiannan Zhao' ; Ke Zheng ; # Attachment 'zhke2nk2.cif' data_zhke2nk2 _database_code_depnum_ccdc_archive 'CCDC 739905' #TrackingRef 'zhke2nk2.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C44 H69 B2 F8 N4 Ni O6' _chemical_formula_weight 982.36 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' B B 0.0013 0.0007 '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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 12.784(3) _cell_length_b 13.268(3) _cell_length_c 34.336(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 5824(2) _cell_formula_units_Z 4 _cell_measurement_temperature 113(2) _cell_measurement_reflns_used 11829 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 26.0 _exptl_crystal_description block _exptl_crystal_colour green _exptl_crystal_size_max 0.52 _exptl_crystal_size_mid 0.46 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 0.922 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1748 _exptl_absorpt_coefficient_mu 0.370 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8307 _exptl_absorpt_correction_T_max 0.8660 _exptl_absorpt_process_details CrystalClear _exptl_special_details ; ? ; _diffrn_ambient_temperature 113(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator confocal _diffrn_measurement_device_type 'Rigaku Saturn CCD area detector' _diffrn_measurement_method '\w and \f scans' _diffrn_detector_area_resol_mean 7.31 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 37884 _diffrn_reflns_av_R_equivalents 0.0526 _diffrn_reflns_av_sigmaI/netI 0.0648 _diffrn_reflns_limit_h_min -15 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -42 _diffrn_reflns_limit_l_max 42 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 26.04 _reflns_number_total 11378 _reflns_number_gt 8925 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear(Rigaku/MSC Inc.,2005)' _computing_cell_refinement CrystalClear _computing_data_reduction CrystalClear _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^)+(0.1379P)^2^+0.4484P] 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 SHELXL _refine_ls_extinction_coef 0.0072(11) _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 0.088(19) _chemical_absolute_configuration ad _refine_ls_number_reflns 11378 _refine_ls_number_parameters 599 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0936 _refine_ls_R_factor_gt 0.0784 _refine_ls_wR_factor_ref 0.2286 _refine_ls_wR_factor_gt 0.2144 _refine_ls_goodness_of_fit_ref 1.048 _refine_ls_restrained_S_all 1.048 _refine_ls_shift/su_max 4.123 _refine_ls_shift/su_mean 0.007 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 Ni1 Ni 0.46580(5) 0.47394(4) 0.386039(17) 0.0568(2) Uani 1 1 d . . . O1 O 0.5680(3) 0.5170(2) 0.42843(10) 0.0601(8) Uani 1 1 d . . . O2 O 0.4196(3) 0.6143(3) 0.37679(9) 0.0603(8) Uani 1 1 d . . . O3 O 0.5852(3) 0.4703(3) 0.34857(9) 0.0580(7) Uani 1 1 d . . . O4 O 0.3635(3) 0.4263(3) 0.34453(11) 0.0654(9) Uani 1 1 d . . . N1 N 0.6650(3) 0.6278(3) 0.46360(12) 0.0563(9) Uani 1 1 d . . . H1 H 0.6726 0.6899 0.4701 0.068 Uiso 1 1 calc R . . N2 N 0.4889(3) 0.6935(3) 0.38499(13) 0.0570(9) Uani 1 1 d . . . N3 N 0.5627(3) 0.4864(3) 0.30867(12) 0.0560(9) Uani 1 1 d . . . N4 N 0.3063(3) 0.3874(4) 0.28441(13) 0.0654(11) Uani 1 1 d . . . H4 H 0.3206 0.3801 0.2601 0.079 Uiso 1 1 calc R . . C1 C 0.7371(4) 0.5555(3) 0.47976(16) 0.0617(12) Uani 1 1 d . . . C2 C 0.8368(4) 0.5529(4) 0.46624(17) 0.0672(13) Uani 1 1 d . . . C3 C 0.9085(5) 0.4898(5) 0.4856(2) 0.0892(19) Uani 1 1 d . . . H3 H 0.9774 0.4878 0.4769 0.107 Uiso 1 1 calc R . . C4 C 0.8813(5) 0.4335(5) 0.5156(2) 0.0837(18) Uani 1 1 d . . . H4A H 0.9304 0.3924 0.5277 0.100 Uiso 1 1 calc R . . C5 C 0.7769(5) 0.4360(4) 0.52921(19) 0.0785(16) Uani 1 1 d . . . H5 H 0.7578 0.3962 0.5503 0.094 Uiso 1 1 calc R . . C6 C 0.7030(4) 0.4966(3) 0.51161(16) 0.0610(12) Uani 1 1 d . . . C7 C 0.5891(4) 0.5026(3) 0.52720(16) 0.0630(12) Uani 1 1 d . . . H7 H 0.5445 0.5249 0.5056 0.076 Uiso 1 1 calc R . . C8 C 0.5481(7) 0.4014(7) 0.5408(3) 0.130(4) Uani 1 1 d . . . H8A H 0.5433 0.3563 0.5190 0.195 Uiso 1 1 calc R . . H8B H 0.4801 0.4100 0.5522 0.195 Uiso 1 1 calc R . . H8C H 0.5950 0.3738 0.5599 0.195 Uiso 1 1 calc R . . C9 C 0.5834(6) 0.5810(8) 0.5582(3) 0.122(3) Uani 1 