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_7128570
_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         'C27 H27 F4 N Si'
_chemical_formula_sum            'C27 H27 F4 N Si'
_chemical_formula_weight         469.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-26
_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                 101.265(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.2725(4)
_cell_length_b                   19.9141(9)
_cell_length_c                   13.8083(7)
_cell_measurement_reflns_used    3957
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.7900
_cell_measurement_theta_min      4.3850
_cell_volume                     2230.95(19)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(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 0.968
_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   -110.00 -17.00   1.00    1.00    --  -42.02 -57.00-120.00   93
  2  \w    -85.00 -12.00   1.00    1.00    --  -42.02 125.00 -30.00   73
  3  \w    -57.00 -15.00   1.00    1.00    --  -42.02 -57.00 120.00   42
  4  \w     21.00  95.00   1.00    1.01    --  104.05 -94.00 -60.00   74
  5  \w    140.00 174.00   1.00    1.01    --  104.05  61.00  30.00   34
  6  \w     51.00 119.00   1.00    1.01    --  104.05 -45.00 -60.00   68
  7  \w    108.00 177.00   1.00    1.01    --  104.05 125.00 -90.00   69
  8  \w    152.00 178.00   1.00    1.01    --  104.05  77.00-120.00   26
  9  \w     21.00 170.00   1.00    1.01    --  104.05   0.00-120.00  149
;
_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      -0.1005962000
_diffrn_orient_matrix_UB_12      0.0549692000
_diffrn_orient_matrix_UB_13      -0.0635043000
_diffrn_orient_matrix_UB_21      0.1025131000
_diffrn_orient_matrix_UB_22      -0.0108513000
_diffrn_orient_matrix_UB_23      -0.0805878000
_diffrn_orient_matrix_UB_31      -0.1243557000
_diffrn_orient_matrix_UB_32      -0.0532916000
_diffrn_orient_matrix_UB_33      -0.0491614000
_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  0.0280
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8851
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.127
_diffrn_reflns_theta_min         3.948
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.359
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.572
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.398
_exptl_crystal_description       block
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     304
_refine_ls_number_reflns         4330
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0377
_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^)+(0.0510P)^2^+0.8252P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0961
_refine_ls_wR_factor_ref         0.1036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3707
_reflns_number_total             4330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02892h2.cif
_cod_data_source_block           5a
_cod_depositor_comments
'Adding full bibliography for 7128568--7128575.cif.'
_cod_database_code               7128570
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C27 H27 F4 N1 Si1'
_reflns_odcompleteness_completeness 99.95
_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.a Ternary CH refined with riding coordinates:
 C19(H19), C22(H22), C25(H25)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              63933
_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 1.141
_oxdiff_exptl_absorpt_empirical_full_min 0.916