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_1565974
_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         'C34 H30 B N'
_chemical_formula_sum            'C34 H30 B N'
_chemical_formula_weight         463.40
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-30
_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                 109.463(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.0461(6)
_cell_length_b                   17.1985(5)
_cell_length_c                   13.0700(6)
_cell_measurement_reflns_used    7492
_cell_measurement_temperature    120.1(4)
_cell_measurement_theta_max      23.9510
_cell_measurement_theta_min      3.6690
_cell_volume                     2553.0(2)
_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      120.1(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.924
_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    -45.00  43.00   1.00   20.00    --  -15.82  81.00 -68.00   88
  2  \w    -10.00  42.00   1.00   20.00    --   17.54  81.00 -68.00   52
  3  \w    -43.00  46.00   1.00   20.00    --   17.54 -81.00 169.00   89
  4  \w    -88.00 -39.00   1.00   20.00    --  -15.82-178.00 -30.00   49
  5  \w    -39.00  11.00   1.00   20.00    --  -15.82 -77.00  90.00   50
  6  \w    -20.00  56.00   1.00   20.00    --   17.54 -99.00 -90.00   76
  7  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00  30.00   48
  8  \w    -52.00  36.00   1.00   20.00    --   17.54 -38.00 120.00   88
  9  \w    -50.00  34.00   1.00   20.00    --   17.54 -57.00  30.00   84
 10  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00  90.00   48
 11  \w     -1.00  87.00   1.00   20.00    --   17.54  38.00  90.00   88
 12  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00 -30.00   48
 13  \w      1.00  85.00   1.00   20.00    --   17.54  57.00-150.00   84
 14  \w    -20.00  29.00   1.00   20.00    --   17.54 -99.00  90.00   49
 15  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00-120.00   48
;
_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      0.0520943000
_diffrn_orient_matrix_UB_12      0.0227106000
_diffrn_orient_matrix_UB_13      0.0141777000
_diffrn_orient_matrix_UB_21      -0.0289719000
_diffrn_orient_matrix_UB_22      0.0275127000
_diffrn_orient_matrix_UB_23      -0.0405494000
_diffrn_orient_matrix_UB_31      -0.0186615000
_diffrn_orient_matrix_UB_32      0.0206868000
_diffrn_orient_matrix_UB_33      0.0383074000
_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  0.0827
_diffrn_reflns_av_unetI/netI     0.0768
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.924
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            55926
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.924
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.485
_diffrn_reflns_theta_min         3.406
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77087
_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_density_diffrn    1.206
_exptl_crystal_description       plate
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.201
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         6564
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.1324
_refine_ls_R_factor_gt           0.0623
_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^)+(0.0480P)^2^+0.8045P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1182
_refine_ls_wR_factor_ref         0.1424
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3743
_reflns_number_total             6564
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc06513k2.cif
_cod_data_source_block           ky463_reprocess
_cod_depositor_comments
'Adding full bibliography for 1565972--1565974.cif.'
_cod_database_code               1565974
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H30 B N'
_chemical_oxdiff_usercomment     '@ 120 K '
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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 Aromatic/amide H refined with riding coordinates:
 C8(H8), C18(H18), C19(H19), C3(H3), C13(H13), C2(H2), C7(H7), C5(H5),
 C14(H14), C21(H21), C30(H30), C6(H6), C28(H28), C20(H20)
2.b Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C24(H24A,H24B,H24C), C32(H32A,H32B,H32C), C25(H25A,H25B,
 H25C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              57702
_shelx_hkl_checksum              42714
_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 1.276
_oxdiff_exptl_absorpt_empirical_full_min 0.738