Predictable site-selective functionalization: Promoter group assisted <i>para</i>-halogenation of <i>N</i>-substituted <b>(</b>hetero<b>)</b>aromatics under metal-free condition.
Gupta, Shiv Shankar; Manisha, ?; Kumar, Rakesh; Dhiman, Ankit Kumar; Sharma, Upendra; Organic & biomolecular chemistry 19 (2021) 9675–9687; doi:10.1039/d1ob02000e

data_7158344
_publ_section_title
;
 Predictable site-selective functionalization: Promoter group assisted
 <i>para</i>-halogenation of <i>N</i>-substituted
 <b>(</b>hetero<b>)</b>aromatics under metal-free condition.
;
_journal_issue                   44
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9675
_journal_page_last               9687
_journal_paper_doi               10.1039/d1ob02000e
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C12 H10 Br N3'
_chemical_formula_sum            'C12 H10 Br N3'
_chemical_formula_weight         276.14
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-07-09
_audit_creation_method
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_audit_update_record
;
2020-11-10 deposited with the CCDC.	2021-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 101.456(5)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   13.4998(6)
_cell_length_b                   21.9675(8)
_cell_length_c                   7.6004(3)
_cell_measurement_reflns_used    2361
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      66.4480
_cell_measurement_theta_min      3.3350
_cell_volume                     2209.05(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9974
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_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     19.00  87.00   1.00    1.00    --   25.69  57.00 -90.00   68
  2  \w     69.00  95.00   1.00    1.00    --   25.69  57.00-180.00   26
  3  \w    -13.00  14.00   1.00    1.00    --   25.69  57.00 -90.00   27
  4  \w    -12.00  59.00   1.00    1.00    --   25.69  57.00-180.00   71
  5  \w     71.00 146.00   1.00    1.50    --   66.85 178.00 150.00   75
  6  \w     62.00  92.00   1.00    1.50    --   66.85 -77.00  30.00   30
  7  \w     33.00 143.00   1.00    1.50    --   66.85  63.00 -30.00  110
  8  \w    116.00 150.00   1.00    1.50    --   66.85 111.00   0.00   34
  9  \w     49.00 136.00   1.00    1.50    --   66.85  63.00  90.00   87
 10  \w    -14.00  15.00   1.00    1.50    --   66.85 -77.00  30.00   29
 11  \w     73.00 161.00   1.00    5.00    --  108.00  43.00-180.00   88
 12  \w    109.00 173.00   1.00    5.00    --  108.00  43.00  90.00   64
 13  \w     40.00 116.00   1.00    5.00    --  108.00 -65.00 -30.00   76
 14  \w     68.00 109.00   1.00    5.00    --  108.00-104.00  90.00   41
 15  \w    105.00 140.00   1.00    5.00    --  108.00 -54.00  60.00   35
 16  \w     40.00  76.00   1.00    5.00    --  108.00 -54.00  60.00   36
 17  \w     69.00 175.00   1.00    5.00    --  108.00  54.00-120.00  106
 18  \w     31.00 103.00   1.00    5.00    --  108.00-104.00   0.00   72
 19  \w     23.00 104.00   1.00    5.00    --  108.00-104.00 -60.00   81
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0154213000
_diffrn_orient_matrix_UB_12      -0.0637252000
_diffrn_orient_matrix_UB_13      0.0856632000
_diffrn_orient_matrix_UB_21      -0.0600654000
_diffrn_orient_matrix_UB_22      -0.0283147000
_diffrn_orient_matrix_UB_23      -0.1743262000
_diffrn_orient_matrix_UB_31      0.0985370000
_diffrn_orient_matrix_UB_32      -0.0073229000
_diffrn_orient_matrix_UB_33      -0.0712522000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7081
_diffrn_reflns_theta_full        66.76
_diffrn_reflns_theta_max         66.76
_diffrn_reflns_theta_min         3.90
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.854
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.407
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.661
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       monoclinic
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.291
_refine_diff_density_min         -0.609
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         3715
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0522
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0501P)^2^+0.8142P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0980
_refine_ls_wR_factor_ref         0.1121
_reflns_number_gt                2958
_reflns_number_total             3715
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d1ob02000e2.cif
_cod_data_source_block           ussgn2_69_1_rt_cu
_cod_depositor_comments
;
          Adding full bibliography for 7158344.cif.

2024-06-28
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C24 H20 Br2 N6'
_cod_original_formula_weight         552.28
_cod_original_formula_moiety         '2(C12 H10 Br N3)'
_cod_original_formula_units_Z            4
_cod_database_code               7158344
_chemical_oxdiff_formula         'C96 H80 Br8 N24'
_reflns_odcompleteness_completeness 94.35
_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:
 C1(H1A,H1B), C2(H2A,H2B), C14(H14A,H14B), C13(H13A,H13B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C18(H18), C19(H19), C4(H4), C6(H6), C16(H16), C10(H10), C22(H22),
 C24(H24), C12(H12), C23(H23), C11(H11)
;
_olex2_date_sample_data_collection 2020-07-08
_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 2.305
_oxdiff_exptl_absorpt_empirical_full_min 0.804