1 d . . . H9A H 0.6159 0.5561 0.5815 0.183 Uiso 1 1 calc R . . H9B H 0.5115 0.5969 0.5634 0.183 Uiso 1 1 calc R . . H9C H 0.6192 0.6406 0.5496 0.183 Uiso 1 1 calc R . . C10 C 0.8702(5) 0.6152(5) 0.4305(2) 0.092(2) Uani 1 1 d . . . H10 H 0.8233 0.6734 0.4290 0.111 Uiso 1 1 calc R . . C11 C 0.9802(9) 0.6552(12) 0.4322(4) 0.186(6) Uani 1 1 d . . . H11A H 1.0060 0.6508 0.4584 0.280 Uiso 1 1 calc R . . H11B H 0.9808 0.7243 0.4239 0.280 Uiso 1 1 calc R . . H11C H 1.0241 0.6160 0.4153 0.280 Uiso 1 1 calc R . . C12 C 0.8529(6) 0.5527(7) 0.3940(2) 0.105(2) Uani 1 1 d . . . H12A H 0.8834 0.4872 0.3975 0.157 Uiso 1 1 calc R . . H12B H 0.8852 0.5856 0.3722 0.157 Uiso 1 1 calc R . . H12C H 0.7793 0.5458 0.3893 0.157 Uiso 1 1 calc R . . C13 C 0.5866(4) 0.6046(3) 0.43901(14) 0.0559(11) Uani 1 1 d . . . C14 C 0.5203(4) 0.6965(3) 0.42811(15) 0.0601(11) Uani 1 1 d . . . H14 H 0.5616 0.7576 0.4328 0.072 Uiso 1 1 calc R . . C15 C 0.4226(5) 0.7004(4) 0.45340(17) 0.0728(15) Uani 1 1 d . . . H15A H 0.4424 0.6993 0.4807 0.087 Uiso 1 1 calc R . . H15B H 0.3793 0.6418 0.4483 0.087 Uiso 1 1 calc R . . C16 C 0.3603(7) 0.7977(6) 0.44445(19) 0.105(3) Uani 1 1 d . . . H16A H 0.2960 0.7988 0.4595 0.126 Uiso 1 1 calc R . . H16B H 0.4014 0.8565 0.4513 0.126 Uiso 1 1 calc R . . C17 C 0.3355(7) 0.7987(6) 0.40109(19) 0.101(2) Uani 1 1 d . . . H17A H 0.2894 0.7428 0.3951 0.121 Uiso 1 1 calc R . . H17B H 0.2988 0.8606 0.3948 0.121 Uiso 1 1 calc R . . C18 C 0.4313(5) 0.7911(4) 0.37631(17) 0.0741(16) Uani 1 1 d . . . H18A H 0.4770 0.8480 0.3815 0.089 Uiso 1 1 calc R . . H18B H 0.4117 0.7929 0.3490 0.089 Uiso 1 1 calc R . . C19 C 0.5871(5) 0.6868(4) 0.36059(16) 0.0671(13) Uani 1 1 d . . . H19A H 0.6292 0.7463 0.3656 0.080 Uiso 1 1 calc R . . H19B H 0.6271 0.6289 0.3693 0.080 Uiso 1 1 calc R . . C20 C 0.5715(5) 0.6782(4) 0.31754(15) 0.0649(13) Uani 1 1 d . . . H20A H 0.6402 0.6799 0.3055 0.078 Uiso 1 1 calc R . . H20B H 0.5349 0.7384 0.3091 0.078 Uiso 1 1 calc R . . C21 C 0.5124(4) 0.5865(3) 0.30044(14) 0.0582(11) Uani 1 1 d . . . H21A H 0.4420 0.5859 0.3109 0.070 Uiso 1 1 calc R . . H21B H 0.5070 0.5950 0.2724 0.070 Uiso 1 1 calc R . . C22 C 0.6690(4) 0.4807(5) 0.28751(18) 0.0734(14) Uani 1 1 d . . . H22A H 0.7162 0.5314 0.2978 0.088 Uiso 1 1 calc R . . H22B H 0.6596 0.4929 0.2599 0.088 Uiso 1 1 calc R . . C23 C 0.7155(5) 0.3737(5) 0.2941(2) 0.0875(19) Uani 1 1 d . . . H23A H 0.7816 0.3686 0.2804 0.105 Uiso 1 1 calc R . . H23B H 0.7294 0.3646 0.3217 0.105 Uiso 1 1 calc R . . C24 C 0.6428(5) 0.2898(5) 0.2801(2) 0.0865(19) Uani 1 1 d . . . H24A H 0.6343 0.2940 0.2521 0.104 Uiso 1 1 calc R . . H24B H 0.6729 0.2247 0.2863 0.104 Uiso 1 1 calc R . . C25 C 0.5411(5) 0.3000(4) 0.29909(19) 0.0735(14) Uani 1 1 d . . . H25A H 0.5494 0.2897 0.3269 0.088 Uiso 1 1 calc R . . H25B H 0.4944 0.2482 0.2894 0.088 Uiso 1 1 calc R . . C26 C 0.4918(4) 0.4038(4) 0.29194(16) 0.0599(12) Uani 1 1 d . . . H26 H 0.4852 0.4142 0.2638 0.072 Uiso 1 1 calc R . . C27 C 0.3837(4) 0.4070(4) 0.30990(16) 0.0619(12) Uani 1 1 d . . . C28 C 0.1991(4) 0.3785(5) 0.29769(16) 0.0724(15) Uani 1 1 d . . . C29 C 0.1659(5) 0.2850(6) 0.31170(17) 0.0834(19) Uani 1 1 d . . . C30 C 0.0617(5) 0.2810(7) 0.3244(2) 0.096(2) Uani 1 1 d . . . H30 H 0.0342 0.2202 0.3332 0.116 Uiso 1 1 calc R . . C31 C 0.0017(6) 0.3627(9) 0.3240(2) 0.112(3) Uani 1 1 d . . . H31 H -0.0667 0.3568 0.3330 0.135 Uiso 1 1 calc R . . C32 C 0.0359(5) 0.4587(8) 0.3108(2) 0.112(3) Uani 1 1 d . . . H32 H -0.0078 0.5146 0.3122 0.134 Uiso 1 1 calc R . . C33 C 0.1374(4) 0.4671(7) 0.2954(2) 0.0880(19) Uani 1 1 d . . . C34 C 0.1772(5) 0.5668(6) 0.2806(2) 0.0890(19) Uani 1 1 d . . . H34 H 0.2451 0.5537 0.2684 0.107 Uiso 1 1 calc R . . C35 C 0.1974(6) 0.6397(6) 0.3146(2) 0.101(2) Uani 1 1 d . . . H35A H 0.1354 0.6451 0.3303 0.152 Uiso 1 1 calc R . . H35B H 0.2154 0.7049 0.3045 0.152 Uiso 1 1 calc R . . H35C H 0.2539 0.6147 0.3303 0.152 Uiso 1 1 calc R . . C36 C 0.1055(7) 0.6165(8) 0.2484(3) 0.115(3) Uani 1 1 d . . . H36A H 0.0383 0.6318 0.2594 0.172 Uiso 1 1 calc R . . H36B H 0.0971 0.5704 0.2271 0.172 Uiso 1 1 calc R . . H36C H 0.1377 0.6774 0.2392 0.172 Uiso 1 1 calc R . . C37 C 0.2313(6) 0.1950(7) 0.3122(2) 0.100(2) Uani 1 1 d . . . H37 H 0.2937 0.2094 0.2965 0.120 