Asymmetric Synthesis of Atropisomeric Pyrazole via an Enantioselective Reaction of Azonaphthalene with Pyrazolone
Li, Wenjun; Yuan, Huijun; Li, Yao; Zhao, Hanhui; Yang, Zhihong; Li, Xin; Chemical Communications  (2019) –; doi:10.1039/C9CC06360A

data_7124254
_publ_section_title
;
 Asymmetric Synthesis of Atropisomeric Pyrazole via an Enantioselective
 Reaction of Azonaphthalene with Pyrazolone
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC06360A
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H25 Br N4 O3'
_chemical_formula_sum            'C25 H25 Br N4 O3'
_chemical_formula_weight         509.40
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9181(4)
_cell_length_b                   12.5117(5)
_cell_length_c                   17.7197(7)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    173
_cell_measurement_theta_max      26.31
_cell_measurement_theta_min      2.30
_cell_volume                     2420.58(16)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'Bruker PHOTO 100 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker CMOS area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21960
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.490
_diffrn_reflns_theta_min         2.191
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.732
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5927
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1027 before and 0.0520 after correction. The Ratio of minimum to maximum transmission is 0.7951. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_description       block
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.39
_exptl_crystal_size_min          0.38
_refine_diff_density_max         0.879
_refine_diff_density_min         -0.704
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 1638 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(3)
_refine_ls_extinction_coef       0.0057(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     303
_refine_ls_number_reflns         5001
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0379
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+1.8811P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0915
_reflns_Friedel_coverage         0.767
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4293
_reflns_number_total             5001
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc06360a3.cif
_cod_data_source_block           cxy0664_0m
_cod_database_code               7124254
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.559
_shelx_estimated_absorpt_t_min   0.510
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2.a Riding coordinates:
 O1(H1), N3(H3), N4(H4)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3A), C13(H13), C24(H24), C2(H2), C12(H12), C25(H25), C17(H17), C16(H16),
 C19(H19), C18(H18)
2.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C11(H11A,H11B,H11C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C)
;
_shelx_res_checksum              94137
_shelx_hkl_checksum              21748
_olex2_submission_special_instructions 'No special instructions were received'