Catalyst-free C-H bond halogenation/imidation of N-heterocycles.
Liu, Miao; Zhang, Xueying; Li, Nan; Zhang, Xu; Zhao, Congyong; Shen, Xiaobao; Zhai, Hongbin; Wu, Fufang; Organic & biomolecular chemistry 23 (2025) 10072–10076; doi:10.1039/d5ob01463h

data_7160816
_publ_section_title
;
 Catalyst-free C-H bond halogenation/imidation of N-heterocycles.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              10072
_journal_page_last               10076
_journal_paper_doi               10.1039/d5ob01463h
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C17 H9 Br N2 O2'
_chemical_formula_sum            'C17 H9 Br N2 O2'
_chemical_formula_weight         353.17
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-25
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-05-29 deposited with the CCDC.	2025-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 121.523(7)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.9318(14)
_cell_length_b                   11.3071(6)
_cell_length_c                   15.6112(10)
_cell_measurement_reflns_used    4033
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      28.3850
_cell_measurement_theta_min      2.1960
_cell_volume                     2848.6(4)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.874
_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    -51.00  -9.00   0.50   21.51    --   24.18 -19.00-120.00   84
  2  \w    -51.00   5.00   0.50   21.51    --   24.18 -19.00-180.00  112
  3  \w    -72.00 -13.00   0.50   21.51    --   24.18 -19.00 -60.00  118
  4  \w    -71.00   5.00   0.50   21.51    --   24.18 -19.00  90.00  152
  5  \w    -88.00 -63.00   0.50   21.51    --  -23.24-144.00  29.00   50
  6  \w     37.00  95.00   0.50   21.51    --   24.18-144.00  29.00  116
  7  \w     41.00  99.00   0.50   21.51    --   24.18-178.00-180.00  116
  8  \w    -90.00 -32.00   0.50   21.51    --  -23.24 144.00  83.00  116
  9  \w     50.00  75.00   0.50   21.51    --   24.18 178.00  90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0171792000
_diffrn_orient_matrix_UB_12      0.0350013000
_diffrn_orient_matrix_UB_13      -0.0362460000
_diffrn_orient_matrix_UB_21      0.0081617000
_diffrn_orient_matrix_UB_22      0.0519051000
_diffrn_orient_matrix_UB_23      0.0246368000
_diffrn_orient_matrix_UB_31      0.0443236000
_diffrn_orient_matrix_UB_32      0.0040040000
_diffrn_orient_matrix_UB_33      -0.0026782000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0477
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.874
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            10889
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.680
_diffrn_reflns_theta_min         2.199
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.894
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.02647
_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_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.647
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.628
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     209
_refine_ls_number_reflns         3529
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0803
_refine_ls_R_factor_gt           0.0522
_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^)+(0.0565P)^2^+4.1567P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1120
_refine_ls_wR_factor_ref         0.1200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2580
_reflns_number_total             3529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01463h2.cif
_cod_data_source_block           lm250225
_cod_depositor_comments          'Adding full bibliography for 7160816.cif.'
_cod_database_code               7160816
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.671
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O1A-C10 \\sim O1-C10
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C10 \\sim O1 \\sim O1A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
4. Others
 Sof(O1A)=1-FVAR(1)
 Sof(O1)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C7(H7), C4(H4), C15(H15), C12(H12), C5(H5), C13(H13), C6(H6), C14(H14)
;
_shelx_res_checksum              10878
_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 16.924
_oxdiff_exptl_absorpt_empirical_full_min 0.469