Uiso 1 1 calc R . . C38 C 0.2688(12) 0.1677(9) 0.3542(3) 0.172(6) Uani 1 1 d . . . H38A H 0.2953 0.2271 0.3667 0.257 Uiso 1 1 calc R . . H38B H 0.3232 0.1180 0.3527 0.257 Uiso 1 1 calc R . . H38C H 0.2111 0.1414 0.3689 0.257 Uiso 1 1 calc R . . C39 C 0.1783(7) 0.0986(11) 0.2948(4) 0.188(7) Uani 1 1 d . . . H39A H 0.1279 0.0727 0.3129 0.281 Uiso 1 1 calc R . . H39B H 0.2306 0.0483 0.2898 0.281 Uiso 1 1 calc R . . H39C H 0.1438 0.1157 0.2708 0.281 Uiso 1 1 calc R . . O5 O 0.3476(3) 0.4561(3) 0.42810(12) 0.0775(11) Uani 1 1 d . . . C40 C 0.2349(5) 0.4685(6) 0.4209(2) 0.0953(19) Uani 1 1 d . . . H40A H 0.2201 0.4700 0.3932 0.114 Uiso 1 1 calc R . . H40B H 0.2093 0.5304 0.4326 0.114 Uiso 1 1 calc R . . C41 C 0.1860(7) 0.3789(7) 0.4396(3) 0.118(3) Uani 1 1 d . . . H41A H 0.1193 0.3965 0.4513 0.141 Uiso 1 1 calc R . . H41B H 0.1748 0.3257 0.4207 0.141 Uiso 1 1 calc R . . C42 C 0.2616(7) 0.3462(5) 0.4699(2) 0.106(3) Uani 1 1 d . . . H42A H 0.2499 0.3812 0.4943 0.127 Uiso 1 1 calc R . . H42B H 0.2580 0.2741 0.4743 0.127 Uiso 1 1 calc R . . C43 C 0.3601(6) 0.3750(4) 0.4524(2) 0.0807(17) Uani 1 1 d . . . H43 H 0.4139 0.3877 0.4721 0.097 Uiso 1 1 calc R . . O6 O 0.4821(5) 0.3260(3) 0.40292(13) 0.0866(13) Uani 1 1 d . . . H6O H 0.551(2) 0.3175(19) 0.3934(8) 0.000(6) Uiso 1 1 d . . . C44 C 0.3903(4) 0.2949(3) 0.42640(15) 0.0599(12) Uani 1 1 d . . . H44A H 0.3324 0.2786 0.4093 0.072 Uiso 1 1 calc R . . H44B H 0.4075 0.2351 0.4414 0.072 Uiso 1 1 calc R . . B1 B 0.5475(19) 0.9911(8) 0.3078(4) 0.188(9) Uani 1 1 d . . . F1 F 0.5566(6) 0.9998(4) 0.34781(13) 0.149(2) Uani 1 1 d . . . F2 F 0.4542(6) 0.9322(7) 0.30068(16) 0.166(3) Uani 1 1 d . . . F3 F 0.6162(9) 0.9018(5) 0.29526(19) 0.212(4) Uani 1 1 d . . . F4 F 0.521(2) 1.0624(5) 0.2912(2) 0.56(2) Uani 1 1 d . . . B2 B 0.2218(6) 0.5983(5) 0.5370(3) 0.0786(18) Uani 1 1 d . . . F5 F 0.1983(5) 0.6290(4) 0.57281(14) 0.139(2) Uani 1 1 d . . . F6 F 0.2186(5) 0.6820(3) 0.51056(16) 0.140(2) Uani 1 1 d . . . F7 F 0.1462(4) 0.5375(5) 0.5221(2) 0.158(2) Uani 1 1 d . . . F8 F 0.3127(3) 0.5477(4) 0.53387(18) 0.1265(17) 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 Ni1 0.0567(3) 0.0551(3) 0.0585(3) 0.0049(3) -0.0022(3) -0.0116(3) O1 0.066(2) 0.0466(16) 0.0679(19) -0.0040(15) -0.0103(15) -0.0009(14) O2 0.0574(19) 0.071(2) 0.0523(18) -0.0014(14) 0.0022(14) 0.0026(15) O3 0.0563(18) 0.0536(16) 0.0642(19) -0.0013(15) -0.0029(14) -0.0014(15) O4 0.053(2) 0.080(2) 0.063(2) -0.0022(17) -0.0009(16) -0.0151(16) N1 0.060(2) 0.0456(18) 0.064(2) -0.0049(16) -0.0048(19) -0.0048(16) N2 0.066(2) 0.0416(16) 0.063(2) 0.0013(17) 0.004(2) 0.0005(15) N3 0.050(2) 0.053(2) 0.065(2) -0.0061(17) 0.0086(16) -0.0008(16) N4 0.043(2) 0.090(3) 0.064(2) -0.010(2) 0.0025(18) 0.001(2) C1 0.059(3) 0.048(2) 0.077(3) -0.017(2) -0.005(2) -0.0016(19) C2 0.061(3) 0.061(3) 0.079(3) -0.009(2) 0.001(3) -0.001(2) C3 0.065(4) 0.098(5) 0.105(5) -0.028(4) 0.011(3) 0.004(3) C4 0.063(4) 0.086(4) 0.102(5) -0.012(4) -0.011(3) 0.026(3) C5 0.083(4) 0.062(3) 0.091(4) -0.007(3) -0.012(3) 0.000(3) C6 0.056(3) 0.054(3) 0.073(3) -0.001(2) -0.012(2) -0.0013(19) C7 0.058(3) 0.058(3) 0.073(3) 0.009(2) -0.007(2) -0.001(2) C8 0.082(5) 0.142(7) 0.166(8) 0.088(6) -0.028(5) -0.038(5) C9 0.063(4) 0.169(8) 0.134(7) -0.062(6) 0.007(4) -0.009(5) C10 0.070(4) 0.088(4) 0.118(6) -0.018(4) 0.011(4) -0.003(3) C11 0.145(10) 0.264(15) 0.151(9) 0.019(9) 0.006(7) -0.133(11) C12 0.099(5) 0.117(6) 0.098(5) -0.016(4) 0.034(4) -0.014(4) C13 0.062(3) 0.049(2) 0.056(3) -0.0035(19) -0.002(2) 0.006(2) C14 0.063(3) 0.046(2) 0.071(3) -0.0035(19) -0.003(2) 0.007(2) C15 0.072(4) 0.076(3) 0.070(3) -0.007(3) 0.004(3) 0.021(3) C16 0.130(7) 0.116(5) 0.069(4) 0.001(3) 0.000(4) 0.076(5) C17 0.121(6) 0.112(5) 0.071(4) -0.001(3) -0.007(4) 0.064(5) C18 0.095(4) 0.063(3) 0.064(3) 0.007(2) -0.004(3) 0.025(3) C19 0.075(3) 0.048(2) 0.078(3) 0.006(2) 0.011(3) -0.007(2) C20 0.077(3) 0.049(2) 0.069(3) 0.000(2) 0.015(2) -0.008(2) C21 0.065(3) 0.051(2) 0.059(3) 0.0087(19) 0.006(2) 0.006(2) C22 0.048(3) 0.084(3) 0.088(4) -0.016(3) 0.017(2) -0.008(3) C23 0.046(3) 0.099(4) 0.117(5) -0.013(4) 0.004(3) 0.013(3) C24 0.062(4) 0.074(4) 0.124(5) -0.024(3) -0.002(3) 0.018(3) C25 0.072(3) 0.053(3) 0.095(4) -0.015(2) -0.014(3) 