The Electrochemically Enabled α-C(sp3)–H Azolation of Ketones
Fang, Songlin; Zhong, Kaihui; Zeng, Shaogao; Hu, Xinwei; Sun, Ping-Hua; Ruan, Zhixiong; Chemical Communications  (2023) –; doi:10.1039/D3CC02852F

data_7132102
_publ_section_title
;
 The Electrochemically Enabled \a-C(sp3)--H Azolation of Ketones
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02852F
_journal_year                    2023
_chemical_formula_moiety         'C21 H16 N4 O'
_chemical_formula_sum            'C21 H16 N4 O'
_chemical_formula_weight         340.38
_chemical_name_systematic        3n
_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             2022-01-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-06-22 deposited with the CCDC.	2023-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.904(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   32.257(5)
_cell_length_b                   6.2874(5)
_cell_length_c                   17.439(2)
_cell_measurement_reflns_used    2519
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      73.0730
_cell_measurement_theta_min      2.7970
_cell_volume                     3433.2(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.976
_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    -63.00  33.00   1.00   10.00    --  -40.73  40.00  79.00   96
  2  \w    -33.00  -2.00   1.00   10.00    --  -40.73 125.00 150.00   31
  3  \w      1.00  61.00   1.00   10.00    --   40.73 -99.00 150.00   60
  4  \w     57.00  96.00   1.00   10.00    --   40.73-125.00  30.00   39
  5  \w     39.00  66.00   1.00    6.00    --  107.58 -45.00 150.00   27
  6  \w     89.00 116.00   1.00    6.00    --  107.58 -45.00 150.00   27
  7  \w     86.00 114.00   1.00    6.00    --  107.58 -45.00  30.00   28
  8  \w     82.00 107.00   1.00    6.00    --  107.58 -95.00 -60.00   25
  9  \w     45.00 119.00   1.00    6.00    --  107.58 -30.00   0.00   74
 10  \w     82.00 174.00   1.00    6.00    --  107.58  45.00 -60.00   92
 11  \w     90.00 115.00   1.00   10.00    --   40.73  38.00-180.00   25
 12  \w     37.00 136.00   1.00    6.00    --  107.58 -30.00 -90.00   99
 13  \w     90.00 117.00   1.00    6.00    --  107.58-125.00  90.00   27
 14  \w     42.00 133.00   1.00    6.00    --  107.58 -77.00   0.00   91
 15  \w     42.00 122.00   1.00    6.00    --  107.58-125.00-150.00   80
 16  \w     37.00 136.00   1.00    6.00    --  107.58 -77.00-150.00   99
 17  \w     33.00  60.00   1.00   10.00    --   40.73  38.00-180.00   27
 18  \w     23.00  80.00   1.00   10.00    --   40.73-125.00 -90.00   57
 19  \w     29.00 157.00   1.00    6.00    --  107.58 -15.00 120.00  128
 20  \w   -113.00 -16.00   1.00   10.00    --  -40.73 -38.00 -90.00   97
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0153444000
_diffrn_orient_matrix_UB_12      -0.0128838000
_diffrn_orient_matrix_UB_13      -0.0770643000
_diffrn_orient_matrix_UB_21      0.0459636000
_diffrn_orient_matrix_UB_22      0.0498286000
_diffrn_orient_matrix_UB_23      0.0463581000
_diffrn_orient_matrix_UB_31      0.0086615000
_diffrn_orient_matrix_UB_32      -0.2394121000
_diffrn_orient_matrix_UB_33      0.0138527000
_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  0.0600
_diffrn_reflns_av_unetI/netI     0.0622
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            11406
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.070
_diffrn_reflns_theta_min         2.822
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80281
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.317
_exptl_crystal_description       block
_exptl_crystal_F_000             1424
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.320
_refine_diff_density_min         -0.202
_refine_diff_density_rms         0.044
_refine_ls_extinction_coef       0.00048(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3400
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0947
_refine_ls_R_factor_gt           0.0555
_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^)+(0.0540P)^2^+0.8717P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1350
_refine_ls_wR_factor_ref         0.1543
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2342
_reflns_number_total             3400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02852f2.cif
_cod_data_source_block           184
_cod_original_cell_volume        3433.2(8)
_cod_database_code               7132102
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.911
_reflns_odcompleteness_completeness 100.00
_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
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C19(H19), C8(H8), C20(H20), C9(H9), C10(H10), C16(H16), C1(H1),
 C17(H17), C5(H5), C18(H18), C2(H2), C4(H4), C3(H3)
;
_shelx_res_checksum              82496
_shelx_hkl_checksum              5782
_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 1.602
_oxdiff_exptl_absorpt_empirical_full_min 0.487