Asymmetric synthesis of atropisomeric arylpyrazoles <i>via</i> direct arylation of 5-aminopyrazoles with naphthoquinones.
Liu, Jiamin; Wei, Xingfu; Wang, Yue; Qu, Jingping; Wang, Baomin; Organic & biomolecular chemistry 22 (2024) 4254–4263; doi:10.1039/d4ob00514g

data_7159941
_publ_section_title
;
 Asymmetric synthesis of atropisomeric arylpyrazoles <i>via</i> direct
 arylation of 5-aminopyrazoles with naphthoquinones.
;
_journal_issue                   21
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4254
_journal_page_last               4263
_journal_paper_doi               10.1039/d4ob00514g
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C25 H24 Br N3 O4'
_chemical_formula_sum            'C25 H24 Br N3 O4'
_chemical_formula_weight         510.38
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-01 deposited with the CCDC.	2024-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5837(8)
_cell_length_b                   16.3187(15)
_cell_length_c                   19.3809(17)
_cell_measurement_reflns_used    9860
_cell_measurement_temperature    299.0
_cell_measurement_theta_max      22.51
_cell_measurement_theta_min      2.44
_cell_volume                     2714.8(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      299.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0755
_diffrn_reflns_av_unetI/netI     0.0490
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            70426
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.102
_diffrn_source_current           40.0
_diffrn_source_power             1.8
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.546
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5745
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1163 before and 0.0729 after correction.
The Ratio of minimum to maximum transmission is 0.7705.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       block
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.333
_refine_diff_density_min         -0.442
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.041(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         5559
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0539
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+1.5119P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1205
_refine_ls_wR_factor_ref         0.1364
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3667
_reflns_number_total             5559
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob00514g2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7159941.cif.'
_cod_database_code               7159941
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.663
_shelx_estimated_absorpt_t_min   0.629
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95903
 0.04097
2.a Rotating group:
 N1(H1A,H1B)
2.b Aromatic/amide H refined with riding coordinates:
 C012(H012), C014(H014), C01G(H01G), C01K(H01K), C01M(H01M), C01Q(H01Q),
 C01U(H01U), C01V(H01V)
2.c Idealised Me refined as rotating group:
 C00W(H00A,H00B,H00C), C01N(H01A,H01B,H01C), C01P(H01D,H01E,H01F), C01W(H01H,
 H01I,H01J)
2.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              12545
_shelx_fab_checksum              85828
_olex2_submission_special_instructions 'No special instructions were received'