0.003(2) C26 0.047(3) 0.060(3) 0.073(3) -0.006(2) 0.004(2) 0.0007(19) C27 0.052(3) 0.061(3) 0.073(3) -0.002(2) -0.006(2) -0.006(2) C28 0.046(3) 0.110(4) 0.061(3) -0.023(3) -0.004(2) -0.006(3) C29 0.063(4) 0.127(5) 0.060(3) -0.015(3) 0.003(3) -0.034(4) C30 0.053(4) 0.137(6) 0.098(5) -0.027(4) 0.004(3) -0.014(4) C31 0.050(4) 0.197(10) 0.090(5) -0.015(5) 0.013(3) -0.045(5) C32 0.056(4) 0.166(8) 0.113(5) -0.051(5) 0.011(4) -0.008(5) C33 0.039(3) 0.128(5) 0.097(4) -0.023(4) 0.002(3) -0.002(3) C34 0.060(4) 0.111(5) 0.096(4) -0.011(4) -0.012(3) 0.026(3) C35 0.086(5) 0.097(5) 0.120(6) 0.004(4) -0.005(4) 0.020(4) C36 0.096(5) 0.139(7) 0.109(6) -0.019(5) -0.005(4) 0.040(5) C37 0.069(4) 0.128(6) 0.105(5) 0.006(4) 0.005(4) -0.028(4) C38 0.297(17) 0.151(8) 0.066(5) -0.008(5) -0.019(7) 0.067(10) C39 0.085(6) 0.281(16) 0.197(11) -0.162(12) -0.006(7) -0.020(8) O5 0.077(3) 0.083(3) 0.072(2) 0.022(2) 0.0049(19) -0.005(2) C40 0.065(4) 0.113(5) 0.107(5) 0.007(4) 0.012(3) -0.004(4) C41 0.087(5) 0.112(6) 0.155(8) -0.019(6) 0.060(6) -0.020(4) C42 0.148(8) 0.064(3) 0.107(5) -0.009(3) 0.063(6) -0.027(4) C43 0.093(5) 0.063(3) 0.085(4) 0.005(3) 0.010(3) -0.013(3) O6 0.117(4) 0.058(2) 0.085(3) -0.0052(18) 0.013(3) -0.015(2) C44 0.072(3) 0.045(2) 0.062(3) -0.0043(19) 0.009(2) -0.020(2) B1 0.35(3) 0.073(6) 0.138(10) 0.009(6) -0.090(13) -0.063(10) F1 0.223(6) 0.144(4) 0.079(3) -0.008(2) 0.008(3) -0.038(4) F2 0.180(6) 0.231(8) 0.088(3) 0.033(4) 0.009(4) 0.001(6) F3 0.418(15) 0.096(4) 0.120(4) 0.001(3) -0.034(7) -0.010(6) F4 1.49(6) 0.076(3) 0.126(5) 0.016(3) -0.226(16) -0.047(12) B2 0.064(4) 0.060(3) 0.111(6) -0.001(3) 0.002(4) 0.010(3) F5 0.185(5) 0.137(4) 0.094(3) -0.009(3) 0.014(3) 0.066(4) F6 0.212(6) 0.058(2) 0.149(4) -0.005(2) 0.049(4) 0.040(3) F7 0.095(3) 0.134(4) 0.246(7) -0.024(5) -0.033(4) -0.021(3) F8 0.071(3) 0.108(3) 0.201(5) -0.021(3) 0.000(3) 0.030(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 Ni1 O2 1.980(3) . ? Ni1 O3 1.996(3) . ? Ni1 O4 2.035(4) . ? Ni1 O1 2.038(3) . ? Ni1 O6 2.057(4) . ? Ni1 O5 2.104(4) . ? O1 C13 1.241(6) . ? O2 N2 1.403(5) . ? O3 N3 1.416(5) . ? O4 C27 1.243(6) . ? N1 C13 1.346(6) . ? N1 C1 1.441(6) . ? N1 H1 0.8600 . ? N2 C19 1.512(7) . ? N2 C18 1.519(6) . ? N2 C14 1.534(7) . ? N3 C21 1.503(6) . ? N3 C26 1.533(6) . ? N3 C22 1.542(6) . ? N4 C27 1.347(7) . ? N4 C28 1.449(7) . ? N4 H4 0.8600 . ? C1 C2 1.357(8) . ? C1 C6 1.413(8) . ? C2 C3 1.407(9) . ? C2 C10 1.538(10) . ? C3 C4 1.321(10) . ? C3 H3 0.9300 . ? C4 C5 1.414(9) . ? C4 H4A 0.9300 . ? C5 C6 1.380(8) . ? C5 H5 0.9300 . ? C6 C7 1.553(8) . ? C7 C9 1.490(9) . ? C7 C8 1.515(9) . ? C7 H7 0.9800 . ? C8 H8A 0.9600 . ? C8 H8B 0.9600 . ? C8 H8C 0.9600 . ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 C11 1.504(11) . ? C10 C12 1.519(10) . ? C10 H10 0.9800 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? C13 C14 1.531(6) . ? C14 C15 1.521(8) . ? C14 H14 0.9800 . ? C15 C16 1.548(8) . ? C15 H15A 0.9700 . ? C15 H15B 0.9700 . ? C16 C17 1.522(9) . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C17 C18 1.495(10) . ? C17 H17A 0.9700 . ? C17 H17B 0.9700 . ? C18 H18A 0.9700 . ? C18 H18B 0.9700 . ? C19 C20 1.496(8) . ? C19 H19A 0.9700 . ? C19 H19B 0.9700 . ? C20 C21 1.548(7) . ? C20 H20A 0.9700 . ? C20 H20B 0.9700 . ? C21 H21A 0.9700 . ? C21 H21B 0.9700 . ? C22 C23 1.555(9) . ? C22 H22A 0.9700 . ? C22 H22B 0.9700 . ? C23 C24 1.528(9) . ? C23 H23A 0.9700 . ? C23 H23B 0.9700 . ? C24 C25 1.460(9) . ? C24 H24A 0.9700 . ? C24 H24B 0.9700 . ? C25 C26 1.535(7) . ? C25 H25A 0.9700 . ? C25 H25B 0.9700 . ? C26 C27 1.513(7) . ? C26 H26 0.9800 . ? C28 C29 1.397(10) . ? C28 C33 1.418(10) . ? C29 C30 1.402(9) . ? C29 C37 1.458(12) . ? C30 C31 1.329(13) . ? C30 H30 0.9300 . ? C31 C32 1.422(14) . ? C31 H31 0.9300 . ? C32 C33 1.406(9) . ? C32 H32 0.9300 . ? C33 C34 1.504(11) . ? C34 C35 1.537(11) . ? C34 C36 1.580(10) . ? C34 H34 0.9800 . ? C35 H35A 0.9600 . ? C35 H35B 0.9600 . ? C35 H35C 0.9600 . ? C36 H36A 0.9600 . ? C36 H36B 0.9600 . ? C36 H36C 0.9600 . ? C37 C38 1.561(12) . ? C37 C39 1.567(13) . ? C37 H37 0.9800 . ? C38 H38A 0.9600 . ? C38 H38B 0.9600 . ? C38 H38C 0.9600 . ? C39 H39A 0.9600 . ? C39 H39B 0.9600 . ? C39 H39C 0.9600 . ? O5 C43 1.371(7) . ? O5 C40 1.471(8) . ? C40 C41 1.489(11) . ? C40 H40A 0.9700 . ? C40 H40B 0.9700 . ? C41 C42 1.484(13) . ? C41 H41A 0.9700 . ? C41 H41B 0.9700 . ? C42 C43 1.447(9) . ? C42 H42A 0.9700 . ? C42 H42B 0.9700 . ? C43 C44 1.440(8) . ? C43 H43 0.9800 . ? O6 C44 1.483(7) . ? O6 H6O 0.95(3) . ? C44 H44A 0.9700 . ? C44 H44B 0.9700 . ? B1 F4 1.154(16) . ? B1 F1 1.384(14) . ? B1 F2 1.446(18) . ? B1 F3 1.54(2) . ? B2 F5 1.328(9) . ? B2 F8 1.346(8) . ? B2 F7 1.360(9) . ? B2 F6 1.435(9) . ? 