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_7128574
_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         'C23 H31 N O Si'
_chemical_formula_sum            'C23 H31 N O Si'
_chemical_formula_weight         365.58
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_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
;
2021-06-01 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            8
_cell_length_a                   9.0996(3)
_cell_length_b                   14.8381(5)
_cell_length_c                   29.5722(8)
_cell_measurement_reflns_used    4113
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.9430
_cell_measurement_theta_min      4.8090
_cell_volume                     3992.9(2)
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1768
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.970
_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   -114.00 -14.00   1.00    2.88    --  -42.02 -57.00 -90.00  100
  2  \w     23.00 104.00   1.00   11.54    --  104.05 -94.00  60.00   81
  3  \w     53.00 169.00   1.00   11.54    --  104.05  15.00-150.00  116
  4  \w     21.00 103.00   1.00   11.54    --  104.05 -94.00 -30.00   82
  5  \w    -62.00 -27.00   1.00    2.88    --  -42.27  77.00-180.00   35
;
_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      -0.1238015000
_diffrn_orient_matrix_UB_12      0.0226658000
_diffrn_orient_matrix_UB_13      0.0336754000
_diffrn_orient_matrix_UB_21      0.0960382000
_diffrn_orient_matrix_UB_22      -0.0342898000
_diffrn_orient_matrix_UB_23      0.0392682000
_diffrn_orient_matrix_UB_31      0.0639980000
_diffrn_orient_matrix_UB_32      0.0953626000
_diffrn_orient_matrix_UB_33      0.0061991000
_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  0.0278
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            9832
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.037
_diffrn_reflns_theta_min         5.709
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.109
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.846
_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    1.216
_exptl_crystal_description       block
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.095
_refine_diff_density_max         0.461
_refine_diff_density_min         -0.199
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     241
_refine_ls_number_reflns         3879
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0659P)^2^+1.3972P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1093
_refine_ls_wR_factor_ref         0.1159
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3383
_reflns_number_total             3879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02892h2.cif
_cod_data_source_block           20a
_cod_depositor_comments
'Adding full bibliography for 7128568--7128575.cif.'
_cod_database_code               7128574
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H31 N1 O1 Si1'
_shelx_estimated_absorpt_t_max   0.902
_shelx_estimated_absorpt_t_min   0.800
_reflns_odcompleteness_completeness 99.55
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              24918
_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 1.215
_oxdiff_exptl_absorpt_empirical_full_min 0.868