# Electronic Supplementary Material (ESI) for Chemical Science # This journal is © The Royal Society of Chemistry 2012 data_global _journal_coden_Cambridge 1475 loop_ _publ_author_name 'Zhong, Fangrui' 'Han, Xiaoyu' 'Wang, Youqing' 'Lu, Yixin' _publ_contact_author_name 'Lu, Yixin' _publ_contact_author_email chmlyx@nus.edu.sg _publ_section_title ; Highly Enantioselective [4 + 2] Annulations Catalyzed by Amino Acid-Based Phosphines: Synthesis of Functionalized Cyclohexenes and 3-Spirocyclohexene-2-oxindoles ; # Attachment '- B286A.cif' data_b286a _database_code_depnum_ccdc_archive 'CCDC 861186' #TrackingRef '- B286A.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29 H26 Cl N3 O5' _chemical_formula_weight 531.98 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) 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 9.5107(4) _cell_length_b 10.1897(5) _cell_length_c 27.7823(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2692.4(2) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5679 _cell_measurement_theta_min 2.26 _cell_measurement_theta_max 24.65 _exptl_crystal_description BLOCK _exptl_crystal_colour COLOURLESS _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.60 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas 'Not measured' _exptl_crystal_density_diffrn 1.312 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 0.186 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.8968 _exptl_absorpt_correction_T_max 0.9781 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 19080 _diffrn_reflns_av_R_equivalents 0.0363 _diffrn_reflns_av_sigmaI/netI 0.0413 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -31 _diffrn_reflns_limit_l_max 35 _diffrn_reflns_theta_min 1.47 _diffrn_reflns_theta_max 27.49 _reflns_number_total 6164 _reflns_number_gt 5688 _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^)+(0.0600P)^2^+0.0773P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.01(6) _refine_ls_number_reflns 6164 _refine_ls_number_parameters 347 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0510 _refine_ls_R_factor_gt 0.0466 _refine_ls_wR_factor_ref 0.1099 _refine_ls_wR_factor_gt 0.1076 _refine_ls_goodness_of_fit_ref 1.097 _refine_ls_restrained_S_all 1.097 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl -0.01569(6) 0.88713(7) 0.06044(2) 0.04987(17) Uani 1 1 d . . . O1 O 0.67604(16) 0.71380(14) 0.17620(6) 0.0383(4) Uani 1 1 d . . . O2 O 0.71301(15) 1.05505(16) 0.30513(5) 0.0363(4) Uani 1 1 d . . . O3 O 0.87205(14) 1.05377(13) 