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_7128568
_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         'C21 H29 N Si'
_chemical_formula_sum            'C21 H29 N Si'
_chemical_formula_weight         323.54
_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     dual
_audit_creation_date             2019-04-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-04-25 deposited with the CCDC.	2021-06-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.469(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3498(4)
_cell_length_b                   7.3678(3)
_cell_length_c                   27.1186(10)
_cell_measurement_reflns_used    2794
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.8550
_cell_measurement_theta_min      4.7460
_cell_volume                     1847.76(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_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 0.994
_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    7.62    --  -42.31 -57.00-120.00   93
  2  \w   -103.00 -23.00   1.00    7.62    --  -42.31 -77.00   0.00   80
  3  \w    -25.00   2.00   1.00    7.62    --   42.31 -77.00 120.00   27
  4  \w     31.00  74.00   1.00    7.62    --   42.31 -77.00 120.00   43
  5  \w     66.00 119.00   1.00   30.48    --  106.63  15.00-150.00   53
  6  \w     84.00 176.00   1.00   30.48    --  106.63  30.00  90.00   92
  7  \w     33.00  97.00   1.00   30.48    --  106.63 -98.00 176.00   64
  8  \w     84.00 178.00   1.00   30.48    --  106.63  30.00  30.00   94
  9  \w     38.00 131.00   1.00   30.48    --  106.63 -45.00 150.00   93
;
_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      -0.1374101000
_diffrn_orient_matrix_UB_12      0.0561112000
_diffrn_orient_matrix_UB_13      -0.0352213000
_diffrn_orient_matrix_UB_21      0.0922215000
_diffrn_orient_matrix_UB_22      0.0441556000
_diffrn_orient_matrix_UB_23      -0.0410628000
_diffrn_orient_matrix_UB_31      -0.0185080000
_diffrn_orient_matrix_UB_32      -0.1966202000
_diffrn_orient_matrix_UB_33      -0.0192866000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0476
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            6721
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.051
_diffrn_reflns_theta_min         4.782
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.093
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.849
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (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_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       needle
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.241
_exptl_crystal_size_mid          0.049
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.383
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     225
_refine_ls_number_reflns         3490
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0679
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0552P)^2^+2.3546P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1456
_refine_ls_wR_factor_ref         0.1522
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2932
_reflns_number_total             3490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02892h2.cif
_cod_data_source_block           1a
_cod_depositor_comments
'Adding full bibliography for 7128568--7128575.cif.'
_cod_original_cell_volume        1847.76(12)
_cod_database_code               7128568
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C21 H29 Si1 N1'
_reflns_odcompleteness_completeness 99.86
_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. Others
 Sof(H20A)=Sof(C22')=Sof(H22D)=Sof(H22E)=Sof(H22F)=1-FVAR(1)
 Sof(H20)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C20(H20), C20(H20A)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8)
3.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C22'(H22D,H22E,H22F)
;
_shelx_res_checksum              2029
_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 2.499
_oxdiff_exptl_absorpt_empirical_full_min 0.652