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_1566155
_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, C29 H51 B N3, C6 H6'
_chemical_formula_sum            'C35 H57 Al B Br4 N3'
_chemical_formula_weight         877.26
_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             2021-04-15
_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                91.982(2)
_cell_angle_beta                 100.812(3)
_cell_angle_gamma                98.869(2)
_cell_formula_units_Z            4
_cell_length_a                   9.7709(3)
_cell_length_b                   20.3965(5)
_cell_length_c                   21.6332(7)
_cell_measurement_reflns_used    13476
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.2180
_cell_measurement_theta_min      3.1020
_cell_volume                     4175.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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     99.00 165.00   1.00    0.48    --  106.49 125.00 -60.00   66
  2  \w     95.00 178.00   1.00    0.48    --  106.49 125.00  30.00   83
  3  \w    110.00 175.00   1.00    0.48    --  106.49  97.00  -5.00   65
  4  \w     94.00 177.00   1.00    0.48    --  106.49  19.00  60.00   83
  5  \w     94.00 177.00   1.00    0.48    --  106.49  19.00 150.00   83
  6  \w     62.00 105.00   1.00    0.48    --  106.49 -97.00-113.00   43
  7  \w     34.00 106.00   1.00    0.48    --  106.49 -99.00-150.00   72
  8  \w     34.00 106.00   1.00    0.48    --  106.49 -99.00 -60.00   72
  9  \w     34.00 106.00   1.00    0.48    --  106.49 -99.00   0.00   72
 10  \w     35.00 108.00   1.00    0.48    --  106.49-111.00  74.17   73
 11  \w     37.00 107.00   1.00    0.48    --  106.49-105.00 178.53   70
 12  \w     34.00 106.00   1.00    0.48    --  106.49 -99.00  90.00   72
 13  \w    -24.00  27.00   1.00    0.12    --   48.45 -19.00 -30.00   51
 14  \w     34.00  99.00   1.00    0.48    --  106.49 -77.00  90.00   65
 15  \w     -3.00  81.00   1.00    0.12    --   48.45 -97.00-113.00   84
 16  \w    -26.00  27.00   1.00    0.12    --  -48.45  19.00 -90.00   53
 17  \w    -75.00  24.00   1.00    0.12    --  -48.45  97.00  -5.00   99
 18  \w    -80.00 -41.00   1.00    0.48    --  -86.25  97.00  -5.00   39
 19  \w   -162.00 -73.00   1.00    0.48    --  -86.25 -19.00 -60.00   89
 20  \w   -151.00 -85.00   1.00    0.48    --  -86.25 -97.00-113.00   66
 21  \w   -120.00 -73.00   1.00    0.12    --  -48.45-125.00   0.00   47
 22  \w   -117.00 -73.00   1.00    0.12    --  -48.45-125.00  60.00   44
;
_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      -0.1384213000
_diffrn_orient_matrix_UB_12      0.0199044000
_diffrn_orient_matrix_UB_13      -0.0349821000
_diffrn_orient_matrix_UB_21      -0.0659520000
_diffrn_orient_matrix_UB_22      -0.0125082000
_diffrn_orient_matrix_UB_23      0.0587277000
_diffrn_orient_matrix_UB_31      0.0544548000
_diffrn_orient_matrix_UB_32      0.0729131000
_diffrn_orient_matrix_UB_33      0.0246201000
_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  0.0952
_diffrn_reflns_av_unetI/netI     0.0956
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            43364
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.080
_diffrn_reflns_theta_max         67.080
_diffrn_reflns_theta_min         2.928
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.093
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72339
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.396
_exptl_crystal_description       needle
_exptl_crystal_F_000             1784
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.924
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     952
_refine_ls_number_reflns         14743
_refine_ls_number_restraints     482
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0710
_refine_ls_R_factor_gt           0.0520
_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^)+(0.0560P)^2^+1.8934P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1293
_refine_ls_wR_factor_ref         0.1452
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11252
_reflns_number_total             14743
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00002d2.cif
_cod_data_source_block           klb-96
_cod_depositor_comments
'Adding full bibliography for 1566151--1566160.cif.'