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 Ni1 O3 98.48(14) . . ? O2 Ni1 O4 89.34(15) . . ? O3 Ni1 O4 91.84(14) . . ? O2 Ni1 O1 92.41(14) . . ? O3 Ni1 O1 88.68(14) . . ? O4 Ni1 O1 178.08(15) . . ? O2 Ni1 O6 166.70(18) . . ? O3 Ni1 O6 94.63(17) . . ? O4 Ni1 O6 88.06(18) . . ? O1 Ni1 O6 90.07(17) . . ? O2 Ni1 O5 90.09(15) . . ? O3 Ni1 O5 171.39(15) . . ? O4 Ni1 O5 89.10(15) . . ? O1 Ni1 O5 90.11(16) . . ? O6 Ni1 O5 76.84(18) . . ? C13 O1 Ni1 126.5(3) . . ? N2 O2 Ni1 118.9(3) . . ? N3 O3 Ni1 117.7(2) . . ? C27 O4 Ni1 126.9(3) . . ? C13 N1 C1 124.4(4) . . ? C13 N1 H1 117.8 . . ? C1 N1 H1 117.8 . . ? O2 N2 C19 111.7(3) . . ? O2 N2 C18 107.0(4) . . ? C19 N2 C18 110.1(4) . . ? O2 N2 C14 112.2(3) . . ? C19 N2 C14 108.6(4) . . ? C18 N2 C14 107.1(4) . . ? O3 N3 C21 113.7(3) . . ? O3 N3 C26 112.0(4) . . ? C21 N3 C26 107.9(4) . . ? O3 N3 C22 105.7(4) . . ? C21 N3 C22 109.4(4) . . ? C26 N3 C22 108.0(4) . . ? C27 N4 C28 120.4(4) . . ? C27 N4 H4 119.8 . . ? C28 N4 H4 119.8 . . ? C2 C1 C6 122.7(5) . . ? C2 C1 N1 119.1(5) . . ? C6 C1 N1 117.9(5) . . ? C1 C2 C3 117.7(6) . . ? C1 C2 C10 121.3(5) . . ? C3 C2 C10 120.9(6) . . ? C4 C3 C2 122.2(6) . . ? C4 C3 H3 118.9 . . ? C2 C3 H3 118.9 . . ? C3 C4 C5 119.5(6) . . ? C3 C4 H4A 120.2 . . ? C5 C4 H4A 120.2 . . ? C6 C5 C4 121.0(6) . . ? C6 C5 H5 119.5 . . ? C4 C5 H5 119.5 . . ? C5 C6 C1 116.7(5) . . ? C5 C6 C7 121.4(5) . . ? C1 C6 C7 121.9(4) . . ? C9 C7 C8 112.4(7) . . ? C9 C7 C6 109.1(5) . . ? C8 C7 C6 112.7(5) . . ? C9 C7 H7 107.5 . . ? C8 C7 H7 107.5 . . ? C6 C7 H7 107.5 . . ? C7 C8 H8A 109.5 . . ? C7 C8 H8B 109.5 . . ? H8A C8 H8B 109.5 . . ? C7 C8 H8C 109.5 . . ? H8A C8 H8C 109.5 . . ? H8B C8 H8C 109.5 . . ? C7 C9 H9A 109.5 . . ? C7 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C7 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C11 C10 C12 111.0(8) . . ? C11 C10 C2 114.8(8) . . ? C12 C10 C2 108.9(6) . . ? C11 C10 H10 107.2 . . ? C12 C10 H10 107.2 . . ? C2 C10 H10 107.2 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C10 C12 H12A 109.5 . . ? C10 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C10 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? O1 C13 N1 122.7(4) . . ? O1 C13 C14 124.7(5) . . ? N1 C13 C14 112.6(4) . . ? C15 C14 C13 110.0(4) . . ? C15 C14 N2 109.7(4) . . ? C13 C14 N2 111.1(4) . . ? C15 C14 H14 108.7 . . ? C13 C14 H14 108.7 . . ? N2 C14 H14 108.7 . . ? C14 C15 C16 109.7(5) . . ? C14 C15 H15A 109.7 . . ? C16 C15 H15A 109.7 . . ? C14 C15 H15B 109.7 . . ? C16 C15 H15B 109.7 . . ? H15A C15 H15B 108.2 . . ? C17 C16 C15 108.0(5) . . ? C17 C16 H16A 110.1 . . ? C15 C16 H16A 110.1 . . ? C17 C16 H16B 110.1 . . ? C15 C16 H16B 110.1 . . ? H16A C16 H16B 108.4 . . ? C18 C17 C16 112.7(7) . . ? C18 C17 H17A 109.1 . . ? C16 C17 H17A 109.1 . . ? C18 C17 H17B 109.1 . . ? C16 C17 H17B 109.1 . . ? H17A C17 H17B 107.8 . . ? C17 C18 N2 110.1(5) . . ? C17 C18 H18A 109.6 . . ? N2 C18 H18A 109.6 . . ? C17 C18 H18B 109.6 . . ? N2 C18 H18B 109.6 . . ? H18A C18 H18B 108.2 . . ? C20 C19 N2 116.2(5) . . ? C20 C19 H19A 108.2 . . ? N2 C19 H19A 108.2 . . ? C20 C19 H19B 108.2 . . ? N2 C19 H19B 108.2 . . ? H19A C19 H19B 107.4 . . ? C19 C20 C21 120.0(4) . . ? C19 C20 H20A 107.3 . . ? C21 C20 H20A 107.3 . . ? C19 C20 H20B 107.3 . . ? C21 C20 H20B 107.3 . . ? H20A C20 H20B 106.9 . . ? N3 C21 C20 114.5(4) . . ? N3 C21 H21A 108.6 . . ? C20 C21 H21A 108.6 . . ? N3 C21 H21B 108.6 . . ? C20 C21 H21B 108.6 . . ? H21A C21 H21B 107.6 . . ? N3 C22 C23 108.2(5) . . ? N3 C22 H22A 110.1 . . ? C23 C22 H22A 110.1 . . ? N3 C22 H22B 110.1 . . ? C23 C22 H22B 110.1 . . ? H22A C22 H22B 108.4 . . ? C24 C23 C22 112.7(5) . . ? C24 C23 H23A 109.0 . . ? C22 C23 H23A 109.0 . . ? C24 C23 H23B 109.0 . . ? C22 C23 H23B 109.0 . . ? H23A C23 H23B 107.8 . . ? C25 C24 C23 109.5(5) . . ? C25 