#------------------------------------------------------------------------------ #$Date: 2021-11-21 01:12:20 +0200 (Sun, 21 Nov 2021) $ #$Revision: 270790 $ #$URL: file:///home/coder/svn-repositories/cod/cif/1/56/53/1565337.cif $ #------------------------------------------------------------------------------ # # This file is available in the Crystallography Open Database (COD), # http://www.crystallography.net/ # # All data on this site have been placed in the public domain by the # contributors. # data_1565337 loop_ _publ_author_name 'Shen, Chong' 'Cheng, Xiang' 'Wei, Liang' 'Wang, Ruo-Qing' 'Wang, Chun-Jiang' _publ_section_title ; Stereodivergent Synthesis via Iridium-Catalyzed Asymmetric Double Allylic Alkylation of Cyanoacetate ; _journal_name_full 'Chemical Science' _journal_paper_doi 10.1039/D1SC06115A _journal_year 2021 _chemical_formula_moiety 'C25 H25 Br2 N O2' _chemical_formula_sum 'C25 H25 Br2 N O2' _chemical_formula_weight 531.28 _space_group_crystal_system monoclinic _space_group_IT_number 11 _space_group_name_Hall '-P 2yb' _space_group_name_H-M_alt 'P 1 21/m 1' _atom_sites_solution_hydrogens mixed _atom_sites_solution_primary direct _audit_creation_date 2021-01-18 _audit_creation_method ; Olex2 1.2 (compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506) ; _audit_update_record ; 2021-07-14 deposited with the CCDC. 2021-11-19 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 104.4620(10) _cell_angle_gamma 90 _cell_formula_units_Z 2 _cell_length_a 5.982 _cell_length_b 20.17050(10) _cell_length_c 9.655 _cell_measurement_reflns_used 2083 _cell_measurement_temperature 100.00(10) _cell_measurement_theta_max 67.495 _cell_measurement_theta_min 4.384 _cell_volume 1128.058(8) _computing_molecular_graphics 'Olex2 (Dolomanov et al., 2009)' _computing_publication_material 'Olex2 (Dolomanov et al., 2009)' _computing_structure_refinement 'ShelXL (Sheldrick, 2015)' _computing_structure_solution 'ShelXS (Sheldrick, 2008)' _diffrn_ambient_temperature 100.00(10) _diffrn_detector 'Bruker APEX2 area detector' _diffrn_detector_area_resol_mean 7.9 _diffrn_detector_type 'CCD area detector' _diffrn_measured_fraction_theta_full 0.996 _diffrn_measured_fraction_theta_max 0.996 _diffrn_measurement_device 'three-circle diffractometer' _diffrn_measurement_device_type 'Bruker SMART APEX2 area detector' _diffrn_measurement_method '\w and \f scans' _diffrn_radiation_monochromator 'mirror optics' _diffrn_radiation_probe x-ray _diffrn_radiation_type CuK\a _diffrn_radiation_wavelength 1.54178 _diffrn_reflns_av_R_equivalents 0.0370 _diffrn_reflns_av_unetI/netI 0.0135 _diffrn_reflns_Laue_measured_fraction_full 0.996 _diffrn_reflns_Laue_measured_fraction_max 0.996 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_k_max 