_cod_database_code               1566155
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CNB
_shelx_estimated_absorpt_t_max   0.630
_shelx_estimated_absorpt_t_min   0.235
_reflns_odcompleteness_completeness 98.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C56-C55 = C55-C2AA = C57-C55 = C55-C1AA = C55-C0AA = C58-C55
 1.5 with sigma of 0.02
 C54B-C51 = C54A-C51 = C52B-C51 = C52A-C51 = C53B-C51 = C53A-C51
 1.5 with sigma of 0.02
 B020-H020 = B1-H1A
 1.13 with sigma of 0.02
 C64-C59 = C64-C63 = C63-C62 = C61-C60 = C60-C59
 1.37 with sigma of 0.02
 C67A-C66A \\sim C66A-C65A \\sim C65A-C70A \\sim C70A-C69A \\sim C69A-C68A
\\sim C68A-C67A
 with sigma of 0.02
 C67A-C69A \\sim C67A-C69A \\sim C70A-C66A \\sim C70A-C68A \\sim C68A-C66A
\\sim C69A-C65A
 with sigma of 0.04
 N6-C36A \\sim N6-C36B
 with sigma of 0.02
 C36B-C35B \\sim C36A-C35A
 with sigma of 0.02
 C37B-C36B \\sim C37A-C36A
 with sigma of 0.02
3. Restrained planarity
 C67A, C66A, C65A, C70A, C69A, C68A
 with sigma of 0.1
 C65B, C66B, C67B, C68B, C69B, C70B
 with sigma of 0.1
 C64, C63, C62, C61, C60, C59
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C67A \\sim C66A \\sim C65A \\sim C70A \\sim C69A \\sim C68A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C69A \\sim C67A \\sim C68A \\sim C65A \\sim C70A \\sim C66A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C67B \\sim C66B \\sim C65B \\sim C70B \\sim C69B \\sim C68B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1AA \\sim C56 \\sim C0AA \\sim C58 \\sim C2AA \\sim C57: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C52A \\sim C52B \\sim C54A \\sim C54B \\sim C53A \\sim C53B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C36A \\sim C36B \\sim C35A \\sim C37B \\sim C37A \\sim C35B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq, Uanis(C69A) \\sim Ueq,
Uanis(C70A) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C65B) \\sim Ueq, Uanis(C70B) \\sim Ueq, Uanis(C66B) \\sim Ueq,
Uanis(C69B) \\sim Ueq, Uanis(C67B) \\sim Ueq, Uanis(C68B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2AA) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C58) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C52A) \\sim Ueq, Uanis(C52B) \\sim Ueq, Uanis(C54A) \\sim Ueq,
Uanis(C54B) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C53B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36A) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C35A) \\sim Ueq,
Uanis(C37B) \\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C35B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C67A, C66A, C65A, C70A, C69A, C68A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C67B)=Sof(H67B)=Sof(C66B)=Sof(H66B)=Sof(C65B)=Sof(H65B)=Sof(C70B)=
 Sof(H70B)=Sof(C69B)=Sof(H69B)=Sof(C68B)=Sof(H68B)=1-FVAR(1)
 Sof(C67A)=Sof(H67A)=Sof(C66A)=Sof(H66A)=Sof(C65A)=Sof(H65A)=Sof(C70A)=
 Sof(H70A)=Sof(C69A)=Sof(H69A)=Sof(C68A)=Sof(H68A)=FVAR(1)
 Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C1AA)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=1-FVAR(2)
 Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(2)
 Sof(C52B)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C53B)=Sof(H53D)=Sof(H53E)=
 Sof(H53F)=Sof(C54B)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(3)
 Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C52A)=Sof(H52A)=Sof(H52B)=
 Sof(H52C)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
 Sof(C36B)=Sof(H36B)=Sof(C37B)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C35B)=
 Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(4)
 Sof(C36A)=Sof(H36A)=Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C37A)=
 Sof(H37D)=Sof(H37E)=Sof(H37F)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C39(H39), C36A(H36A), C36B(H36B)
7.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N4(H4), C43(H43), C3(H3), C5(H5), C45(H45), C63(H63), C62(H62),
 C61(H61), C60(H60), C59(H59), C64(H64), C67A(H67A), C66A(H66A), C65A(H65A),
 C70A(H70A), C69A(H69A), C68A(H68A), C67B(H67B), C66B(H66B), C65B(H65B),
 C70B(H70B), C69B(H69B), C68B(H68B)
7.c Fitted hexagon refined as free rotating group:
 C63(C62,C61,C60,C59,C64), C67B(C66B,C65B,C70B,C69B,C68B)
7.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C23(H23A,H23B,H23C), C9(H9A,H9B,
 H9C), C25(H25A,H25B,H25C), C22(H22A,H22B,H22C), C10(H10A,H10B,H10C), C34(H34A,
 H34B,H34C), C12(H12A,H12B,H12C), C26(H26A,H26B,H26C), C31(H31A,H31B,H31C),
 C38(H38A,H38B,H38C), C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C48(H48A,H48B,
 H48C), C18(H18A,H18B,H18C), C8(H8A,H8B,H8C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C40(H40A,H40B,H40C),
 C53A(H53A,H53B,H53C), C52A(H52A,H52B,H52C), C54A(H54A,H54B,H54C), C57(H57A,
 H57B,H57C), C58(H58A,H58B,H58C), C56(H56A,H56B,H56C), C2AA(H2AA,H2AB,H2AC),
 C1AA(H1AA,H1AB,H1AC), C0AA(H0AA,H0AB,H0AC), C52B(H52D,H52E,H52F), C53B(H53D,
 H53E,H53F), C54B(H54D,H54E,H54F), C35A(H35A,H35B,H35C), C37B(H37A,H37B,H37C),
 C37A(H37D,H37E,H37F), C35B(H35D,H35E,H35F)
;
_shelx_res_checksum              63356
_shelx_hkl_checksum              77850
_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 2.649
_oxdiff_exptl_absorpt_empirical_full_min 0.337