Unraveling the reactivity of a cationic iminoborane: avenues to unusual boron cations
Guo, Rui; Zhang, Xin; Li, Tong; Li, Qianli; Ruiz, David A.; Liu, Liu Leo; Tung, Chen-Ho; Kong, Lingbing; Chemical Science 13 (2022) 2303–2309; doi:10.1039/D2SC00002D

data_1566160
_publ_section_title
;
 Unraveling the reactivity of a cationic iminoborane: avenues to unusual
 boron cations
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              2303
_journal_page_last               2309
_journal_paper_doi               10.1039/D2SC00002D
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'Al Br4, C36 H59 B N5, 3(C6 H6)'
_chemical_formula_sum            'C54 H77 Al B Br4 N5'
_chemical_formula_weight         1153.63
_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             2021-04-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-04-16 deposited with the CCDC.	2022-01-26 downloaded from the CCDC.
;
_cell_angle_alpha                82.612(3)
_cell_angle_beta                 72.270(3)
_cell_angle_gamma                89.201(3)
_cell_formula_units_Z            2
_cell_length_a                   14.3058(5)
_cell_length_b                   14.4769(5)
_cell_length_c                   14.7822(5)
_cell_measurement_reflns_used    9030
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.1450
_cell_measurement_theta_min      3.0600
_cell_volume                     2890.80(18)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_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     94.00 173.00   1.00    0.96    --  106.49  19.00 120.00   79
  2  \w     30.00 119.00   1.00    0.12    --   48.45  69.00 -17.00   89
  3  \w     89.00 178.00   1.00    0.96    --  106.49  77.00-180.00   89
  4  \w     94.00 178.00   1.00    0.96    --  106.49  19.00 -90.00   84
  5  \w     92.00 178.00   1.00    0.96    --  106.49  57.00 -60.00   86
  6  \w     87.00 150.00   1.00    0.96    --  106.49  69.00 -17.00   63
  7  \w     34.00 106.00   1.00    0.96    --  106.49 -99.00 120.00   72
  8  \w     40.00 107.00   1.00    0.96    --  106.49-104.00 114.81   67
  9  \w     63.00 107.00   1.00    0.96    --  106.49-105.00  13.54   44
 10  \w     35.00  61.00   1.00    0.96    --  106.49-105.00  13.54   26
 11  \w     34.00 106.00   1.00    0.96    --  106.49 -99.00 -60.00   72
 12  \w     34.00 106.00   1.00    0.96    --  106.49-101.00-176.72   72
 13  \w    -25.00  27.00   1.00    0.12    --   48.45 -19.00-150.00   52
 14  \w    -15.00  21.00   1.00    0.12    --   48.45 -69.00-149.00   36
 15  \w     35.00  67.00   1.00    0.12    --   48.45 -69.00-149.00   32
 16  \w     44.00  84.00   1.00    0.96    --  106.49 -69.00-149.00   40
 17  \w     95.00 178.00   1.00    0.96    --  106.49 125.00   0.00   83
 18  \w   -103.00 -13.00   1.00    0.96    --  -86.25  77.00  60.00   90
 19  \w    -28.00  23.00   1.00    0.12    --  -48.45  69.00 -17.00   51
 20  \w    -42.00 -17.00   1.00    0.96    --  -86.25  69.00 -17.00   25
 21  \w    -85.00 -47.00   1.00    0.96    --  -86.25  69.00 -17.00   38
 22  \w    -68.00 -31.00   1.00    0.12    --  -48.45  69.00 -17.00   37
 23  \w    -66.00 -16.00   1.00    0.96    --  -86.25  57.00-180.00   50
 24  \w   -108.00 -30.00   1.00    0.12    --  -48.45 -69.00-149.00   78
 25  \w   -116.00 -67.00   1.00    0.96    --  -86.25 -69.00-149.00   49
 26  \w   -151.00-124.00   1.00    0.96    --  -86.25 -69.00-149.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0834153000
_diffrn_orient_matrix_UB_12      0.0093998000
_diffrn_orient_matrix_UB_13      -0.0460829000
_diffrn_orient_matrix_UB_21      0.0394669000
_diffrn_orient_matrix_UB_22      -0.0832032000
_diffrn_orient_matrix_UB_23      -0.0545458000
_diffrn_orient_matrix_UB_31      -0.0653880000
_diffrn_orient_matrix_UB_32      -0.0671690000
_diffrn_orient_matrix_UB_33      0.0841442000
_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  0.0556
_diffrn_reflns_av_unetI/netI     0.0602
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            28932
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         3.079
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.821
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70115
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       block
_exptl_crystal_F_000             1188
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         1.438
_refine_diff_density_min         -1.106
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     687
_refine_ls_number_reflns         10120
_refine_ls_number_restraints     637
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0382P)^2^+3.7827P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1105
_refine_ls_wR_factor_ref         0.1185
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7889
_reflns_number_total             10120
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00002d2.cif
_cod_data_source_block           klb-100
_cod_depositor_comments
'Adding full bibliography for 1566151--1566160.cif.'