24 _diffrn_reflns_limit_k_min -24 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_number 22395 _diffrn_reflns_point_group_measured_fraction_full 0.996 _diffrn_reflns_point_group_measured_fraction_max 0.996 _diffrn_reflns_theta_full 66.500 _diffrn_reflns_theta_max 67.495 _diffrn_reflns_theta_min 4.384 _diffrn_source 'microfocus sealed X-ray tube' _diffrn_source_type 'Incoatec I\ms' _exptl_absorpt_coefficient_mu 4.724 _exptl_absorpt_correction_T_max 0.685 _exptl_absorpt_correction_T_min 0.449 _exptl_absorpt_correction_type multi-scan _exptl_crystal_colour colourless _exptl_crystal_colour_primary colourless _exptl_crystal_density_diffrn 1.564 _exptl_crystal_description prism _exptl_crystal_F_000 536 _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.08 _refine_diff_density_max 0.343 _refine_diff_density_min -0.351 _refine_diff_density_rms 0.058 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.074 _refine_ls_hydrogen_treatment mixed _refine_ls_matrix_type full _refine_ls_number_parameters 162 _refine_ls_number_reflns 2083 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.074 _refine_ls_R_factor_all 0.0206 _refine_ls_R_factor_gt 0.0205 _refine_ls_shift/su_max 0.002 _refine_ls_shift/su_mean 0.000 _refine_ls_structure_factor_coef Fsqd _refine_ls_weighting_details ; w=1/[\s^2^(Fo^2^)+(0.0236P)^2^+0.9886P] where P=(Fo^2^+2Fc^2^)/3 ; _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0514 _refine_ls_wR_factor_ref 0.0514 _reflns_Friedel_coverage 0.000 _reflns_number_gt 2075 _reflns_number_total 2083 _reflns_threshold_expression 'I > 2\s(I)' _cod_data_source_file d1sc06115a2.cif _cod_data_source_block wang1 _cod_database_code 1565337 _shelxl_version_number 2013-2 _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; _shelx_estimated_absorpt_t_max 0.704 _shelx_estimated_absorpt_t_min 0.331 _olex2_refinement_description ; 1. Fixed Uiso At 1.2 times of: All C(H) groups At 1.5 times of: All C(H,H,H) groups 2. Others Fixed Sof: H15A(0.5) H15B(0.5) H15C(0.5) 3.a Ternary CH refined with riding coordinates: C3(H3) 3.b Aromatic/amide H refined with riding coordinates: C7(H7), C8(H8), C10(H10), C11(H11) 3.c Idealised Me refined as rotating group: C14(H14A,H14B,H14C), C15(H15A,H15B,H15C) ; _shelx_res_file ; TITL WANG1 in P21/m #11 REM reset to P21/m #11 CELL 1.54178 5.9821 20.1705 9.6547 90 104.462 90 ZERR 2 0 0.0001 0 0 0.001 0 LATT 1 SYMM -X,0.5+Y,-Z SFAC C H Br N O UNIT 50 50 4 2 4 L.S. 6 0 0 PLAN 10 SIZE 0.3 0.15 0.08 TEMP -173.15(10) BOND fmap 2 53 acta 133 OMIT 0 135 OMIT 1 0 1 OMIT 2 6 2 REM REM REM WGHT 0.023600 0.988600 FVAR 0.60789 BR1 3 0.426392 0.559192 0.163875 11.00000 0.02342 0.01668 = 0.02672 0.00457 0.01025 -0.00454 O1 5 0.120061 0.250000 0.164047 10.50000 0.01178 0.01543 = 