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_1565973
_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         '1(C33 H26 B1 N1)'
_chemical_formula_sum            'C33 H26 B N'
_chemical_formula_weight         447.36
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-10
_audit_creation_method
;
Olex2 1.3-beta
(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                78.061(3)
_cell_angle_beta                 78.902(3)
_cell_angle_gamma                79.901(3)
_cell_formula_units_Z            2
_cell_length_a                   6.6409(2)
_cell_length_b                   12.0504(4)
_cell_length_c                   15.9138(6)
_cell_measurement_reflns_used    8254
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      76.2060
_cell_measurement_theta_min      3.7780
_cell_volume                     1210.42(7)
_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-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -73.00 -14.00   1.00    1.00    --    0.00 142.00  26.00   59
  2  \w    -64.00  -8.00   1.00    1.00    --    0.00 128.00-145.00   56
  3  \w   -143.00 -74.00   1.00    3.00    --  -59.00-128.00 140.00   69
  4  \w   -100.00 -14.00   1.00    3.00    --  -59.00 142.00  26.00   86
  5  \w   -144.00 -66.00   1.00    3.00    --  -59.00-142.00 -30.00   78
  6  \w     36.00 125.00   1.00    3.00    --   59.00-142.00 -30.00   89
  7  \w     30.00 114.00   1.00    3.00    --   59.00-128.00 140.00   84
  8  \w     96.00 143.00   1.00    3.00    --   59.00 128.00-145.00   47
  9  \w     88.00 143.00   1.00    3.00    --   59.00 142.00  26.00   55
 10  \w     36.00 125.00   1.00    3.00    --  118.00-142.00 -30.00   89
 11  \w     96.00 178.00   1.00    3.00    --  118.00 128.00-145.00   82
 12  \w     87.00 172.00   1.00    3.00    --  118.00 142.00  26.00   85
 13  \w     34.00 114.00   1.00    3.00    --  118.00-128.00 140.00   80
 14  \w    -96.00 -39.00   1.00    1.00    --    0.00-178.00  90.00   57
 15  \w    -95.00 -37.00   1.00    1.00    --    0.00 178.00 -90.00   58
 16  \w    -39.00  42.00   1.00    1.00    --    0.00  77.00   0.00   81
 17  \w   -151.00 -82.00   1.00    3.00    --  -59.00 -77.00-120.00   69
 18  \w   -143.00 -22.00   1.00    3.00    --  -59.00 -38.00 -60.00  121
 19  \w   -151.00 -82.00   1.00    3.00    --  -59.00 -77.00   0.00   69
 20  \w    103.00 151.00   1.00    3.00    --   59.00  77.00   0.00   48
 21  \w     97.00 143.00   1.00    3.00    --   59.00 125.00 -60.00   46
 22  \w     97.00 143.00   1.00    3.00    --   59.00 125.00-180.00   46
 23  \w     97.00 143.00   1.00    3.00    --   59.00 125.00 120.00   46
 24  \w    103.00 151.00   1.00    3.00    --   59.00  77.00 -30.00   48
 25  \w     32.00 109.00   1.00    3.00    --  118.00-111.00 150.00   77
 26  \w     82.00 178.00   1.00    3.00    --  118.00  45.00 -90.00   96
 27  \w     81.00 178.00   1.00    3.00    --  118.00  61.00-150.00   97
 28  \w     32.00 109.00   1.00    3.00    --  118.00-111.00  90.00   77
 29  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00  30.00   79
 30  \w     26.00 157.00   1.00    3.00    --  118.00 -77.00-120.00  131
 31  \w    104.00 178.00   1.00    3.00    --  118.00 111.00 -90.00   74
 32  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00 -60.00   79
 33  \w     28.00 178.00   1.00    3.00    --  118.00  15.00 -90.00  150
 34  \w     82.00 178.00   1.00    3.00    --  118.00  50.00-177.08   96
 35  \w     34.00 154.00   1.00    3.00    --  118.00 -45.00   0.00  120
 36  \w    104.00 178.00   1.00    3.00    --  118.00 111.00  90.00   74
 37  \w    103.00 178.00   1.00    3.00    --  118.00  77.00 -30.00   75
 38  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00-150.00   79
 39  \w     33.00 155.00   1.00    3.00    --  118.00 -61.00 -30.00  122