0.24449(4) 0.0269(3) Uani 1 1 d . . . O4 O 0.71521(16) 1.23909(14) 0.17835(6) 0.0364(3) Uani 1 1 d . . . O5 O 0.84985(16) 1.11924(15) 0.12862(5) 0.0369(4) Uani 1 1 d . . . N1 N 0.51241(16) 0.64342(15) 0.12181(5) 0.0239(3) Uani 1 1 d . . . N2 N 0.6351(2) 0.9597(2) 0.05078(6) 0.0429(5) Uani 1 1 d . . . N3 N 0.3778(2) 1.17768(18) 0.14558(7) 0.0421(5) Uani 1 1 d . . . C1 C 0.1430(2) 0.8139(2) 0.07627(7) 0.0313(4) Uani 1 1 d . . . C2 C 0.2323(2) 0.8782(2) 0.10809(6) 0.0263(4) Uani 1 1 d . . . H2 H 0.2097 0.9603 0.1205 0.032 Uiso 1 1 calc R . . C3 C 0.35631(18) 0.81528(17) 0.12051(6) 0.0220(4) Uani 1 1 d . . . C4 C 0.38616(19) 0.69159(19) 0.10191(6) 0.0241(4) Uani 1 1 d . . . C5 C 0.2982(2) 0.6297(2) 0.06970(7) 0.0341(5) Uani 1 1 d . . . H5 H 0.3210 0.5481 0.0569 0.041 Uiso 1 1 calc R . . C6 C 0.1752(2) 0.6928(2) 0.05704(7) 0.0363(5) Uani 1 1 d . . . H6 H 0.1137 0.6534 0.0354 0.044 Uiso 1 1 calc R . . C7 C 0.5696(2) 0.73074(18) 0.15325(6) 0.0242(4) Uani 1 1 d . . . C8 C 0.47199(19) 0.85262(18) 0.15569(6) 0.0216(4) Uani 1 1 d . . . C9 C 0.5566(2) 0.50725(19) 0.11886(7) 0.0283(4) Uani 1 1 d . . . H9A H 0.4746 0.4517 0.1229 0.034 Uiso 1 1 calc R . . H9B H 0.6202 0.4892 0.1453 0.034 Uiso 1 1 calc R . . C10 C 0.6289(2) 0.47007(19) 0.07222(6) 0.0270(4) Uani 1 1 d . . . C11 C 0.7339(2) 0.5493(2) 0.05310(8) 0.0370(5) Uani 1 1 d . . . H11 H 0.7561 0.6286 0.0678 0.044 Uiso 1 1 calc R . . C12 C 0.8054(3) 0.5102(3) 0.01214(9) 0.0519(7) Uani 1 1 d . . . H12 H 0.8753 0.5635 -0.0007 0.062 Uiso 1 1 calc R . . C13 C 0.7735(3) 0.3931(3) -0.00953(9) 0.0596(8) Uani 1 1 d . . . H13 H 0.8230 0.3666 -0.0367 0.071 Uiso 1 1 calc R . . C14 C 0.6680(3) 0.3140(3) 0.00881(9) 0.0550(7) Uani 1 1 d . . . H14 H 0.6456 0.2352 -0.0062 0.066 Uiso 1 1 calc R . . C15 C 0.5960(3) 0.3532(2) 0.04971(8) 0.0405(5) Uani 1 1 d . . . H15 H 0.5250 0.3004 0.0621 0.049 Uiso 1 1 calc R . . C16 C 0.42025(19) 0.8710(2) 0.20772(6) 0.0258(4) Uani 1 1 d . . . H16A H 0.3365 0.9254 0.2073 0.031 Uiso 1 1 calc R . . H16B H 0.3941 0.7861 0.2207 0.031 Uiso 1 1 calc R . . C17 C 0.5261(2) 0.93230(19) 0.24025(6) 0.0256(4) Uani 1 1 d . . . H17 H 0.5087 0.9287 0.2732 0.031 Uiso 1 1 calc R . . C18 C 0.64305(19) 0.99164(17) 0.22598(6) 0.0223(4) Uani 1 1 d . . . C19 C 0.68533(19) 1.00312(18) 0.17380(6) 0.0217(4) Uani 1 1 d . . . H19 H 0.7548 0.9347 0.1669 0.026 Uiso 1 1 calc R . . C20 C 0.55439(18) 0.97994(18) 0.14061(6) 0.0213(4) Uani 1 1 d . . . C21 C 0.7449(2) 1.03765(19) 0.26373(6) 0.0242(4) Uani 1 1 d . . . C22 C 0.99206(19) 1.10708(18) 