0.00957 0.00000 0.00353 0.00000 O2 5 0.484514 0.250000 0.306625 10.50000 0.01061 0.01770 = 0.01640 0.00000 0.00427 0.00000 N1 4 0.462689 0.250000 0.657164 10.50000 0.01601 0.02332 = 0.01690 0.00000 0.00152 0.00000 C1 1 0.154352 0.250000 0.410473 10.50000 0.00959 0.01076 = 0.01124 0.00000 0.00306 0.00000 C2 1 0.331683 0.250000 0.547953 10.50000 0.01260 0.01155 = 0.01467 0.00000 0.00676 0.00000 C3 1 0.003241 0.315499 0.397290 11.00000 0.00887 0.01103 = 0.01389 0.00027 0.00262 0.00059 AFIX 13 H3 2 -0.143161 0.306272 0.323243 11.00000 -1.20000 AFIX 0 C4 1 -0.066119 0.331785 0.534155 11.00000 0.01661 0.01513 = 0.02051 0.00305 0.01037 0.00329 H4 2 -0.169329 0.302543 0.557279 11.00000 0.02869 C5 1 -0.005391 0.384397 0.614461 11.00000 0.02268 0.02544 = 0.02069 -0.00351 0.01034 -0.00035 H5A 2 -0.058230 0.389984 0.695349 11.00000 0.02459 H5B 2 0.087057 0.415220 0.590055 11.00000 0.03489 C6 1 0.114519 0.374658 0.343473 11.00000 0.01395 0.01028 = 0.01289 -0.00201 0.00550 0.00027 C7 1 0.344267 0.392837 0.399068 11.00000 0.01461 0.01322 = 0.01539 0.00033 0.00338 0.00115 AFIX 43 H7 2 0.438461 0.367440 0.474248 11.00000 -1.20000 AFIX 0 C8 1 0.437856 0.447592 0.346209 11.00000 0.01253 0.01546 = 0.02054 -0.00361 0.00568 -0.00228 AFIX 43 H8 2 0.595552 0.459032 0.383229 11.00000 -1.20000 AFIX 0 C9 1 0.298013 0.485068 0.239087 11.00000 0.01973 0.01092 = 0.01879 -0.00048 0.01024 -0.00171 C10 1 0.066904 0.469945 0.184926 11.00000 0.01853 0.01555 = 0.01449 0.00109 0.00485 0.00224 AFIX 43 H10 2 -0.028666 0.497125 0.113837 11.00000 -1.20000 AFIX 0 C11 1 -0.022621 0.414188 0.236615 11.00000 0.01157 0.01562 = 0.01480 -0.00074 0.00421 -0.00014 AFIX 43 H11 2 -0.180076 0.402772 0.198504 11.00000 -1.20000 AFIX 0 C12 1 0.277789 0.250000 0.287728 10.50000 0.01343 0.00712 = 0.01330 0.00000 0.00301 0.00000 C13 1 0.188161 0.250000 0.024846 10.50000 0.01902 0.01678 = 0.00984 0.00000 0.00765 0.00000 C14 1 0.322970 0.312700 0.012639 11.00000 0.03012 0.01915 = 0.01968 0.00088 0.01184 -0.00564 AFIX 137 H14A 2 0.234539 0.351505 0.029218 11.00000 -1.50000 H14B 2 0.349721 0.315332 -0.083299 11.00000 -1.50000 H14C 2 0.471551 0.311682 0.084127 11.00000 -1.50000 AFIX 0 C15 1 -0.044205 0.250000 -0.082391 10.50000 0.02451 0.03326 = 0.01241 0.00000 0.00223 0.00000 PART -1 AFIX 137 H15A 2 -0.021944 0.252848 -0.179392 10.50000 -1.50000 H15B 2 -0.134564 0.288169 -0.064665 10.50000 -1.50000 H15C 2 -0.126743 0.208982 -0.072632 10.50000 -1.50000 AFIX 0 HKLF 4 REM WANG1 in P21/m #11 REM R1 = 0.0205 for 2075 Fo > 4sig(Fo) and 0.0206 for all 2083 data REM 162 parameters refined using 0 restraints END WGHT 0.0236 0.9887 REM Highest difference peak 0.343, deepest hole -0.351, 1-sigma level 0.058 Q1 1 0.2194 0.2500 0.3538 10.50000 0.05 0.34 Q2 1 0.0873 0.2176 0.4019 