I2-Mediated transition-metal-free aromatic C–H amination for the synthesis of benzimidazol-2-ones and related heterocycles
Meng, Yinggao; Wang, Bingnan; Ren, Linning; Zhao, Qiongli; Yu, Wenquan; Chang, Junbiao; New Journal of Chemistry 42 (2018) 13790–; doi:10.1039/C8NJ03166E

data_7057563
_publ_section_title
;
 I2-Mediated transition-metal-free aromatic C--H amination for the
 synthesis of benzimidazol-2-ones and related heterocycles
;
_journal_issue                   16
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              13790
_journal_paper_doi               10.1039/C8NJ03166E
_journal_volume                  42
_journal_year                    2018
_chemical_formula_moiety         'C14 H11 Br N2 O'
_chemical_formula_sum            'C14 H11 Br N2 O'
_chemical_formula_weight         303.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2017-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.07.20 svn.r3457 for OlexSys, GUI svn.r5370)
;
_audit_update_record
;
2018-04-08 deposited with the CCDC.
2018-07-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 130.314(18)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   7.7776(8)
_cell_length_b                   25.3003(11)
_cell_length_c                   16.5229(19)
_cell_measurement_reflns_used    2392
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.0240
_cell_measurement_theta_min      3.5220
_cell_volume                     2479.2(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega  -88.00  -51.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   30.0000 37

  2 omega -101.00  -37.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   90.0000 64

  3 omega   47.00   72.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  -99.0000    0.0000 25

  4 omega   26.00   66.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  -99.0000 -180.0000 40

  5 omega   58.00  110.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  178.0000  120.0000 52

  6 omega   -4.00   27.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  -99.0000    0.0000 31

  7 omega   80.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015   37.0000   30.0000 27

  8 omega   57.00   82.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  178.0000 -150.0000 25

  9 omega   66.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  178.0000 -120.0000 41

 10 omega   76.00  105.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  178.0000  -60.0000 29

 11 omega   32.00   59.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015   37.0000   30.0000 27

 12 omega  -27.00   47.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       36.7015  -57.0000  -90.0000 74

 13 omega   61.00  115.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -180.0000 54

 14 omega   88.00  176.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 88

 15 omega  126.00  174.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000    0.0000 48

 16 omega   38.00   86.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 48

 17 omega   52.00  119.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 67

 18 omega   38.00   90.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 52

 19 omega   45.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 46

 20 omega   44.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 44

 21 omega   87.00  136.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  120.0000 49

 22 omega   89.00  148.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 59
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0232263000
_diffrn_orient_matrix_UB_12      -0.0591127000
_diffrn_orient_matrix_UB_13      0.0138487000
_diffrn_orient_matrix_UB_21      -0.2358125000
_diffrn_orient_matrix_UB_22      -0.0007675000
_diffrn_orient_matrix_UB_23      -0.1109756000
_diffrn_orient_matrix_UB_31      0.1066975000
_diffrn_orient_matrix_UB_32      -0.0145798000
_diffrn_orient_matrix_UB_33      -0.0494604000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0314
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10371
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.081
_diffrn_reflns_theta_max         67.081
_diffrn_reflns_theta_min         3.494
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.426
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70776
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.624
_exptl_crystal_description       needle
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         2.406
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         4435
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1075
_refine_ls_R_factor_gt           0.0872
_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^)+(0.1682P)^2^+1.9551P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2419
_refine_ls_wR_factor_ref         0.2746
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3046
_reflns_number_total             4435
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8nj03166e2.cif
_cod_data_source_block           201707144a
_cod_depositor_comments          'Adding full bibliography for 7057563.cif.'
_cod_original_cell_volume        2479.1(6)
_cod_database_code               7057563
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C14H10N2O5Br1
_shelx_estimated_absorpt_t_max   0.576
_shelx_estimated_absorpt_t_min   0.457
_reflns_odcompleteness_completeness 99.93
_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. Uiso/Uaniso restraints and constraints
Uanis(Br1) = Uanis(Br1A)
Uanis(Br1') = Uanis(Br)
3. Others
 Sof(Br1A)=1-FVAR(1)
 Sof(Br1)=FVAR(1)
 Sof(Br)=1-FVAR(2)
 Sof(Br1')=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C1'(H1'), C2'(H2'), C4'(H4'), C5'(H5'), C10'(H10'), C11'(H11'), C12'(H12'),
 C13'(H13'), C1(H1), C2(H2), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12),
 C13(H13)
4.b Idealised Me refined as rotating group:
 C14'(H14A,H14B,H14C), C14(H14D,H14E,H14F)
;
_olex2_submission_special_instructions 'No special instructions were received'