0.27309(6) 0.0262(4) Uani 1 1 d . . . C23 C 1.0311(3) 1.0106(2) 0.31190(8) 0.0413(5) Uani 1 1 d . . . H23A H 0.9526 0.9984 0.3331 0.062 Uiso 1 1 calc R . . H23B H 1.1098 1.0438 0.3298 0.062 Uiso 1 1 calc R . . H23C H 1.0559 0.9282 0.2975 0.062 Uiso 1 1 calc R . . C24 C 0.9541(2) 1.2401(2) 0.29358(9) 0.0373(5) Uani 1 1 d . . . H24A H 0.9131 1.2933 0.2688 0.056 Uiso 1 1 calc R . . H24B H 1.0373 1.2821 0.3056 0.056 Uiso 1 1 calc R . . H24C H 0.8878 1.2292 0.3193 0.056 Uiso 1 1 calc R . . C25 C 1.1054(2) 1.1197(2) 0.23515(8) 0.0381(5) Uani 1 1 d . . . H25A H 1.1193 1.0364 0.2197 0.057 Uiso 1 1 calc R . . H25B H 1.1916 1.1473 0.2500 0.057 Uiso 1 1 calc R . . H25C H 1.0773 1.1835 0.2116 0.057 Uiso 1 1 calc R . . C26 C 0.7508(2) 1.13636(19) 0.16164(6) 0.0240(4) Uani 1 1 d . . . C27 C 0.9196(3) 1.2338(3) 0.10973(9) 0.0465(6) Uani 1 1 d . . . H27A H 0.8509 1.2994 0.1019 0.070 Uiso 1 1 calc R . . H27B H 0.9712 1.2104 0.0813 0.070 Uiso 1 1 calc R . . H27C H 0.9833 1.2680 0.1335 0.070 Uiso 1 1 calc R . . C28 C 0.6009(2) 0.96859(19) 0.08970(6) 0.0256(4) Uani 1 1 d . . . C29 C 0.4562(2) 1.09308(18) 0.14377(6) 0.0250(4) Uani 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cl1 0.0270(3) 0.0641(4) 0.0585(4) -0.0082(3) -0.0182(2) 0.0089(3) O1 0.0322(8) 0.0323(8) 0.0505(9) -0.0071(7) -0.0185(7) 0.0074(6) O2 0.0341(8) 0.0530(10) 0.0218(7) -0.0095(6) -0.0007(6) -0.0106(7) O3 0.0212(6) 0.0361(8) 0.0234(6) -0.0068(5) -0.0047(5) -0.0011(6) O4 0.0382(8) 0.0257(7) 0.0454(9) -0.0049(6) 0.0034(7) -0.0030(6) O5 0.0413(8) 0.0370(8) 0.0325(7) -0.0077(6) 0.0139(6) -0.0125(7) N1 0.0233(7) 0.0237(8) 0.0247(7) -0.0044(6) -0.0004(6) 0.0015(6) N2 0.0416(10) 0.0622(13) 0.0249(9) -0.0066(8) -0.0020(8) -0.0024(10) N3 0.0372(10) 0.0322(10) 0.0568(12) 0.0000(8) -0.0012(9) 0.0060(9) C1 0.0192(9) 0.0448(12) 0.0299(10) 0.0010(8) -0.0051(8) 0.0005(9) C2 0.0233(9) 0.0298(10) 0.0260(9) -0.0019(7) -0.0027(7) -0.0005(8) C3 0.0225(9) 0.0245(9) 0.0191(8) -0.0006(7) -0.0016(7) -0.0040(7) C4 0.0217(9) 0.0288(10) 0.0219(9) -0.0014(7) 0.0010(7) -0.0004(8) C5 0.0326(11) 0.0360(11) 0.0335(10) -0.0140(9) -0.0028(8) -0.0016(9) C6 0.0272(10) 0.0480(13) 0.0336(11) -0.0128(10) -0.0079(9) -0.0044(10) C7 0.0236(9) 0.0240(9) 0.0251(9) 0.0005(7) -0.0024(7) 0.0014(7) C8 0.0203(8) 0.0234(9) 0.0210(8) -0.0020(7) -0.0027(7) 0.0011(7) C9 0.0295(10) 0.0232(9) 0.0323(10) 0.0004(7) 0.0025(8) 0.0017(8) C10 0.0277(9) 0.0252(9) 0.0280(9) 0.0008(7) -0.0005(8) 0.0074(8) C11 0.0336(11) 0.0404(12) 0.0369(11) 0.0003(9) 0.0045(9) 0.0001(10) C12 