C24 H24A 109.8 . . ? C23 C24 H24A 109.8 . . ? C25 C24 H24B 109.8 . . ? C23 C24 H24B 109.8 . . ? H24A C24 H24B 108.2 . . ? C24 C25 C26 112.1(5) . . ? C24 C25 H25A 109.2 . . ? C26 C25 H25A 109.2 . . ? C24 C25 H25B 109.2 . . ? C26 C25 H25B 109.2 . . ? H25A C25 H25B 107.9 . . ? C27 C26 N3 111.5(4) . . ? C27 C26 C25 109.5(4) . . ? N3 C26 C25 109.8(4) . . ? C27 C26 H26 108.6 . . ? N3 C26 H26 108.6 . . ? C25 C26 H26 108.6 . . ? O4 C27 N4 120.6(5) . . ? O4 C27 C26 125.8(5) . . ? N4 C27 C26 113.6(5) . . ? C29 C28 C33 125.9(6) . . ? C29 C28 N4 117.9(6) . . ? C33 C28 N4 116.2(6) . . ? C28 C29 C30 115.4(8) . . ? C28 C29 C37 123.8(6) . . ? C30 C29 C37 120.7(7) . . ? C31 C30 C29 121.0(8) . . ? C31 C30 H30 119.5 . . ? C29 C30 H30 119.5 . . ? C30 C31 C32 123.8(7) . . ? C30 C31 H31 118.1 . . ? C32 C31 H31 118.1 . . ? C33 C32 C31 118.4(8) . . ? C33 C32 H32 120.8 . . ? C31 C32 H32 120.8 . . ? C32 C33 C28 115.2(8) . . ? C32 C33 C34 120.5(7) . . ? C28 C33 C34 124.0(5) . . ? C33 C34 C35 110.8(6) . . ? C33 C34 C36 114.0(7) . . ? C35 C34 C36 111.4(6) . . ? C33 C34 H34 106.7 . . ? C35 C34 H34 106.7 . . ? C36 C34 H34 106.7 . . ? C34 C35 H35A 109.5 . . ? C34 C35 H35B 109.5 . . ? H35A C35 H35B 109.5 . . ? C34 C35 H35C 109.5 . . ? H35A C35 H35C 109.5 . . ? H35B C35 H35C 109.5 . . ? C34 C36 H36A 109.5 . . ? C34 C36 H36B 109.5 . . ? H36A C36 H36B 109.5 . . ? C34 C36 H36C 109.5 . . ? H36A C36 H36C 109.5 . . ? H36B C36 H36C 109.5 . . ? C29 C37 C38 112.1(7) . . ? C29 C37 C39 114.6(7) . . ? C38 C37 C39 107.3(10) . . ? C29 C37 H37 107.5 . . ? C38 C37 H37 107.5 . . ? C39 C37 H37 107.5 . . ? C37 C38 H38A 109.5 . . ? C37 C38 H38B 109.5 . . ? H38A C38 H38B 109.5 . . ? C37 C38 H38C 109.5 . . ? H38A C38 H38C 109.5 . . ? H38B C38 H38C 109.5 . . ? C37 C39 H39A 109.5 . . ? C37 C39 H39B 109.5 . . ? H39A C39 H39B 109.5 . . ? C37 C39 H39C 109.5 . . ? H39A C39 H39C 109.5 . . ? H39B C39 H39C 109.5 . . ? C43 O5 C40 107.7(5) . . ? C43 O5 Ni1 114.9(4) . . ? C40 O5 Ni1 125.2(4) . . ? O5 C40 C41 104.5(7) . . ? O5 C40 H40A 110.9 . . ? C41 C40 H40A 110.9 . . ? O5 C40 H40B 110.9 . . ? C41 C40 H40B 110.9 . . ? H40A C40 H40B 108.9 . . ? C42 C41 C40 105.2(7) . . ? C42 C41 H41A 110.7 . . ? C40 C41 H41A 110.7 . . ? C42 C41 H41B 110.7 . . ? C40 C41 H41B 110.7 . . ? H41A C41 H41B 108.8 . . ? C43 C42 C41 101.5(6) . . ? C43 C42 H42A 111.5 . . ? C41 C42 H42A 111.5 . . ? C43 C42 H42B 111.5 . . ? C41 C42 H42B 111.5 . . ? H42A C42 H42B 109.3 . . ? O5 C43 C44 103.6(5) . . ? O5 C43 C42 111.0(6) . . ? C44 C43 C42 107.2(5) . . ? O5 C43 H43 111.6 . . ? C44 C43 H43 111.6 . . ? C42 C43 H43 111.6 . . ? C44 O6 Ni1 109.8(3) . . ? C44 O6 H6O 153.1(17) . . ? Ni1 O6 H6O 96.4(16) . . ? C43 C44 O6 110.1(4) . . ? C43 C44 H44A 109.6 . . ? O6 C44 H44A 109.6 . . ? C43 C44 H44B 109.6 . . ? O6 C44 H44B 109.6 . . ? H44A C44 H44B 108.2 . . ? F4 B1 F1 116.5(13) . . ? F4 B1 F2 97.0(19) . . ? F1 B1 F2 106.4(14) . . ? F4 B1 F3 131.2(18) . . ? F1 B1 F3 107.1(11) . . ? F2 B1 F3 90.4(7) . . ? F5 B2 F8 115.0(7) . . ? F5 B2 F7 111.7(7) . . ? F8 B2 F7 106.7(6) . . ? F5 B2 F6 110.0(5) . . ? F8 B2 F6 111.1(6) . . ? F7 B2 F6 101.5(7) . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 26.04 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.676 _refine_diff_density_min -0.380 _refine_diff_density_rms 0.065 # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 0.135 0.521 0.134 319 62 ' ' 2 -0.135 1.021 0.366 319 62 ' ' 3 0.365 0.479 0.634 319 62 ' ' 4 0.635 -0.021 0.866 319 62 ' ' _platon_squeeze_details ; ; # Attachment 'CIF for the product 5l.CIF' data_cd4 _database_code_depnum_ccdc_archive 'CCDC 750144' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H13 Br O3' _chemical_formula_weight 333.17 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 Orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 5.5934(11) _cell_length_b 7.4974(15) _cell_length_c 31.910(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1338.2(5) _cell_formula_units_Z 4 _cell_measurement_temperature 113(2) _cell_measurement_reflns_used 4553 _cell_measurement_theta_min 2.60 _cell_measurement_theta_max 27.90 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.654 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 672 _exptl_absorpt_coefficient_mu 