Synthesis of carbinoxamine via α-C(sp3)–H 2-pyridylation of O, S or N-containing compounds enabled by non-D–A-type super organoreductants and sulfoxide- or sulfide HAT reagents
Cui, Xian-Chao; Zhang, Hu; Wang, Yi-Ping; Qu, Jian-Ping; Kang, Yan-Biao; Chemical Science 13 (2022) 11246–11251; doi:10.1039/D2SC03504A

data_1567652
_publ_section_title
;
 Synthesis of carbinoxamine via \a-C(sp3)--H 2-pyridylation of O, S or
 N-containing compounds enabled by non-D--A-type super organoreductants
 and sulfoxide- or sulfide HAT reagents
;
_journal_issue                   37
_journal_name_full               'Chemical Science'
_journal_page_first              11246
_journal_page_last               11251
_journal_paper_doi               10.1039/D2SC03504A
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C0.5 H Cl, C29 H30 N2'
_chemical_formula_sum            'C29.5 H31 Cl N2'
_chemical_formula_weight         449.01
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-09-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-01-02 deposited with the CCDC.	2022-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.612(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.0567(3)
_cell_length_b                   7.51330(10)
_cell_length_c                   32.5379(6)
_cell_measurement_reflns_used    5039
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.9610
_cell_measurement_theta_min      4.1090
_cell_volume                     5079.32(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2013/4 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2169
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.972
_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   -112.00 -29.00   1.00    4.00    --  -41.05 -57.00 150.00   83
  2  \w   -126.00 -98.00   1.00    4.00    --  -41.05-178.00 -60.00   28
  3  \w   -101.00 -20.00   1.00    4.00    --  -41.05 -38.00-150.00   81
  4  \w     44.00 107.00   1.00    8.00    --   99.68-125.00 -60.00   63
  5  \w     75.00 156.00   1.00    8.00    --   99.68  45.00-150.00   81
  6  \w     23.00 126.00   1.00    8.00    --   99.68 -30.00  30.00  103
  7  \w     97.00 138.00   1.00    8.00    --   99.68  45.00-180.00   41
  8  \w     24.00 130.00   1.00    8.00    --   99.68 -77.00 -60.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0701362000
_diffrn_orient_matrix_UB_12      0.0030603000
_diffrn_orient_matrix_UB_13      -0.0006601000
_diffrn_orient_matrix_UB_21      -0.0236417000
_diffrn_orient_matrix_UB_22      0.0263600000
_diffrn_orient_matrix_UB_23      -0.0498323000
_diffrn_orient_matrix_UB_31      -0.0041191000
_diffrn_orient_matrix_UB_32      -0.2034033000
_diffrn_orient_matrix_UB_33      -0.0064974000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0183
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            9093
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.068
_diffrn_reflns_theta_min         4.256
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.458
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64790
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.174
_exptl_crystal_description       block
_exptl_crystal_F_000             1912
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.691
_refine_diff_density_min         -0.841
_refine_diff_density_rms         0.047
_refine_ls_extinction_coef       0.00031(7)
_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   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         4699
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0655
_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^)+(0.0916P)^2^+5.0799P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1823
_refine_ls_wR_factor_ref         0.1908
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4002
_reflns_number_total             4699
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03504a2.cif
_cod_data_source_block           cxc-2-me
_cod_depositor_comments
'Adding full bibliography for 1567652--1567653.cif.'
_cod_original_formula_sum        'C29.50 H31 Cl N2'
_cod_database_code               1567652
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C20H20N2
_shelx_estimated_absorpt_t_max   0.759
_shelx_estimated_absorpt_t_min   0.712
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C30) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
2. Others
 Fixed Sof: H30A(0.5) H30B(0.5)
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C22(H22A,H22B), C30(H30A,H30B)
3.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C3(H3), C24(H24), C6(H6), C8(H8), C4(H4), C17(H17), C5(H5),
 C19(H19), C18(H18), C11(H11), C9(H9), C25(H25), C10(H10), C26(H26), C27(H27)
3.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C13(H13A,H13B,H13C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              46197
_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 1.410
_oxdiff_exptl_absorpt_empirical_full_min 0.684