The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies
Yuan, K.; Kahan, R. J.; Si, C.; Williams, A.; Kirschner, S.; Uzelac, M.; Zysman-Colman, E.; Ingleson, M. J.; Chemical Science 11 (2020) 3258–3267; doi:10.1039/C9SC05404A

data_1557404
_publ_section_title
;
 The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration:
 mechanistic and functionalisation studies
;
_journal_issue                   12
_journal_name_full               'Chemical Science'
_journal_page_first              3258
_journal_page_last               3267
_journal_paper_doi               10.1039/C9SC05404A
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         '2(C50 H54 B2 Br2)'
_chemical_formula_sum            'C100 H108 B4 Br4'
_chemical_formula_weight         1672.74
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-10-25 deposited with the CCDC.	2020-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                64.933(4)
_cell_angle_beta                 86.117(3)
_cell_angle_gamma                77.027(3)
_cell_formula_units_Z            1
_cell_length_a                   8.0182(3)
_cell_length_b                   16.5443(7)
_cell_length_c                   17.4491(8)
_cell_measurement_reflns_used    7998
_cell_measurement_temperature    99.8(5)
_cell_measurement_theta_max      68.1390
_cell_measurement_theta_min      2.9750
_cell_volume                     2042.20(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.26a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.26a (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      99.8(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.977
_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     80.00 110.00   1.00    3.00    --   44.70  30.00-180.00   30
  2  \w    -44.00  93.00   1.00    3.00    --   44.70  60.00-150.00  137
  3  \w     95.00 134.00   1.00    3.00    --   44.70  60.00-150.00   39
  4  \w    -44.00   6.00   1.00    3.00    --   44.70  60.00  30.00   50
  5  \w     98.00 134.00   1.00    3.00    --   44.70  60.00  90.00   36
  6  \w    -43.00  90.00   1.00    3.00    --   44.70  60.00  90.00  133
  7  \w     66.00  93.00   1.00    3.00    --   44.70  60.00   0.00   27
  8  \w    -45.00  53.00   1.00    3.00    --   44.70  60.00-180.00   98
  9  \w    -44.00  24.00   1.00    3.00    --   44.70  60.00 -60.00   68
 10  \w     84.00 112.00   1.00    3.00    --   44.70  60.00  30.00   28
 11  \w    -43.00 -16.00   1.00    3.00    --   44.70  60.00   0.00   27
 12  \w     23.00  49.00   1.00   10.00    --  108.20  50.00 -30.00   26
 13  \w     97.00 197.00   1.00   10.00    --  108.20  50.00  90.00  100
 14  \w     52.00 105.00   1.00   10.00    --  108.20  50.00 -30.00   53
 15  \w    130.00 191.00   1.00   10.00    --  108.20  50.00 -90.00   61
 16  \w     53.00  87.00   1.00   10.00    --  108.20  50.00  90.00   34
 17  \w     91.00 196.00   1.00   10.00    --  108.20  50.00-180.00  105
 18  \w     83.00 175.00   1.00   10.00    --  108.20  50.00-150.00   92
 19  \w    109.00 158.00   1.00   10.00    --  108.20  50.00 120.00   49
 20  \w     19.00 198.00   1.00   10.00    --  108.20  10.00   0.00  179
 21  \w     50.00  77.00   1.00   10.00    --  108.20  50.00-180.00   27
 22  \w     95.00 196.00   1.00   10.00    --  108.20  50.00 150.00  101
 23  \w     80.00 126.00   1.00   10.00    --  108.20  50.00-120.00   46
 24  \w     20.00  47.00   1.00   10.00    --  108.20  50.00 150.00   27
 25  \w    111.00 197.00   1.00   10.00    --  108.20  50.00 -30.00   86
 26  \w    146.00 173.00   1.00   10.00    --  108.20  50.00  30.00   27
 27  \w     21.00 196.00   1.00   10.00    --  108.20  50.00 -60.00  175
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0187266000
_diffrn_orient_matrix_UB_12      -0.0447332000
_diffrn_orient_matrix_UB_13      0.0973128000
_diffrn_orient_matrix_UB_21      -0.0583892000
_diffrn_orient_matrix_UB_22      0.0948019000
_diffrn_orient_matrix_UB_23      0.0010648000
_diffrn_orient_matrix_UB_31      -0.1874891000
_diffrn_orient_matrix_UB_32      -0.0099892000
_diffrn_orient_matrix_UB_33      0.0062049000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0441
_diffrn_reflns_av_unetI/netI     0.0511
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            22412
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.245
_diffrn_reflns_theta_min         2.797
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    2.763
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66623
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.26a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       block
_exptl_crystal_F_000             868
_exptl_crystal_size_max          0.075
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.954
_refine_diff_density_min         -1.445
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     541
_refine_ls_number_reflns         7310
_refine_ls_number_restraints     225
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0552
_refine_ls_R_factor_gt           0.0457
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0557P)^2^+2.2522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1204
_refine_ls_wR_factor_ref         0.1272
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6080
_reflns_number_total             7310
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc05404a2.cif
_cod_data_source_block           s5385l
_cod_depositor_comments
;Adding full bibliography for 1557396--1557406.cif.