3.076 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4681 _exptl_absorpt_correction_T_max 0.5410 _exptl_absorpt_process_details CrystalClear _exptl_special_details ; ? ; _diffrn_ambient_temperature 113(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator confocal _diffrn_measurement_device_type 'Rigaku Saturn CCD detector' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 7.31 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10559 _diffrn_reflns_av_R_equivalents 0.0691 _diffrn_reflns_av_sigmaI/netI 0.0830 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 4 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -38 _diffrn_reflns_limit_l_max 41 _diffrn_reflns_theta_min 2.55 _diffrn_reflns_theta_max 27.89 _reflns_number_total 3171 _reflns_number_gt 2776 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear(Rigaku/MSC Inc.,2005)' _computing_cell_refinement CrystalClear _computing_data_reduction CrystalClear _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 w=1/[\s^2^(Fo^2^)+(0.0111P)^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 SHELXL _refine_ls_extinction_coef 0.043(2) _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 0.003(10) _chemical_absolute_configuration unk _refine_ls_number_reflns 3171 _refine_ls_number_parameters 183 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0395 _refine_ls_R_factor_gt 0.0347 _refine_ls_wR_factor_ref 0.0684 _refine_ls_wR_factor_gt 0.0666 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.026 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.60671(5) 0.25889(4) 0.766762(7) 0.02381(12) Uani 1 d . . . O1 O 0.1143(4) -0.0356(2) 0.94981(5) 0.0161(5) Uani 1 d . . . C10 C 0.5935(6) -0.0627(3) 1.05359(8) 0.0118(6) Uani 1 d . . . C4 C 0.3949(5) 0.0773(3) 0.90164(7) 0.0108(5) Uani 1 d . . . O2 O 0.5555(3) 0.2092(2) 0.98838(6) 0.0138(4) Uani 1 d . . . H2 H 0.4291 0.2688 0.9909 0.021 Uiso 1 calc R . . C1 C 0.5200(5) 0.1829(4) 0.82177(8) 0.0148(6) Uani 1 d . . . C15 C 0.6237(5) -0.0787(4) 1.17152(8) 0.0171(6) Uani 1 d . . . H15 H 0.7318 -0.0444 1.1930 0.020 Uiso 1 calc R . . C8 C 0.4967(4) 0.0257(3) 0.98008(7) 0.0107(6) Uani 1 d . . . H8 H 0.6460 -0.0358 0.9707 0.013 Uiso 1 calc R . . C3 C 0.2440(5) 0.0426(4) 0.86761(8) 0.0136(6) Uani 1 d . . . H3 H 0.0975 -0.0186 0.8722 0.016 Uiso 1 calc R . . C12 C 0.3021(5) -0.1740(4) 1.10857(8) 0.0120(6) Uani 1 d . . . H12 H 0.1907 -0.2042 1.0872 0.014 Uiso 1 calc R . . O3 O 0.8045(4) -0.0374(3) 1.04553(6) 0.0198(5) Uani 1 d . . . C14 C 0.4073(5) -0.1625(3) 1.18158(8) 0.0175(6) Uani 1 d . . . H14 H 0.3697 -0.1871 1.2100 0.021 Uiso 1 calc R . . C16 C 0.6783(5) -0.0462(4) 1.12959(8) 0.0139(6) Uani 1 d . . . H16 H 0.8257 0.0091 1.1225 0.017 Uiso 1 calc R . . C7 C 0.3177(5) 0.0173(4) 0.94425(8) 0.0113(6) Uani 1 d . . . C9 C 0.4091(4) -0.0672(3) 1.01950(7) 0.0112(6) Uani 1 d . . . H9A H 0.2614 -0.0082 1.0295 0.013 Uiso 1 calc R . . H9B H 0.3696 -0.1928 1.0128 0.013 Uiso 1 calc R . . C6 C 0.6752(5) 0.2180(3) 0.85427(8) 0.0143(6) Uani 1 d . . . H6 H 0.8217 0.2785 0.8494 0.017 Uiso 1 calc R . . C5 C 0.6132(5) 0.1632(3) 0.89422(8) 0.0131(6) Uani 1 d . . . H5 H 0.7199 0.1840 0.9169 0.016 Uiso 1 calc R . . C13 C 0.2490(5) -0.2096(4) 1.15043(8) 0.0151(6) Uani 1 d . . . H13 H 0.1028 -0.2666 1.1575 0.018 Uiso 1 calc R . . C2 C 0.3046(5) 0.0961(4) 0.82737(8) 0.0154(6) Uani 1 d . . . H2A H 0.2010 0.0737 0.8044 0.019 Uiso 1 calc R . . C11 C 0.5194(4) -0.0937(3) 1.09804(7) 0.0110(6) Uani 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 0.03383(19) 0.02567(19) 0.01193(15) 0.00131(13) 0.00395(13) -0.00565(19) O1 0.0140(11) 0.0177(11) 0.0165(10) -0.0003(8) 0.0010(10) -0.0045(11) C10 0.0141(14) 0.0077(14) 0.0138(14) 0.0012(10) 0.0024(13) -0.0011(13) C4 0.0129(13) 0.0082(13) 0.0114(12) -0.0010(10) 0.0006(12) 0.0014(13) O2 0.0165(9) 0.0048(10) 0.0203(9) -0.0010(7) -0.0015(9) -0.0016(8) C1 0.0223(15) 0.0125(15) 0.0095(13) 0.0001(10) 0.0053(12) 0.0025(12) C15 0.0203(15) 0.0184(15) 0.0125(13) -0.0021(11) -0.0058(14) -0.0008(14) C8 0.0142(14) 0.0052(13) 0.0127(13) 0.0007(10) 0.0014(12) 0.0012(12) C3 0.0132(14) 0.0112(15) 0.0165(14) 0.0011(12) -0.0001(12) -0.0020(12) C12 0.0140(14) 0.0089(14) 0.0130(14) -0.0005(10) -0.0012(12) -0.0004(12) O3 0.0114(10) 