Asymmetric synthesis of axially chiral N,N′-carbazolepyrrole via copper-catalyzed Friedel–Crafts reaction
Wang, Xin-Ru; Zhang, Yingying; New Journal of Chemistry 49 (2025) 3849–3854; doi:10.1039/D5NJ00200A

data_7063650
_publ_section_title
;
 Asymmetric synthesis of axially chiral N,N&#x2032;-carbazolepyrrole via
 copper-catalyzed Friedel--Crafts reaction
;
_journal_issue                   10
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              3849
_journal_page_last               3854
_journal_paper_doi               10.1039/D5NJ00200A
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C25 H25 Br N2 O5'
_chemical_formula_sum            'C25 H25 Br N2 O5'
_chemical_formula_weight         513.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-11-26 deposited with the CCDC.	2025-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.416(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9596(5)
_cell_length_b                   7.6809(3)
_cell_length_c                   24.4062(10)
_cell_measurement_reflns_used    9882
_cell_measurement_temperature    258.00
_cell_measurement_theta_max      54.752
_cell_measurement_theta_min      3.240
_cell_volume                     2363.13(16)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      258.00
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0828
_diffrn_reflns_av_unetI/netI     0.0787
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            25114
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.928
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.640
_diffrn_reflns_theta_min         3.239
_diffrn_source_current           2.86
_diffrn_source_power             0.1995708
_diffrn_source_voltage           69.78
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.772
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.4349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1638 before and 0.1061 after correction.
The Ratio of minimum to maximum transmission is 0.5792.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.464
_refine_diff_density_min         -0.812
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Flack x determined using 2498 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.082(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     593
_refine_ls_number_reflns         8578
_refine_ls_number_restraints     185
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.0880
_refine_ls_R_factor_gt           0.0767
_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^)+(0.1541P)^2^+0.2304P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2132
_refine_ls_wR_factor_ref         0.2269
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    0.886
_reflns_Friedel_fraction_max     0.868
_reflns_number_gt                6940
_reflns_number_total             8578
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00200a2.cif
_cod_data_source_block           231026lty_wxr_2_83
_cod_depositor_comments          'Adding full bibliography for 7063650.cif.'
_cod_database_code               7063650
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.917
_shelx_estimated_absorpt_t_min   0.886
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 H1-H1A = H1-H4_$1
 2.1 with sigma of 0.01
3. Rigid bond restraints
 C11A, C12A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C24, C25
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
O4A \\sim O5A \\sim C23A \\sim C24A \\sim C25A: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
O2A \\sim O3A \\sim C19A \\sim C20A \\sim C21A \\sim C22A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O4 \\sim O5 \\sim C19 \\sim C23 \\sim C24 \\sim C25: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O2 \\sim O3 \\sim C20 \\sim C21 \\sim C22: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
5.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C24(H24A,H24B), C21A(H21C,H21D), C24A(H24C,H24D)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C3A(H3A), C4A(H4A), C5A(H5A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A),
 C14A(H14A)
5.c Fitted hexagon refined as free rotating group:
 C12A(C7A,C8A,C9A,C10A,C11A)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C22(H22A,H22B,H22C), C25(H25A,H25B,
 H25C), C17A(H17D,H17E,H17F), C18A(H18D,H18E,H18F), C22A(H22D,H22E,H22F),
 C25A(H25D,H25E,H25F)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O1A(H1A)
;
_shelx_res_checksum              98288
_shelx_hkl_checksum              38335
_olex2_submission_special_instructions 'No special instructions were received'