_cod_original_cell_volume        2890.79(18)
_cod_database_code               1566160
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CNB
_shelx_estimated_absorpt_t_max   0.310
_shelx_estimated_absorpt_t_min   0.310
_reflns_odcompleteness_completeness 98.15
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Restrained distances
 C48A-C47A \\sim C47A-C46A \\sim C46A-C45A \\sim C45A-C44A \\sim C44A-C43A
\\sim C43A-C48A
 with sigma of 0.02
 C48A-C44A \\sim C48A-C44A \\sim C45A-C47A \\sim C45A-C43A \\sim C43A-C47A
\\sim C44A-C46A
 with sigma of 0.04
 C47A-C48A \\sim C48A-C43A \\sim C43A-C44A \\sim C45A-C44A \\sim C45A-C46A
\\sim C46A-C47A
 with sigma of 0.02
 C40A-C41A \\sim C39A-C40A \\sim C38A-C39A \\sim C37A-C38A \\sim C37A-C42A
\\sim C41A-C42A
 with sigma of 0.02
 C41B-C40B \\sim C40B-C39B \\sim C39B-C38B \\sim C38B-C37B \\sim C37B-C42B
\\sim C41B-C42B
 with sigma of 0.02
 C45B-C44B \\sim C46B-C45B \\sim C47B-C46B \\sim C47B-C48B \\sim C43B-C48B
\\sim C44B-C43B
 with sigma of 0.02
3. Restrained planarity
 C43A, C44A, C45A, C46A, C47A, C48A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Br2A \\sim Br2B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37A \\sim C37B \\sim C38A \\sim C38B \\sim C39A \\sim C39B \\sim C40A \\sim
C40B \\sim C41A \\sim C41B \\sim C42A \\sim C42B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C43A \\sim C43B \\sim C44A \\sim C44B \\sim C45A \\sim C45B \\sim C46A \\sim
C46B \\sim C47A \\sim C47B \\sim C48A \\sim C48B: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(Br2B) \\sim Ueq, Uanis(Br2A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.002
Uanis(C48A) \\sim Ueq, Uanis(C43A) \\sim Ueq, Uanis(C44A) \\sim Ueq,
Uanis(C45A) \\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C47A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C42B) \\sim Ueq, Uanis(C40B) \\sim Ueq, Uanis(C41B) \\sim Ueq,
Uanis(C39B) \\sim Ueq, Uanis(C38B) \\sim Ueq, Uanis(C37B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C42B) \\sim Ueq, Uanis(C37B) \\sim Ueq, Uanis(C38B) \\sim Ueq,
Uanis(C39B) \\sim Ueq, Uanis(C40B) \\sim Ueq, Uanis(C41B) \\sim Ueq,
Uanis(C42A) \\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C38A) \\sim Ueq,
Uanis(C39A) \\sim Ueq, Uanis(C40A) \\sim Ueq, Uanis(C41A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C48A) \\sim Ueq, Uanis(C43A) \\sim Ueq, Uanis(C44A) \\sim Ueq,
Uanis(C45A) \\sim Ueq, Uanis(C46A) \\sim Ueq, Uanis(C47A) \\sim Ueq,
Uanis(C47B) \\sim Ueq, Uanis(C46B) \\sim Ueq, Uanis(C48B) \\sim Ueq,
Uanis(C43B) \\sim Ueq, Uanis(C44B) \\sim Ueq, Uanis(C45B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C43A, C44A, C45A, C46A, C47A, C48A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Br2B)=1-FVAR(1)
 Sof(Br2A)=FVAR(1)
 Sof(C42B)=Sof(H42B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=
 Sof(H39B)=Sof(C40B)=Sof(H40B)=Sof(C41B)=Sof(H41B)=1-FVAR(2)
 Sof(C42A)=Sof(H42A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=
 Sof(H39A)=Sof(C40A)=Sof(H40A)=Sof(C41A)=Sof(H41A)=FVAR(2)
 Sof(C43B)=Sof(H43B)=Sof(C44B)=Sof(H44B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=
 Sof(H46B)=Sof(C47B)=Sof(H47B)=Sof(C48B)=Sof(H48B)=1-FVAR(3)
 Sof(C48A)=Sof(H48A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=
 Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C30(H30), C31(H31), C33(H33), C34(H34), C42A(H42A),
 C37A(H37A), C38A(H38A), C39A(H39A), C40A(H40A), C41A(H41A), C42B(H42B),
 C37B(H37B), C38B(H38B), C39B(H39B), C40B(H40B), C41B(H41B), C43B(H43B),
 C44B(H44B), C45B(H45B), C46B(H46B), C47B(H47B), C48A(H48A), C43A(H43A),
 C44A(H44A), C45A(H45A), C46A(H46A), C47A(H47A), C48B(H48B), C49(H49), C50(H50),
  C51(H51), C52(H52), C53(H53), C54(H54)
7.c Fitted hexagon refined as free rotating group:
 C42A(C37A,C38A,C39A,C40A,C41A), C42B(C37B,C38B,C39B,C40B,C41B), C48A(C43A,
 C44A,C45A,C46A,C47A)
7.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,
 H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              64346
_shelx_hkl_checksum              57528
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.518