0.0319(13) 0.0163(11) 0.0057(9) -0.0006(9) -0.0008(10) C14 0.0242(15) 0.0167(15) 0.0115(13) 0.0035(11) 0.0009(14) 0.0072(14) C16 0.0134(14) 0.0113(15) 0.0170(14) 0.0021(11) -0.0029(13) -0.0004(13) C7 0.0149(14) 0.0042(13) 0.0149(14) -0.0025(11) -0.0012(13) 0.0000(12) C9 0.0103(13) 0.0108(14) 0.0126(13) 0.0040(10) 0.0001(12) -0.0012(12) C6 0.0141(12) 0.0136(16) 0.0153(13) -0.0006(11) 0.0041(12) -0.0007(13) C5 0.0141(14) 0.0109(14) 0.0144(14) 0.0014(11) -0.0025(13) -0.0005(13) C13 0.0159(14) 0.0128(16) 0.0167(14) 0.0033(11) 0.0055(12) -0.0023(12) C2 0.0184(14) 0.0153(16) 0.0126(14) -0.0025(11) -0.0056(13) -0.0015(13) C11 0.0112(13) 0.0115(15) 0.0104(13) 0.0009(10) -0.0009(12) 0.0039(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 C1 1.908(3) . ? O1 C7 1.218(3) . ? C10 O3 1.223(4) . ? C10 C11 1.496(3) . ? C10 C9 1.500(4) . ? C4 C3 1.400(3) . ? C4 C5 1.400(4) . ? C4 C7 1.496(3) . ? O2 C8 1.439(3) . ? O2 H2 0.8400 . ? C1 C6 1.378(3) . ? C1 C2 1.381(4) . ? C15 C16 1.394(3) . ? C15 C14 1.401(4) . ? C15 H15 0.9500 . ? C8 C9 1.519(3) . ? C8 C7 1.521(3) . ? C8 H8 1.0000 . ? C3 C2 1.387(4) . ? C3 H3 0.9500 . ? C12 C13 1.394(3) . ? C12 C11 1.397(3) . ? C12 H12 0.9500 . ? C14 C13 1.377(4) . ? C14 H14 0.9500 . ? C16 C11 1.389(3) . ? C16 H16 0.9500 . ? C9 H9A 0.9900 . ? C9 H9B 0.9900 . ? C6 C5 1.384(3) . ? C6 H6 0.9500 . ? C5 H5 0.9500 . ? C13 H13 0.9500 . ? C2 H2A 0.9500 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O3 C10 C11 119.4(3) . . ? O3 C10 C9 121.0(2) . . ? C11 C10 C9 119.6(3) . . ? C3 C4 C5 118.7(2) . . ? C3 C4 C7 118.3(2) . . ? C5 C4 C7 122.9(2) . . ? C8 O2 H2 109.5 . . ? C6 C1 C2 122.8(2) . . ? C6 C1 Br1 118.4(2) . . ? C2 C1 Br1 118.8(2) . . ? C16 C15 C14 119.2(3) . . ? C16 C15 H15 120.4 . . ? C14 C15 H15 120.4 . . ? O2 C8 C9 111.11(19) . . ? O2 C8 C7 109.2(2) . . ? C9 C8 C7 113.0(2) . . ? O2 C8 H8 107.8 . . ? C9 C8 H8 107.8 . . ? C7 C8 H8 107.8 . . ? C2 C3 C4 121.1(3) . . ? C2 C3 H3 119.4 . . ? C4 C3 H3 119.4 . . ? C13 C12 C11 119.9(3) . . ? C13 C12 H12 120.1 . . ? C11 C12 H12 120.1 . . ? C13 C14 C15 120.3(2) . . ? C13 C14 H14 119.8 . . ? C15 C14 H14 119.8 . . ? C11 C16 C15 120.7(3) . . ? C11 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? O1 C7 C4 120.0(2) . . ? O1 C7 C8 121.3(2) . . ? C4 C7 C8 118.7(2) . . ? C10 C9 C8 111.6(2) . . ? C10 C9 H9A 109.3 . . ? C8 C9 H9A 109.3 . . ? C10 C9 H9B 109.3 . . ? C8 C9 H9B 109.3 . . ? H9A C9 H9B 108.0 . . ? C1 C6 C5 118.6(3) . . ? C1 C6 H6 120.7 . . ? C5 C6 H6 120.7 . . ? C6 C5 C4 120.7(3) . . ? C6 C5 H5 119.6 . . ? C4 C5 H5 119.6 . . ? C14 C13 C12 120.4(3) . . ? C14 C13 H13 119.8 . . ? C12 C13 H13 119.8 . . ? C1 C2 C3 118.0(3) . . ? C1 C2 H2A 121.0 . . ? C3 C2 H2A 121.0 . . ? C16 C11 C12 119.5(2) . . ? C16 C11 C10 118.1(2) . . ? C12 C11 C10 122.4(2) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C5 C4 C3 C2 -1.8(4) . . . . ? C7 C4 C3 C2 179.5(2) . . . . ? C16 C15 C14 C13 -1.0(4) . . . . ? C14 C15 C16 C11 0.9(4) . . . . ? C3 C4 C7 O1 -10.8(4) . . . . ? C5 C4 C7 O1 170.5(3) . . . . ? C3 C4 C7 C8 169.8(2) . . . . ? C5 C4 C7 C8 -8.9(4) . . . . ? O2 C8 C7 O1 -113.9(3) . . . . ? C9 C8 C7 O1 10.2(4) . . . . ? O2 C8 C7 C4 65.5(3) . . . . ? C9 C8 C7 C4 -170.4(2) . . . . ? O3 C10 C9 C8 -20.5(3) . . . . ? C11 C10 C9 C8 160.9(2) . . . . ? O2 C8 C9 C10 -59.2(3) . . . . ? C7 C8 C9 C10 177.7(2) . . . . ? C2 C1 C6 C5 0.3(4) . . . . ? Br1 C1 C6 C5 180.00(19) . . . . ? C1 C6 C5 C4 -1.4(4) . . . . ? C3 C4 C5 C6 2.1(4) . . . . ? C7 C4 C5 C6 -179.2(2) . . . . ? C15 C14 C13 C12 -0.1(4) . . . . ? C11 C12 C13 C14 1.5(4) . . . . ? C6 C1 C2 C3 0.0(4) . . . . ? Br1 C1 C2 C3 -179.7(2) . . . . ? C4 C3 C2 C1 0.7(4) . . . . ? C15 C16 C11 C12 0.4(4) . . . . ? C15 C16 C11 C10 -177.3(2) . . . . ? C13 C12 C11 C16 -1.6(4) . . . . ? C13 C12 C11 C10 176.0(2) . . . . ? O3 C10 C11 C16 17.0(4) . . . . ? C9 C10 C11 C16 -164.4(2) . . . . ? O3 C10 C11 C12 -160.7(3) . . . . ? C9 C10 C11 C12 18.0(4) . . . . ? 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 O2 H2 O2 0.84 2.20 2.9573(12) 150.3 4_457 O2 H2 O3 0.84 2.43 3.032(3) 129.6 4_457 _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 27.89 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.525 _refine_diff_density_min -0.509 _refine_diff_density_rms 0.084