11.00000 0.05 0.32 Q3 1 0.0599 0.3440 0.3754 11.00000 0.05 0.30 Q4 1 0.0467 0.3993 0.3075 11.00000 0.05 0.27 Q5 1 0.2618 0.2818 0.0210 11.00000 0.05 0.26 Q6 1 0.2352 0.3807 0.3536 11.00000 0.05 0.24 Q7 1 -0.0265 0.3201 0.4668 11.00000 0.05 0.23 Q8 1 0.1860 0.4809 0.2133 11.00000 0.05 0.22 Q9 1 0.3601 0.4631 0.2811 11.00000 0.05 0.22 Q10 1 0.3811 0.4189 0.3623 11.00000 0.05 0.21 ; _shelx_res_checksum 28497 _olex2_submission_special_instructions 'No special instructions were received' loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y+1/2, -z' '-x, -y, -z' 'x, -y-1/2, z' 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group Br1 Br 0.42639(3) 0.55919(2) 0.16388(2) 0.02157(8) Uani 1 1 d . . . . . O1 O 0.1201(3) 0.2500 0.16405(16) 0.0121(3) Uani 1 2 d S T P . . O2 O 0.4845(3) 0.2500 0.30663(17) 0.0147(3) Uani 1 2 d S T P . . N1 N 0.4627(4) 0.2500 0.6572(2) 0.0192(4) Uani 1 2 d S T P . . C1 C 0.1544(4) 0.2500 0.4105(2) 0.0104(4) Uani 1 2 d S T P . . C2 C 0.3317(4) 0.2500 0.5480(2) 0.0123(4) Uani 1 2 d S T P . . C3 C 0.0032(3) 0.31550(8) 0.39729(16) 0.0113(3) Uani 1 1 d . . . . . H3 H -0.1432 0.3063 0.3232 0.014 Uiso 1 1 calc R . . . . C4 C -0.0661(3) 0.33179(8) 0.53416(18) 0.0164(3) Uani 1 1 d . . . . . H4 H -0.169(4) 0.3025(11) 0.557(2) 0.029(6) Uiso 1 1 d . . . . . C5 C -0.0054(3) 0.38440(10) 0.6145(2) 0.0221(4) Uani 1 1 d . . . . . H5A H -0.058(4) 0.3900(11) 0.695(2) 0.025(5) Uiso 1 1 d . . . . . H5B H 0.087(4) 0.4152(13) 0.590(3) 0.035(6) Uiso 1 1 d . . . . . C6 C 0.1145(3) 0.37466(8) 0.34347(16) 0.0120(3) Uani 1 1 d . . . . . C7 C 0.3443(3) 0.39284(8) 0.39907(17) 0.0145(3) Uani 1 1 d . . . . . H7 H 0.4385 0.3674 0.4742 0.017 Uiso 1 1 calc R . . . . C8 C 0.4379(3) 0.44759(8) 0.34621(18) 0.0159(3) Uani 1 1 d . . . . . H8 H 0.5956 0.4590 0.3832 0.019 Uiso 1 1 calc R . . . . C9 C 0.2980(3) 0.48507(8) 0.23909(17) 0.0155(3) Uani 1 1 d . . . . . C10 C 0.0669(3) 0.46994(8) 0.18493(17) 0.0161(3) Uani 1 1 d . . . . . H10 H -0.0287 0.4971 0.1138 0.019 Uiso 1 1 calc R . . . . C11 C -0.0226(3) 0.41419(8) 0.23661(17) 0.0138(3) Uani 1 1 d . . . . . H11 H -0.1801 0.4028 0.1985 0.017 Uiso 1 1 calc R . . . . C12 C 0.2778(4) 0.2500 0.2877(2) 0.0113(4) Uani 1 2 d S T P . . C13 C 0.1882(4) 0.2500 0.0248(2) 0.0145(5) Uani 1 2 d S T P . . C14 C 0.3230(3) 0.31270(9) 0.01264(19) 0.0220(4) Uani 1 1 d . . . . . H14A H 0.2345 0.3515 0.0292 0.033 Uiso 1 1 calc GR . . . . H14B H 0.3497 0.3153 -0.0833 0.033 Uiso 1 1 calc GR . . . . H14C H 0.4716 0.3117 0.0841 0.033 Uiso 1 1 calc GR . . . . C15 C -0.0442(5) 0.2500 -0.0824(3) 0.0238(5) Uani 1 2 d S T P . . H15A H -0.0219 0.2528 -0.1794 0.036 Uiso 0.5 1 calc GR . . A -1 H15B H -0.1346 0.2882 -0.0647 0.036 Uiso 0.5 1 calc GR . . A -1 H15C H -0.1267 0.2090 -0.0726 0.036 Uiso 