Enhanced N-directed electrophilic C–H borylation generates BN–[5]- and [6]helicenes with improved photophysical properties
Yuan, Kang; Volland, Daniel; Kirschner, Sven; Uzelac, Marina; Nichol, Gary S.; Nowak-Król, Agnieszka; Ingleson, Michael J.; Chemical Science 13 (2022) 1136–1145; doi:10.1039/D1SC06513K

data_1565972
_publ_section_title
;
 Enhanced N-directed electrophilic C--H borylation generates BN--[5]- and
 [6]helicenes with improved photophysical properties
;
_journal_issue                   4
_journal_name_full               'Chemical Science'
_journal_page_first              1136
_journal_page_last               1145
_journal_paper_doi               10.1039/D1SC06513K
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C20 H13 B Br N'
_chemical_formula_sum            'C20 H13 B Br N'
_chemical_formula_weight         358.03
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-05-18 deposited with the CCDC.	2022-01-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.9580(7)
_cell_length_b                   9.4271(3)
_cell_length_c                   7.0146(3)
_cell_measurement_reflns_used    8543
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      25.2870
_cell_measurement_theta_min      3.7160
_cell_volume                     1518.15(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.931
_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    -87.00  20.00   1.00   17.50    --  -15.66 -16.00 -72.00  107
  2  \w    -52.00  56.00   1.00   17.50    --  -15.66  16.00  97.00  108
  3  \w    -54.00  54.00   1.00   17.50    --   17.38 -16.00 -72.00  108
  4  \w    -19.00  89.00   1.00   17.50    --   17.38  16.00  97.00  108
  5  \w    -83.00   1.00   1.00   17.50    --  -15.66 -57.00  90.00   84
  6  \w    -39.00  11.00   1.00   17.50    --  -15.66 -77.00-120.00   50
  7  \w     -9.00  39.00   1.00   17.50    --   17.38  77.00-120.00   48
  8  \w     -9.00  39.00   1.00   17.50    --   17.38  77.00 -90.00   48
  9  \w     39.00  90.00   1.00   17.50    --   17.38 178.00 120.00   51
 10  \w    -52.00  37.00   1.00   17.50    --   17.38 -37.00  60.00   89
 11  \w     -9.00  39.00   1.00   17.50    --   17.38  77.00  30.00   48
 12  \w     -9.00  39.00   1.00   17.50    --   17.38  77.00 150.00   48
 13  \w    -20.00  56.00   1.00   17.50    --   17.38 -99.00 -90.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0062351000
_diffrn_orient_matrix_UB_12      0.0675046000
_diffrn_orient_matrix_UB_13      0.0396748000
_diffrn_orient_matrix_UB_21      -0.0015177000
_diffrn_orient_matrix_UB_22      -0.0308001000
_diffrn_orient_matrix_UB_23      0.0921593000
_diffrn_orient_matrix_UB_31      0.0302129000
_diffrn_orient_matrix_UB_32      0.0124691000
_diffrn_orient_matrix_UB_33      0.0127897000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            31855
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.906
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.344
_diffrn_reflns_theta_min         3.404
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.704
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79306
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.566
_exptl_crystal_description       plate
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.232
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.378
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 1186 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         3769
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0544
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0262P)^2^+0.6498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0624
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.804
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.876
_reflns_number_gt                3087
_reflns_number_total             3769
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06513k2.cif
_cod_data_source_block           ky409_reprocess
_cod_depositor_comments
'Adding full bibliography for 1565972--1565974.cif.'
_cod_database_code               1565972
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H13 B Br N'
_reflns_odcompleteness_completeness 99.56
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C18(H18), C3(H3), C13(H13), C19(H19), C6(H6), C7(H7), C14(H14),
 C5(H5), C16(H16), C17(H17), C8(H8), C2(H2)
;
_shelx_res_checksum              25156
_shelx_hkl_checksum              30434
_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 1.317
_oxdiff_exptl_absorpt_empirical_full_min 0.852