Organocatalytic asymmetric synthesis of axially and centrally chiral heterotriarylmethanes by a Friedel-Crafts reaction.
Min, Yang; Shen, Hanxiao; Huang, Shaoying; Gu, Haorui; Lin, Xufeng; Organic & biomolecular chemistry 23 (2025) 5359–5372; doi:10.1039/d5ob00532a

data_7160524
_publ_section_title
;
 Organocatalytic asymmetric synthesis of axially and centrally chiral
 heterotriarylmethanes by a Friedel-Crafts reaction.
;
_journal_issue                   22
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5359
_journal_page_last               5372
_journal_paper_doi               10.1039/d5ob00532a
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C H Cl3), C33 H27 F N2 O3'
_chemical_formula_sum            'C33.5 H27.5 Cl1.5 F N2 O3'
_chemical_formula_weight         578.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-09-19
_audit_creation_method
;
FinalCif V65 by Daniel Kratzert, Freiburg 2019,
https://github.com/dkratzert/FinalCif
;
_audit_update_record
;
2025-03-17 deposited with the CCDC.	2025-05-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.022(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5056(7)
_cell_length_b                   13.8298(8)
_cell_length_c                   18.2204(11)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      60.617
_cell_measurement_theta_min      4.263
_cell_volume                     2870.9(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON III M28'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'ZJU Bruker D8 VENTURE Metaljet PHOTON III'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            47692
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         60.801
_diffrn_reflns_theta_min         4.264
_diffrn_source                   'liquid Metal X-ray source'
_diffrn_source_current           3.57
_diffrn_source_power             0.24954300000000001
_diffrn_source_type              'Bruker Excillum Metaljet D2+'
_diffrn_source_voltage           69.9
_exptl_absorpt_coefficient_mu    1.295
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6891
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1049 before and 0.0635 after correction.
The Ratio of minimum to maximum transmission is 0.9165.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             1204
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.379
_refine_diff_density_min         -0.456
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2792 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.097(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         6564
_refine_ls_number_restraints     47
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0801P)^2^+1.4501P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1264
_refine_ls_wR_factor_ref         0.1294
_reflns_Friedel_coverage         0.913
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                6203
_reflns_number_total             6564
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob00532a2.cif
_cod_data_source_block           240918_my0918_f1_tscl
_cod_depositor_comments          'Adding full bibliography for 7160524.cif.'
_cod_original_formula_sum        'C33.50 H27.50 Cl1.50 F N2 O3'
_cod_database_code               7160524
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_min   0.820
_shelx_estimated_absorpt_t_max   0.926
_olex2_diffrn_ambient_temperature_device 'Oxford Cryostream 800'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C34-Cl1 \\sim C34-Cl2 \\sim C34-Cl3
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl2-Cl3 \\sim Cl3-Cl1
 with sigma of 0.04
 C32-C33 \\sim C32-C33A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
O3 \\sim C32 \\sim C33 \\sim C33A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 Cl1, Cl2, Cl3, C34
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H32C)=Sof(H32D)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
 Fixed Sof: Cl1(0.5) Cl2(0.5) Cl3(0.5) C34(0.5) H34(0.5)
6.a Ternary CH refined with riding coordinates:
 C34(H34), C20(H20)
6.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C32(H32C,H32D)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C1(H1A), C2(H2A), C3(H3), C4(H4), C7(H7), C8(H8), C16(H16),
 C17(H17), C18(H18), C19(H19), C22(H22), C24(H24), C25(H25), C26(H26), C28(H28),
  C30(H30)
6.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C33(H33A,H33B,H33C), C33A(H33D,H33E,H33F)
;
_olex2_submission_special_instructions 'No special instructions were received'