 40  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00 150.00   79
 41  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00 120.00   79
 42  \w     82.00 178.00   1.00    3.00    --  118.00  45.00  30.00   96
 43  \w     27.00 106.00   1.00    3.00    --  118.00 -94.00-120.00   79
 44  \w     32.00 109.00   1.00    3.00    --  118.00-111.00 120.00   77
 45  \w    104.00 178.00   1.00    3.00    --  118.00 111.00 -30.00   74
 46  \w     61.00 146.00   1.00    3.00    --  118.00 178.00  30.00   85
 47  \w     57.00  83.00   1.00    3.00    --  118.00 -94.00-180.00   26
 48  \w    105.00 152.00   1.00    3.00    --  118.00  30.00  60.00   47
 49  \w     72.00 103.00   1.00    3.00    --  118.00-111.00  30.00   31
 50  \w    153.00 178.00   1.00    3.00    --  118.00  77.00  60.00   25
 51  \w     61.00 109.00   1.00    3.00    --  118.00-111.00-150.00   48
 52  \w     74.00 116.00   1.00    3.00    --  118.00 -61.00-120.00   42
 53  \w     37.00  62.00   1.00    3.00    --  118.00-111.00  30.00   25
 54  \w    104.00 134.00   1.00    3.00    --  118.00  77.00  60.00   30
 55  \w    106.00 135.00   1.00    3.00    --  118.00  77.00  90.00   29
 56  \w     87.00 128.00   1.00    3.00    --  118.00 -77.00  60.00   41
 57  \w    124.00 150.00   1.00    3.00    --  118.00 111.00 150.00   26
 58  \w     66.00 108.00   1.00    3.00    --  118.00 178.00 120.00   42
 59  \w     68.00 105.00   1.00    3.00    --  118.00-111.00 -60.00   37
 60  \w    111.00 147.00   1.00    3.00    --  118.00  45.00 -30.00   36
 61  \w     91.00 117.00   1.00    3.00    --  118.00 -61.00 150.00   26
 62  \w     97.00 123.00   1.00    3.00    --  118.00 -83.00 -64.23   26
 63  \w     81.00 134.00   1.00    3.00    --  118.00  61.00 -30.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0239555000
_diffrn_orient_matrix_UB_12      -0.0230180000
_diffrn_orient_matrix_UB_13      0.1000672000
_diffrn_orient_matrix_UB_21      0.0960733000
_diffrn_orient_matrix_UB_22      0.1087885000
_diffrn_orient_matrix_UB_23      -0.0039554000
_diffrn_orient_matrix_UB_31      -0.2172990000
_diffrn_orient_matrix_UB_32      0.0711121000
_diffrn_orient_matrix_UB_33      0.0050904000
_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  0.0614
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            19449
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.684
_diffrn_reflns_theta_min         3.787
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.528
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79195
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.227
_exptl_crystal_description       plate
_exptl_crystal_F_000             472
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hexane and dichloromethane  by slow evaporation'
_exptl_crystal_size_max          0.368
_exptl_crystal_size_mid          0.251
_exptl_crystal_size_min          0.033
_refine_diff_density_max         0.184
_refine_diff_density_min         -0.208
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0081(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     592
_refine_ls_number_reflns         9193
_refine_ls_number_restraints     64
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0683
_refine_ls_R_factor_gt           0.0571
_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^)+(0.1151P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1596
_refine_ls_wR_factor_ref         0.1660
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7191
_reflns_number_total             9193
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9876\% 
 around [-0.00 0.00 1.00] (reciprocal) or [-0.35 -0.21 0.91] (direct)
;
_cod_data_source_file            d1sc06513k2.cif
_cod_data_source_block           mi21007c
_cod_depositor_comments
'Adding full bibliography for 1565972--1565974.cif.'
