Cobalt(II)-Catalyzed Activation of C(sp3)–H Bonds: Organic Oxidant Enabled Selective Functionalization
Zhang, He; Sun, Meng-Chan; Yang, Dandan; Li, Tong; Song, Mao-Ping; Niu, Jun-Long; ACS Catalysis  (2022) 1650–1656; doi:10.1021/acscatal.1c05250

data_4519295
_publ_section_title
;
 Cobalt(II)-Catalyzed Activation of C(sp3)--H Bonds: Organic Oxidant
 Enabled Selective Functionalization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1650
_journal_page_last               1656
_journal_paper_doi               10.1021/acscatal.1c05250
_journal_year                    2022
_chemical_formula_moiety         'C26 H20 N2 O'
_chemical_formula_sum            'C26 H20 N2 O'
_chemical_formula_weight         376.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0459(16)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.4714(6)
_cell_length_b                   7.81348(13)
_cell_length_c                   16.8852(3)
_cell_measurement_reflns_used    3129
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8500
_cell_measurement_theta_min      5.7640
_cell_volume                     3997.80(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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   -103.00  -5.00   0.50    1.50    --  -33.50 -77.00 -30.00  196
  2  \w   -101.00 -55.00   0.50    1.50    --  -33.50-153.00 -86.00   92
  3  \w    -43.00  -7.00   0.50    1.50    --  -33.50 -77.00  90.00   72
  4  \w     40.00  94.00   0.50    1.50    --   36.47  37.00 120.00  108
  5  \w    -21.00  15.00   0.50    1.50    --   36.47 -37.00 150.00   72
  6  \w     24.00  56.00   0.50    1.50    --   36.47 -77.00 120.00   64
  7  \w    -30.00  63.00   0.50    1.50    --   36.47 -77.00   0.00  186
  8  \w     28.00  59.00   0.50    1.50    --   36.47 -37.00 150.00   62
  9  \w    -16.00  10.00   0.50    1.50    --   36.47 -77.00 120.00   52
 10  \w     37.00 128.00   0.50   10.00    --  108.00 -30.00-120.00  182
 11  \w    125.00 160.00   0.50   10.00    --  108.00  45.00-120.00   70
 12  \w     42.00 105.00   0.50   10.00    --  108.00 -94.00  30.00  126
 13  \w    118.00 160.00   0.50   10.00    --  108.00 111.00-180.00   84
 14  \w     39.00 137.00   0.50   10.00    --  108.00 -77.00-120.00  196
 15  \w     59.00 108.00   0.50   10.00    --  108.00 -94.00 150.00   98
 16  \w    107.00 134.00   0.50   10.00    --  108.00 -30.00 -30.00   54
 17  \w     38.00  97.00   0.50   10.00    --  108.00 -30.00 -30.00  118
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0206865000
_diffrn_orient_matrix_UB_12      -0.0424114000
_diffrn_orient_matrix_UB_13      -0.0771036000
_diffrn_orient_matrix_UB_21      -0.0461784000
_diffrn_orient_matrix_UB_22      0.0019844000
_diffrn_orient_matrix_UB_23      -0.0469118000
_diffrn_orient_matrix_UB_31      0.0050081000
_diffrn_orient_matrix_UB_32      0.1925062000
_diffrn_orient_matrix_UB_33      -0.0164810000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0189
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            7268
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.039
_diffrn_reflns_theta_max         67.039
_diffrn_reflns_theta_min         5.750
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89416
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.251
_exptl_crystal_description       prism
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.152
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.036
_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     263
_refine_ls_number_reflns         3561
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0778P)^2^+0.9267P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1261
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2968
_reflns_number_total             3561
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c05250_si_002.cif
_cod_data_source_block           201911274
_cod_original_cell_volume        3997.79(12)
_cod_database_code               4519295
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H40O2N4Cl4
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.910
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C16(H16), C17(H17), C19(H19), C23(H23), C24(H24), C25(H25), C26(H26)
2.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_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 1.237
_oxdiff_exptl_absorpt_empirical_full_min 0.882