0.5 1 calc GR . . A -1 loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.02342(13) 0.01668(11) 0.02672(12) 0.00457(7) 0.01025(8) -0.00454(6) O1 0.0118(8) 0.0154(8) 0.0096(7) 0.000 0.0035(6) 0.000 O2 0.0106(8) 0.0177(8) 0.0164(8) 0.000 0.0043(6) 0.000 N1 0.0160(10) 0.0233(11) 0.0169(11) 0.000 0.0015(9) 0.000 C1 0.0096(10) 0.0108(10) 0.0112(10) 0.000 0.0031(8) 0.000 C2 0.0126(11) 0.0116(10) 0.0147(11) 0.000 0.0068(10) 0.000 C3 0.0089(7) 0.0110(7) 0.0139(7) 0.0003(6) 0.0026(6) 0.0006(6) C4 0.0166(8) 0.0151(8) 0.0205(8) 0.0031(7) 0.0104(7) 0.0033(7) C5 0.0227(9) 0.0254(10) 0.0207(9) -0.0035(7) 0.0103(7) -0.0003(8) C6 0.0139(8) 0.0103(7) 0.0129(7) -0.0020(6) 0.0055(6) 0.0003(6) C7 0.0146(8) 0.0132(8) 0.0154(7) 0.0003(6) 0.0034(6) 0.0011(6) C8 0.0125(8) 0.0155(8) 0.0205(8) -0.0036(6) 0.0057(7) -0.0023(6) C9 0.0197(9) 0.0109(7) 0.0188(8) -0.0005(6) 0.0102(7) -0.0017(6) C10 0.0185(8) 0.0156(8) 0.0145(7) 0.0011(6) 0.0048(6) 0.0022(6) C11 0.0116(8) 0.0156(8) 0.0148(7) -0.0007(6) 0.0042(6) -0.0001(6) C12 0.0134(12) 0.0071(10) 0.0133(11) 0.000 0.0030(9) 0.000 C13 0.0190(12) 0.0168(11) 0.0098(10) 0.000 0.0077(9) 0.000 C14 0.0301(10) 0.0192(9) 0.0197(8) 0.0009(7) 0.0118(7) -0.0056(7) C15 0.0245(14) 0.0333(14) 0.0124(11) 0.000 0.0022(10) 0.000 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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' Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 C12 O1 C13 121.11(17) . . ? C2 C1 C3 109.79(11) . 4_565 ? C2 C1 C3 109.79(11) . . ? C2 C1 C12 108.40(18) . . ? C3 C1 C3 112.61(17) 4_565 . ? C12 C1 C3 108.07(11) . . ? C12 C1 C3 108.07(11) . 4_565 ? N1 C2 C1 177.4(2) . . ? C4 C3 C1 112.62(13) . . ? C4 C3 C6 111.49(13) . . ? C6 C3 C1 113.05(13) . . ? C5 C4 C3 126.51(16) . . ? C7 C6 C3 123.29(14) . . ? C7 C6 C11 118.36(15) . . ? C11 C6 C3 118.31(14) . . ? C8 C7 C6 121.06(15) . . ? C9 C8 C7 119.01(15) . . ? C8 C9 Br1 119.23(12) . . ? C8 C9 C10 121.54(15) . . ? C10 C9 Br1 119.24(12) . . ? C9 C10 C11 118.71(15) . . ? C10 C11 C6 121.26(15) . . ? O1 C12 C1 108.80(18) . . ? O2 C12 O1 127.6(2) . . ? O2 C12 C1 123.6(2) . . ? O1 C13 C14 109.74(12) . 4_565 ? O1 C13 C14 109.74(12) . . ? O1 C13 C15 101.82(18) . . ? C14 C13 C14 112.6(2) 4_565 . ? C15 C13 C14 111.21(13) . . ? C15 C13 C14 111.21(13) . 4_565 ? 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 C9 1.9055(16) . ? O1 C12 1.324(3) . ? O1 C13 1.499(3) . ? O2 C12 1.204(3) . ? N1 C2 1.146(3) . ? C1 C2 1.478(3) . ? C1 C3 1.5879(19) . ? C1 C3 1.5878(19) 4_565 ? C1 C12 1.545(3) . ? C3 C4 1.517(2) . ? C3 C6 1.520(2) . ? C4 C5 1.311(3) . ? C6 C7 1.394(2) . ? C6 C11 1.397(2) . ? C7 C8 1.392(2) . ? C8 C9 1.382(2) . ? C9 C10 1.384(2) . ? C10 C11 1.391(2) . ? C13 C14 1.520(2) . ? C13 C14 1.520(2) 4_565 ? C13 C15 1.512(3) . ?