0.0419(13) 0.0703(19) 0.0433(13) 0.0091(12) 0.0150(11) 0.0079(13) C13 0.0695(18) 0.075(2) 0.0340(12) 0.0014(12) 0.0148(12) 0.0356(17) C14 0.085(2) 0.0435(14) 0.0370(13) -0.0135(10) -0.0018(13) 0.0167(15) C15 0.0551(14) 0.0293(11) 0.0372(11) -0.0020(9) 0.0017(10) 0.0004(10) C16 0.0225(9) 0.0305(10) 0.0245(9) -0.0012(8) 0.0004(7) -0.0027(8) C17 0.0273(9) 0.0313(10) 0.0182(8) -0.0025(7) 0.0013(7) -0.0020(8) C18 0.0226(9) 0.0240(9) 0.0204(8) -0.0038(7) -0.0015(7) 0.0010(7) C19 0.0183(8) 0.0252(9) 0.0215(8) -0.0037(7) -0.0014(7) 0.0002(7) C20 0.0203(8) 0.0229(9) 0.0206(8) -0.0026(7) -0.0022(7) -0.0016(7) C21 0.0260(9) 0.0246(9) 0.0218(9) -0.0022(7) -0.0021(7) -0.0021(8) C22 0.0211(9) 0.0284(10) 0.0290(9) -0.0038(7) -0.0071(7) -0.0019(8) C23 0.0419(13) 0.0395(12) 0.0426(12) 0.0045(9) -0.0165(10) -0.0006(10) C24 0.0347(11) 0.0289(10) 0.0483(12) -0.0094(9) -0.0032(10) -0.0026(9) C25 0.0233(10) 0.0488(14) 0.0420(11) -0.0105(10) 0.0009(9) -0.0027(10) C26 0.0231(9) 0.0280(10) 0.0208(8) -0.0017(7) -0.0051(7) -0.0037(8) C27 0.0527(15) 0.0476(14) 0.0391(12) 0.0025(10) 0.0100(11) -0.0193(12) C28 0.0236(9) 0.0296(10) 0.0236(9) -0.0025(7) -0.0044(7) -0.0025(8) C29 0.0239(9) 0.0257(9) 0.0254(9) -0.0011(7) 0.0005(7) -0.0008(8) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cl1 C1 1.740(2) . ? O1 C7 1.209(2) . ? O2 C21 1.203(2) . ? O3 C21 1.332(2) . ? O3 C22 1.493(2) . ? O4 C26 1.194(2) . ? O5 C26 1.326(2) . ? O5 C27 1.442(3) . ? N1 C7 1.360(2) . ? N1 C4 1.410(2) . ? N1 C9 1.452(2) . ? N2 C28 1.133(2) . ? N3 C29 1.141(3) . ? C1 C6 1.379(3) . ? C1 C2 1.391(3) . ? C2 C3 1.386(3) . ? C3 C4 1.391(3) . ? C3 C8 1.520(2) . ? C4 C5 1.378(3) . ? C5 C6 1.381(3) . ? C7 C8 1.552(3) . ? C8 C16 1.539(2) . ? C8 C20 1.573(2) . ? C9 C10 1.515(3) . ? C10 C15 1.381(3) . ? C10 C11 1.390(3) . ? C11 C12 1.385(3) . ? C12 C13 1.370(4) . ? C13 C14 1.384(4) . ? C14 C15 1.385(3) . ? C16 C17 1.490(3) . ? C17 C18 1.327(3) . ? C18 C21 1.503(2) . ? C18 C19 1.509(2) . ? C19 C26 1.531(3) . ? C19 C20 1.567(2) . ? C20 C29 1.486(3) . ? C20 C28 1.486(2) . ? C22 C23 1.505(3) . ? C22 C25 1.513(3) . ? C22 C24 1.514(3) . ? 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 C21 O3 C22 121.68(13) . . ? C26 O5 C27 118.17(17) . . ? C7 N1 C4 111.36(15) . . ? C7 N1 C9 123.07(15) . . ? C4 N1 C9 123.85(15) . . ? C6 C1 C2 122.18(19) . . ? C6 C1 Cl1 118.60(15) . . ? C2 C1 Cl1 119.21(17) . . ? C3 C2 C1 117.36(18) . . ? C2 C3 C4 120.03(17) . . ? C2 C3 C8 131.30(17) . . ? C4 C3 C8 108.53(15) . . ? C5 C4 C3 122.12(18) . . ? C5 