1,5-Hydrogen atom transfer of α-iminyl radical cations: a new platform for relay annulation for pyridine derivatives and axially chiral heterobiaryls.
Zhou, Yu-Qiang; He, Kui-Cheng; Zheng, Wei-Hao; Lv, Jing-Fang; He, Shi-Mei; Yu, Ning; Yang, Yun-Bo; Liu, Lv-Yan; Jiang, Kun; Wei, Ye; Chemical science 15 (2024) 7502–7514; doi:10.1039/d4sc01858c

data_1572056
_publ_section_title
;
 1,5-Hydrogen atom transfer of &#x3b1;-iminyl radical cations: a new
 platform for relay annulation for pyridine derivatives and axially chiral
 heterobiaryls.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              7502
_journal_page_last               7514
_journal_paper_doi               10.1039/d4sc01858c
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C21 H19 N'
_chemical_formula_sum            'C21 H19 N'
_chemical_formula_weight         285.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-04-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-11-09 deposited with the CCDC.	2024-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.672(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.2995(4)
_cell_length_b                   25.7122(17)
_cell_length_c                   12.4585(16)
_cell_measurement_reflns_used    8115
_cell_measurement_temperature    290.19(10)
_cell_measurement_theta_max      71.6550
_cell_measurement_theta_min      3.6400
_cell_volume                     3191.7(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      290.19(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0243
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -65.00  36.00   1.00    1.00    --  -35.72  19.00  30.00  101
  2  \w    -52.00  32.00   1.00    1.00    --  -35.72  57.00  90.00   84
  3  \w   -103.00 -19.00   1.00    1.00    --  -35.72 -57.00-150.00   84
  4  \w    -33.00  55.00   1.00    1.00    --   35.72 -38.00  60.00   88
  5  \w     24.00  90.00   1.00    1.00    --   35.72-126.00  30.00   66
  6  \w      1.00  75.00   1.00    1.00    --   35.72 -99.00 -30.00   74
  7  \w     39.00 110.00   1.00    1.17    --  107.97 -95.00 -90.00   71
  8  \w    101.00 178.00   1.00    1.17    --  107.97 112.00 -30.00   77
  9  \w     38.00 129.00   1.00    1.17    --  107.97 -30.00-150.00   91
 10  \w     38.00 112.00   1.00    1.17    --  107.97-112.00  30.00   74
 11  \w     87.00 178.00   1.00    1.17    --  107.97  30.00 -60.00   91
 12  \w     38.00 129.00   1.00    1.17    --  107.97 -30.00 120.00   91
 13  \w     81.00 176.00   1.00    1.17    --  107.97  77.00-150.00   95
 14  \w     40.00 125.00   1.00    1.17    --  107.97 -45.00  60.00   85
 15  \w     40.00 135.00   1.00    1.17    --  107.97 -77.00 -60.00   95
 16  \w   -103.00  -9.00   1.00    1.00    --  -35.72 -77.00 120.00   94
 17  \w   -103.00 -19.00   1.00    1.00    --  -35.72 -57.00 -60.00   84
 18  \w   -103.00 -19.00   1.00    1.00    --  -35.72 -57.00  30.00   84
 19  \w    -32.00  52.00   1.00    1.00    --   35.72 -57.00-180.00   84
 20  \w     24.00  90.00   1.00    1.00    --   35.72-126.00-180.00   66
 21  \w     70.00 178.00   1.00    1.17    --  107.97  15.00  60.00  108
 22  \w     70.00 178.00   1.00    1.17    --  107.97  15.00-180.00  108
 23  \w     91.00 176.00   1.00    1.17    --  107.97  45.00 -30.00   85
 24  \w     91.00 176.00   1.00    1.17    --  107.97  45.00  90.00   85
 25  \w     39.00 110.00   1.00    1.17    --  107.97 -95.00 120.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0072829000
_diffrn_orient_matrix_UB_12      -0.1218067000
_diffrn_orient_matrix_UB_13      0.0055524000
_diffrn_orient_matrix_UB_21      -0.0072283000
_diffrn_orient_matrix_UB_22      0.0099885000
_diffrn_orient_matrix_UB_23      0.0596260000
_diffrn_orient_matrix_UB_31      -0.1542827000
_diffrn_orient_matrix_UB_32      0.0377573000
_diffrn_orient_matrix_UB_33      -0.0030933000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            30577
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.748
_diffrn_reflns_theta_min         4.051
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.520
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55655
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.188
_exptl_crystal_description       prism
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.29
_refine_diff_density_max         0.145
_refine_diff_density_min         -0.175
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.0035(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         6172
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0584P)^2^+0.5057P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1146
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5627
_reflns_number_total             6172
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01858c2.cif
_cod_data_source_block           zyq-1-2021
_cod_depositor_comments
;

2025-05-14
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C42 H38 N2'
_cod_original_formula_weight         570.74
_cod_original_formula_moiety         '2(C21 H19 N)'
_cod_original_formula_units_Z            4
_cod_database_code               1572056
_shelxl_version_number           2014-1
_chemical_oxdiff_usercomment     'C1 H1 N1'
_reflns_odcompleteness_completeness 99.18
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C34(H34A,H34B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C7(H7), C8(H8), C9(H9), C10(H10), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C28(H28), C29(H29), C30(H30),
  C31(H31), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.721
_oxdiff_exptl_absorpt_empirical_full_min 0.574