_cod_original_cell_volume        1210.41(8)
_cod_database_code               1565973
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C33H26BN
_chemical_oxdiff_usercomment     '@ 120 K KY461'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.829
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7527(12)
 0.2473(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Shared sites
{N1, C1A}
{C1, N1A}
{C4, C17A}
{C17, C4A}
{C7, C20A}
{C20, C7A}
4. Restrained distances
 N1A-H1AA
 0.83 with sigma of 0.02
 N1-H1
 0.84 with sigma of 0.02
 C26-C31 \\sim C26A-C31A
 with sigma of 0.02
 C29-C30 \\sim C29A-C30A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C25-C30 \\sim C25A-C30A
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 C25-B1 \\sim C25A-B1
 with sigma of 0.02
 C25-B1A \\sim C25A-B1A
 with sigma of 0.02
 C30-B1A \\sim C30A-B1A
 with sigma of 0.04
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C27-C32 \\sim C27A-C32A
 with sigma of 0.04
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C29-C32 \\sim C29A-C32A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C27-C31 \\sim C27A-C31A
 with sigma of 0.04
 C28-C32 \\sim C28A-C32A
 with sigma of 0.02
 C29-C33 \\sim C29A-C33A
 with sigma of 0.04
 C30-B1 \\sim C30A-B1
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C25-C29 \\sim C25A-C29A
 with sigma of 0.04
 C25-C31 \\sim C25A-C31A
 with sigma of 0.04
 C25-C33 \\sim C25A-C33A
 with sigma of 0.04
 C30-C33 \\sim C30A-C33A
 with sigma of 0.02
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C26-C30 \\sim C26A-C30A
 with sigma of 0.04
 C26-B1 \\sim C26A-B1
 with sigma of 0.04
 C26-B1A \\sim C26A-B1A
 with sigma of 0.04
5. Restrained planarity
 C26, C27, C28, C29, C30
 with sigma of 0.1
 C25, C26, C27, C28, C29, C30
 with sigma of 0.1
6. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C1A)
Uanis(C1) = Uanis(N1A)
Uanis(C4) = Uanis(C17A)
Uanis(C17) = Uanis(C4A)
Uanis(C7) = Uanis(C20A)
Uanis(C20) = Uanis(C7A)
7. Rigid body (RIGU) restrains
 C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=
 Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(C12A)=Sof(C13A)=Sof(C15A)=Sof(C16A)=
 Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=
 Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(C24A)=Sof(C40)=
 Sof(N1A)=Sof(H1AA)=Sof(B1A)=Sof(C25A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33A)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=1-FVAR(1)
 Sof(N1)=Sof(H1)=Sof(C1)=Sof(H1B)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=
 Sof(C10)=Sof(H10)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(C14)=Sof(C15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=
 Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(C24)=Sof(C25)=Sof(C26)=
 Sof(C27)=Sof(H27)=Sof(C28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(C31)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=Sof(C32)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(B1)=FVAR(1)
9.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1(H1B), C2(H2), C2A(H2A), C4(H4), C4A(H4A), C5(H5), C5A(H5A),
 C7(H7), C7A(H7A), C8(H8), C8A(H8A), C9(H9), C9A(H9A), C10(H10), C10A(H10A),
 C16(H16), C16A(H16A), C17(H17), C17A(H17A), C19(H19), C19A(H19A), C20(H20),
 C20A(H20A), C21(H21), C21A(H21A), C22(H22), C22A(H22A), C27(H27), C29(H29),
 C27A(H27A), C29A(H29A)
9.b Idealised Me refined as rotating group:
 C31(H31D,H31E,H31F), C32(H32D,H32E,H32F), C33(H33D,H33E,H33F), C31A(H31A,H31B,
 H31C), C32A(H32A,H32B,H32C), C33A(H33A,H33B,H33C)
;
_shelx_res_checksum              77693
_shelx_hkl_checksum              80918
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id KY-461
_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 1.639
_oxdiff_exptl_absorpt_empirical_full_min 0.719
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2