C4 N1 127.76(18) . . ? C3 C4 N1 110.10(15) . . ? C4 C5 C6 117.85(19) . . ? C1 C6 C5 120.41(18) . . ? O1 C7 N1 125.45(18) . . ? O1 C7 C8 126.30(17) . . ? N1 C7 C8 108.22(15) . . ? C3 C8 C16 113.78(14) . . ? C3 C8 C7 101.80(14) . . ? C16 C8 C7 109.26(14) . . ? C3 C8 C20 113.33(14) . . ? C16 C8 C20 108.00(14) . . ? C7 C8 C20 110.53(14) . . ? N1 C9 C10 114.74(15) . . ? C15 C10 C11 119.38(19) . . ? C15 C10 C9 120.01(18) . . ? C11 C10 C9 120.52(18) . . ? C12 C11 C10 120.0(2) . . ? C13 C12 C11 120.2(2) . . ? C12 C13 C14 120.4(2) . . ? C13 C14 C15 119.5(2) . . ? C10 C15 C14 120.5(2) . . ? C17 C16 C8 113.90(15) . . ? C18 C17 C16 125.17(16) . . ? C17 C18 C21 118.29(16) . . ? C17 C18 C19 123.09(16) . . ? C21 C18 C19 118.33(15) . . ? C18 C19 C26 112.90(14) . . ? C18 C19 C20 109.99(14) . . ? C26 C19 C20 109.07(14) . . ? C29 C20 C28 107.66(15) . . ? C29 C20 C19 110.34(14) . . ? C28 C20 C19 109.59(14) . . ? C29 C20 C8 108.13(14) . . ? C28 C20 C8 109.72(14) . . ? C19 C20 C8 111.32(14) . . ? O2 C21 O3 126.46(17) . . ? O2 C21 C18 123.44(17) . . ? O3 C21 C18 110.09(14) . . ? O3 C22 C23 109.41(16) . . ? O3 C22 C25 101.82(14) . . ? C23 C22 C25 112.25(18) . . ? O3 C22 C24 110.08(15) . . ? C23 C22 C24 111.98(17) . . ? C25 C22 C24 110.84(17) . . ? O4 C26 O5 125.83(18) . . ? O4 C26 C19 125.19(17) . . ? O5 C26 C19 108.96(16) . . ? N2 C28 C20 179.4(2) . . ? N3 C29 C20 178.0(2) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.304 _refine_diff_density_min -0.173 _refine_diff_density_rms 0.048 _chemical_absolute_configuration ad # Attachment '- b478.cif' data_b478 _database_code_depnum_ccdc_archive 'CCDC 861187' #TrackingRef '- b478.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H21 Br N2 O4' _chemical_formula_weight 445.31 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' 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 C2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 21.316(2) _cell_length_b 6.3205(6) _cell_length_c 17.4926(17) _cell_angle_alpha 90.00 _cell_angle_beta 112.859(2) _cell_angle_gamma 90.00 _cell_volume 2171.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 2749 _cell_measurement_theta_min 2.53 _cell_measurement_theta_max 19.56 _exptl_crystal_description Plate _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas 'Not Measured' _exptl_crystal_density_diffrn 1.362 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 912 _exptl_absorpt_coefficient_mu 1.920 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.3921 _exptl_absorpt_correction_T_max 