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_7128571
_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 H33 N O2 Si'
_chemical_formula_sum            'C23 H33 N O2 Si'
_chemical_formula_weight         383.59
_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_Hall           'P 61'
_space_group_name_H-M_alt        'P 61'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-28
_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                120
_cell_formula_units_Z            6
_cell_length_a                   19.2612(6)
_cell_length_b                   19.2612(6)
_cell_length_c                   9.9892(5)
_cell_measurement_reflns_used    6527
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.0440
_cell_measurement_theta_min      4.5130
_cell_volume                     3209.4(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 2014/5 (Sheldrick, 2014)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -63.00  33.00   1.00    4.21    --  -41.77  38.00-150.00   96
  2  \w     58.00  84.00   1.00    4.21    --   41.77-127.00 -35.00   26
  3  \w    -64.00 -10.00   1.00    4.21    --  -42.27 -26.00  -0.62   54
  4  \w      9.00  34.00   1.00    4.21    --   42.27  80.00  46.55   25
  5  \w     14.00  41.00   1.00    4.21    --   42.27  57.00  30.00   27
  6  \w     73.00  99.00   1.00    5.00    --  102.47  63.00  15.07   26
  7  \w     72.00  98.00   1.00    5.00    --  102.47  66.00  35.01   26
  8  \w     72.00  98.00   1.00    5.00    --  102.47  71.00  34.83   26
  9  \w    138.00 164.00   1.00    5.00    --  102.47  57.00  78.35   26
 10  \w     72.00  98.00   1.00    5.00    --  102.47  71.00 -63.63   26
 11  \w     73.00  99.00   1.00    5.00    --  102.47  62.00   3.66   26
 12  \w    110.00 146.00   1.00    5.00    --  102.47 125.00 120.00   36
 13  \w     29.00 112.00   1.00    5.00    --  102.47-125.00 -60.00   83
 14  \w     73.00  99.00   1.00    5.00    --  102.47  61.00  30.00   26
 15  \w     73.00  99.00   1.00    5.00    --  102.47  61.00   0.00   26
 16  \w     71.00  96.00   1.00    5.00    --  102.47  72.00   3.13   25
 17  \w     74.00 100.00   1.00    5.00    --  102.47  57.00  78.35   26
 18  \w     79.00 104.00   1.00    5.00    --  102.47  45.00  30.00   25
 19  \w     80.00 175.00   1.00    5.00    --  102.47  49.00 -22.22   95
 20  \w     73.00  99.00   1.00    5.00    --  102.47  61.00 -30.00   26
 21  \w     77.00 103.00   1.00    5.00    --  102.47  56.00  -6.09   26
 22  \w   -114.00 -30.00   1.00    4.21    --  -42.27 -57.00 120.00   84
 23  \w   -114.00 -14.00   1.00    4.21    --  -42.27 -57.00-150.00  100
;
_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      0.0438452000
_diffrn_orient_matrix_UB_12      0.0921639000
_diffrn_orient_matrix_UB_13      -0.0083468000
_diffrn_orient_matrix_UB_21      0.0812790000
_diffrn_orient_matrix_UB_22      0.0025856000
_diffrn_orient_matrix_UB_23      -0.0005801000
_diffrn_orient_matrix_UB_31      -0.0025834000
_diffrn_orient_matrix_UB_32      -0.0048660000
_diffrn_orient_matrix_UB_33      -0.1539824000
_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  0.0319
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            18641
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.043
_diffrn_reflns_theta_min         4.591
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.092
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.737
_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    1.191
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.075
_refine_diff_density_max         1.249
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 1387 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         3827
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0684
_refine_ls_R_factor_gt           0.0611
_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^)+(0.1152P)^2^+1.8207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1663
_refine_ls_wR_factor_ref         0.1764
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    0.896
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                3457
_reflns_number_total             3827
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc02892h2.cif
_cod_data_source_block           3a
_cod_depositor_comments
'Adding full bibliography for 7128568--7128575.cif.'
_cod_original_cell_volume        3209.4(3)
_cod_database_code               7128571
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C23 H33 N1 O2 Si1'
_reflns_odcompleteness_completeness 99.90
_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, All O(H) groups
2. Restrained distances
 O2-C14
 1.42 with sigma of 0.02
 O1-C13
 1.42 with sigma of 0.02
 C13-C4
 1.51 with sigma of 0.02
 O1A-C13A
 1.42 with sigma of 0.02
 C13A-C4
 1.51 with sigma of 0.02
 O1-C4
 2.37 with sigma of 0.04
 O1A-C4
 2.37 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C4 \\sim C13 \\sim O1: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C4 \\sim C13A \\sim O1A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C4, C13, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C13A, O1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(O1A)=Sof(H1AA)=1-FVAR(1)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(O1)=Sof(H1A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18), C21(H21)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13A(H13C,H13D), C14(H14A,H14B)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C8(H8)
6.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)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1A), O1A(H1AA), O2(H2A)
;
_shelx_res_checksum              37570
_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.823