 Adding full bibliography for 1557396--1557406.cif.
;
_cod_original_cell_volume        2042.19(16)
_cod_database_code               1557404
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.820
_diffrn_oxdiff_ac4_digest_frames
;
013ea0ff094b66a9b768e70e4a74c82dc700026825f
;
_reflns_odcompleteness_completeness 97.69
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C31-C0 = C30-C31 = C29-C30 = C0AA-C0 = C0AA-C01H = C28-C29 = C27-C28 = C4A-
 C01H = C4A-C1A = C27-C26
 1.54 with sigma of 0.02
 C26-C28 = C1A-C01H = C27-C29 = C28-C30 = C01H-C0 = C29-C31 = C0AA-C31 = C4A-
 C0AA
 2.4 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C30 \\sim C29 \\sim C28 \\sim C26 \\sim C27 \\sim C0 \\sim C0AA \\sim C01H
\\sim C1A \\sim C4A: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
4. Rigid body (RIGU) restrains
 C30, C29, C28, C27, C0, C0AA, C01H, C1A, C4A, C26, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C4, C3, C2, C1, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: H31A(0.5) H31B(0.5) H01C(0.5) H01D(0.5) C30(0.5) H30A(0.5)
 H30B(0.5) C29(0.5) H29A(0.5) H29B(0.5) C28(0.5) H28A(0.5) H28B(0.5) C26(0.5)
 H26A(0.5) H26B(0.5) H26C(0.5) C27(0.5) H27A(0.5) H27B(0.5) C0(0.5) H0A(0.5)
 H0B(0.5) C0AA(0.5) H0AA(0.5) H0AB(0.5) C01H(0.5) H01Q(0.5) H01R(0.5) C1A(0.5)
 H1AA(0.5) H1AB(0.5) H1AC(0.5) C4A(0.5) H4AA(0.5) H4AB(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C5(H5A,H5B), C4(H4A,H4B), C31(H31A,H31B), C31(H01C,H01D),
 C30(H30A,H30B), C3(H3A,H3B), C2(H2A,H2B), C29(H29A,H29B), C28(H28A,H28B),
 C27(H27A,H27B), C0(H0A,H0B), C0AA(H0AA,H0AB), C01H(H01Q,H01R), C4A(H4AA,H4AB)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C15(H15), C36(H36), C11(H11), C35(H35), C41(H41), C20(H20),
 C23(H23), C45(H45), C48(H48)
6.c Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C50(H50A,H50B,H50C), C19(H19A,H19B,H19C), C22(H22A,H22B,
 H22C), C47(H47A,H47B,H47C), C44(H44A,H44B,H44C), C1(H1A,H1B,H1C), C26(H26A,
 H26B,H26C), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              69694
_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 1.661
_oxdiff_exptl_absorpt_empirical_full_min 0.689