0.8312 _exptl_absorpt_process_details 'Sadabs, (Sheldrick 2001)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13985 _diffrn_reflns_av_R_equivalents 0.0454 _diffrn_reflns_av_sigmaI/netI 0.0736 _diffrn_reflns_limit_h_min -27 _diffrn_reflns_limit_h_max 27 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.26 _diffrn_reflns_theta_max 27.50 _reflns_number_total 4967 _reflns_number_gt 3130 _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^)+(0.0532P)^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 0.024(11) _refine_ls_number_reflns 4967 _refine_ls_number_parameters 257 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0884 _refine_ls_R_factor_gt 0.0479 _refine_ls_wR_factor_ref 0.1286 _refine_ls_wR_factor_gt 0.1018 _refine_ls_goodness_of_fit_ref 1.010 _refine_ls_restrained_S_all 1.010 _refine_ls_shift/su_max 0.000 _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 0.56936(2) 0.72875(10) 0.96059(3) 0.0914(2) Uani 1 1 d . . . O1 O 0.8659(2) 0.5121(5) 0.6444(2) 0.0888(10) Uani 1 1 d . . . O2 O 0.80754(16) 0.7876(6) 0.57393(17) 0.0781(10) Uani 1 1 d . . . O3 O 1.03328(14) 0.8055(6) 0.8100(2) 0.0834(11) Uani 1 1 d . . . O4 O 0.95278(13) 0.9261(5) 0.69081(17) 0.0600(7) Uani 1 1 d . . . N1 N 0.7842(3) 0.3107(6) 0.7532(3) 0.0936(14) Uani 1 1 d . . . N2 N 0.6724(2) 0.8565(9) 0.6427(3) 0.0879(14) Uani 1 1 d . . . C1 C 0.74534(18) 0.7823(5) 0.8663(2) 0.0427(8) Uani 1 1 d . . . C2 C 0.7356(2) 0.5952(7) 0.9021(2) 0.0527(10) Uani 1 1 d . . . H2 H 0.7648 0.4796 0.9077 0.063 Uiso 1 1 calc R . . C3 C 0.6834(2) 0.5790(7) 0.9295(3) 0.0586(11) Uani 1 1 d . . . H3 H 0.6763 0.4518 0.9527 0.070 Uiso 1 1 calc R . . C4 C 0.64189(19) 0.7497(8) 0.9226(2) 0.0564(10) Uani 1 1 d . . . C5 C 0.6497(2) 0.9351(7) 0.8874(3) 0.0585(11) Uani 1 1 d . . . H5 H 0.6204 1.0501 0.8825 0.070 Uiso 1 1 calc R . . C6 C 0.70196(19) 0.9497(6) 0.8587(2) 0.0522(10) Uani 1 1 d . . . H6 H 0.7078 1.0759 0.8337 0.063 Uiso 1 1 calc R . . C7 C 0.80384(17) 0.8082(5) 0.8372(2) 0.0418(8) Uani 1 1 d . . . H7 H 0.8112 0.9624 0.8350 0.050 Uiso 1 1 calc R . . C8 C 0.87130(17) 0.7161(10) 0.8970(2) 0.0594(9) Uani 1 1 d . . . H8A H 0.8848 0.7872 0.9508 0.071 Uiso 1 1 calc R . . H8B H 0.8652 0.5654 0.9054 0.071 Uiso 1 1 calc R . . C9 C 0.92643(17) 0.7413(9) 0.8653(2) 0.0589(9) Uani 1 1 d . . . H9 H 0.9717 0.7246 0.9029 0.071 Uiso 1 1 calc R . . C10 C 0.91542(17) 0.7854(6) 0.7877(2) 0.0468(9) Uani 1 1 d . . . C11 C 0.84516(17) 0.8017(5) 0.7189(2) 0.0407(8) Uani 1 1 d . . . H11 H 0.8361 0.9529 0.7038 0.049 