Direct formation of 4,5-disubstituted carbazoles via regioselective dilithiation.
Pocock, Ian A.; Alotaibi, Alya M.; Jagdev, Kesar; Prior, Connor; Burgess, Gregory R.; Male, Louise; Grainger, Richard S.; Chemical communications (Cambridge, England) 57 (2021) 7252–7255; doi:10.1039/d1cc02892h

data_7128573
_publ_section_title
;
 Direct formation of 4,5-disubstituted carbazoles via regioselective
 dilithiation.
;
_journal_issue                   59
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              7252
_journal_page_last               7255
_journal_paper_doi               10.1039/d1cc02892h
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C12 H7 Cl2 N'
_chemical_formula_sum            'C12 H7 Cl2 N'
_chemical_formula_weight         236.09
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-25
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-04-28 deposited with the CCDC.	2021-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   3.8267(2)
_cell_length_b                   14.2898(6)
_cell_length_c                   17.5522(7)
_cell_measurement_reflns_used    4133
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.8170
_cell_measurement_theta_min      3.8780
_cell_volume                     959.80(7)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1768
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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    -67.00  32.00   1.00    1.00    --  -42.02  38.00 -60.00   99
  2  \w    -70.00  31.00   1.00    1.00    --  -42.02  57.00  30.00  101
  3  \w     28.00 137.00   1.00    2.26    --  104.05 -77.00-120.00  109
  4  \w     28.00 132.00   1.00    2.26    --  104.05 -30.00 -90.00  104
  5  \w     28.00 132.00   1.00    2.26    --  104.05 -30.00-180.00  104
  6  \w     97.00 177.00   1.00    2.26    --  104.05 125.00 -60.00   80
  7  \w     30.00 110.00   1.00    2.26    --  104.05-120.00  87.00   80
  8  \w   -116.00 -17.00   1.00    1.00    --  -42.02 -38.00 -90.00   99
  9  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00  30.00  100
 10  \w    103.00 178.00   1.00    2.26    --  104.05  77.00-120.00   75
 11  \w     51.00 178.00   1.00    2.26    --  104.05  15.00-150.00  127
 12  \w     51.00 178.00   1.00    2.26    --  104.05  15.00 120.00  127
 13  \w     76.00 178.00   1.00    2.26    --  104.05  30.00   0.00  102
 14  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00-120.00  100
 15  \w   -114.00 -14.00   1.00    1.00    --  -42.02 -57.00 150.00  100
 16  \w     75.00 100.00   1.00    2.26    --  104.05  61.00 -90.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0445517000
_diffrn_orient_matrix_UB_12      0.0675672000
_diffrn_orient_matrix_UB_13      0.0677139000
_diffrn_orient_matrix_UB_21      0.0270952000
_diffrn_orient_matrix_UB_22      -0.0829995000
_diffrn_orient_matrix_UB_23      0.0557220000
_diffrn_orient_matrix_UB_31      0.3990997000
_diffrn_orient_matrix_UB_32      0.0131338000
_diffrn_orient_matrix_UB_33      0.0037890000
_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  0.0352
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            9168
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.841
_diffrn_reflns_theta_min         3.989
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.725
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.814
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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_colour            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.634
_exptl_crystal_description       plate
_exptl_crystal_F_000             480
_exptl_crystal_size_max          0.205
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.247
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 674 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.045(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     140
_refine_ls_number_reflns         1895
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0318P)^2^+0.4595P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0664
_refine_ls_wR_factor_ref         0.0683
_reflns_Friedel_coverage         0.628
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                1785
_reflns_number_total             1895
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02892h2.cif
_cod_data_source_block           6b
_cod_depositor_comments
'Adding full bibliography for 7128568--7128575.cif.'
_cod_database_code               7128573
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C21 H27 Cl2 N1 Si1'
_shelx_estimated_absorpt_t_max   0.763
_shelx_estimated_absorpt_t_min   0.387
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8)
;
_shelx_res_checksum              53107
_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 1.943
_oxdiff_exptl_absorpt_empirical_full_min 0.749