Uiso 1 1 calc R . . C12 C 0.78938(15) 0.7217(7) 0.74875(19) 0.0410(7) Uani 1 1 d . . . C13 C 0.7866(2) 0.4885(7) 0.7499(3) 0.0583(10) Uani 1 1 d . . . C14 C 0.72263(19) 0.7980(6) 0.6891(2) 0.0524(10) Uani 1 1 d . . . C15 C 0.9754(2) 0.8357(7) 0.7652(3) 0.0569(10) Uani 1 1 d . . . C16 C 0.9988(2) 1.0172(9) 0.6533(3) 0.0729(13) Uani 1 1 d . . . C17 C 1.0404(3) 1.1891(13) 0.7081(4) 0.119(3) Uani 1 1 d . . . H17A H 1.0109 1.2834 0.7227 0.178 Uiso 1 1 calc R . . H17B H 1.0634 1.2681 0.6791 0.178 Uiso 1 1 calc R . . H17C H 1.0739 1.1276 0.7581 0.178 Uiso 1 1 calc R . . C18 C 1.0416(4) 0.8440(14) 0.6395(5) 0.145(3) Uani 1 1 d . . . H18A H 1.0658 0.8981 0.6067 0.218 Uiso 1 1 calc R . . H18B H 1.0126 0.7276 0.6104 0.218 Uiso 1 1 calc R . . H18C H 1.0742 0.7948 0.6927 0.218 Uiso 1 1 calc R . . C19 C 0.9489(3) 1.1087(10) 0.5729(3) 0.0905(16) Uani 1 1 d . . . H19A H 0.9169 1.1994 0.5843 0.136 Uiso 1 1 calc R . . H19B H 0.9244 0.9947 0.5364 0.136 Uiso 1 1 calc R . . H19C H 0.9733 1.1907 0.5465 0.136 Uiso 1 1 calc R . . C20 C 0.8421(2) 0.6813(7) 0.6419(3) 0.0543(11) Uani 1 1 d . . . C21 C 0.8017(4) 0.6876(14) 0.4955(3) 0.122(3) Uani 1 1 d . . . H21A H 0.8423 0.7171 0.4851 0.182 Uiso 1 1 calc R . . H21B H 0.7622 0.7439 0.4504 0.182 Uiso 1 1 calc R . . H21C H 0.7966 0.5359 0.4992 0.182 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 0.0964(4) 0.0961(4) 0.1179(4) -0.0261(4) 0.0813(3) -0.0268(4) O1 0.125(3) 0.062(2) 0.099(2) -0.0182(19) 0.064(2) 0.012(2) O2 0.084(2) 0.101(3) 0.0459(16) -0.0033(17) 0.0217(15) 0.0036(19) O3 0.0427(16) 0.112(3) 0.095(2) 0.017(2) 0.0262(16) 0.0129(16) O4 0.0477(15) 0.083(2) 0.0565(17) 0.0042(15) 0.0280(13) -0.0059(14) N1 0.144(4) 0.044(2) 0.120(3) -0.005(2) 0.081(3) -0.013(2) N2 0.053(2) 0.141(4) 0.068(2) 0.031(3) 0.022(2) 0.005(2) C1 0.0505(19) 0.039(2) 0.0389(18) 0.0046(15) 0.0176(16) -0.0028(15) C2 0.068(3) 0.048(2) 0.051(2) 0.0117(19) 0.033(2) 0.014(2) C3 0.077(3) 0.050(2) 0.060(3) 0.005(2) 0.039(2) -0.009(2) C4 0.060(2) 0.063(3) 0.059(2) -0.019(2) 0.0368(19) -0.017(3) C5 0.053(2) 0.060(3) 0.070(3) -0.004(2) 0.031(2) 0.004(2) C6 0.060(2) 0.048(2) 0.053(2) 0.0045(18) 0.026(2) -0.0011(19) C7 0.0490(19) 0.0335(17) 0.046(2) 0.0066(15) 0.0225(17) 0.0004(15) C8 0.058(2) 0.076(3) 0.0445(19) 0.005(3) 0.0203(17) 0.004(3) C9 0.0429(18) 0.073(3) 0.055(2) 0.012(3) 0.0123(16) 0.008(2) C10 0.0399(18) 0.051(2) 0.049(2) 0.0005(17) 0.0167(16) 0.0037(16) C11 0.0489(19) 0.0336(17) 0.0434(19) 0.0027(14) 0.0221(16) -0.0010(14) C12 0.0495(17) 0.0334(16) 0.0445(17) 0.0032(19) 0.0232(15) -0.003(2) C13 0.078(3) 0.041(2) 0.067(3) 0.001(2) 0.039(2) -0.008(2) C14 0.045(2) 0.068(3) 0.046(2) 0.0130(19) 0.0201(19) -0.0035(19) C15 0.048(2) 0.064(2) 0.063(3) -0.003(2) 0.027(2) 0.0036(19) C16 0.063(3) 0.099(4) 0.073(3) -0.004(3) 0.045(2) -0.008(3) C17 0.106(4) 0.141(6) 0.108(4) -0.002(4) 0.040(3) -0.069(5) C18 0.158(6) 0.167(7) 0.170(7) 0.030(6) 0.130(6) 0.060(5) C19 0.096(4) 0.116(4) 0.075(3) 0.011(3) 0.051(3) -0.003(3) C20 0.060(2) 0.054(3) 0.059(3) -0.011(2) 0.034(2) -0.008(2) C21 0.148(5) 0.159(7) 0.058(3) -0.034(4) 0.041(3) -0.027(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 C4 1.910(3) . ? O1 C20 1.178(5) . ? O2 C20 1.314(5) . ? O2 C21 1.471(6) . ? O3 C15 1.193(5) . ? O4 C15 1.329(5) . ? O4 C16 1.492(5) . ? N1 C13 1.127(5) . ? N2 C14 1.125(5) . ? C1 C6 1.378(5) . ? C1 C2 1.391(5) . ? C1 C7 1.527(5) . ? C2 C3 1.375(6) . ? C3 C4 1.371(6) . ? C4 C5 1.364(7) . ? C5 C6 1.392(5) . ? C7 C8 1.527(5) . ? C7 C12 1.555(5) . ? C8 C9 1.490(5) . ? C9 C10 1.313(5) . ? C10 C15 1.510(5) . ? C10 C11 1.517(5) . ? C11 C20 1.526(5) . ? C11 C12 1.557(4) . ? C12 C13 1.476(6) . ? C12 C14 1.481(5) . ? C16 C17 1.492(8) . ? C16 C18 1.502(8) . ? C16 C19 1.510(7) . ? 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 C20 O2 C21 116.1(5) . . ? C15 O4 C16 123.1(3) . . ? C6 C1 C2 119.0(3) . . ? C6 C1 C7 119.3(3) . . ? C2 C1 C7 121.7(3) . . ? C3 C2 C1 120.2(4) . . ? C4 C3 C2 119.5(4) . . ? C5 C4 C3 121.9(3) . . ? C5 C4 Br1 118.3(3) . . ? C3 C4 Br1 119.8(3) . . ? C4 C5 C6 118.4(4) . . ? C1 C6 C5 121.0(4) . . ? C1 C7 C8 113.9(3) . . ? C1 C7 C12 114.9(3) . . ? C8 C7 C12 108.5(3) . . ? C9 C8 C7 111.9(3) . . ? C10 C9 C8 123.9(3) . . ? C9 C10 C15 119.0(3) . . ? C9 C10 C11 124.0(3) . . ? C15 C10 C11 116.9(3) . . ? C10 C11 C20 110.9(3) . . ? C10 C11 C12 111.0(3) . . ? C20 C11 C12 110.9(3) . . ? C13 C12 C14 107.6(3) . . ? C13 C12 C7 109.3(3) . . ? C14 C12 C7 110.6(3) . . ? C13 C12 C11 111.6(3) . . ? C14 C12 C11 107.9(3) . . ? C7 C12 C11 109.7(3) . . ? N1 C13 C12 177.7(5) . . ? N2 C14 C12 178.7(4) . . ? O3 C15 O4 126.9(4) . . ? O3 C15 C10 124.0(4) . . ? O4 C15 C10 109.0(3) . . ? C17 C16 O4 109.0(4) . . ? C17 C16 C18 112.8(5) . . ? O4 C16 C18 109.5(5) . . ? C17 C16 C19 110.3(5) . . ? O4 C16 C19 102.2(3) . . ? C18 C16 C19 112.5(5) . . ? O1 C20 O2 125.4(4) . . ? O1 C20 C11 123.4(4) . . ? O2 C20 C11 111.1(3) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.362 _refine_diff_density_min -0.328 _refine_diff_density_rms 0.093 _chemical_absolute_configuration ad