Hexamethylbenzene elimination enables the generation of transient, sterically unhindered multiply bonded boron species
Zhang, Chonghe; Dabringhaus, Philipp; Tra, Bi Youan E.; Gilliard, Robert J.; Cummins, Christopher C.; Chemical Science 16 (2025) 11841–11848; doi:10.1039/D5SC02645H

data_1574654
_publ_section_title
;
 Hexamethylbenzene elimination enables the generation of transient,
 sterically unhindered multiply bonded boron species
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              11841
_journal_page_last               11848
_journal_paper_doi               10.1039/D5SC02645H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C66 H64 B2 N6, 2(C6 H6)'
_chemical_formula_sum            'C78 H76 B2 N6'
_chemical_formula_weight         1119.06
_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
_audit_creation_date             2023-10-01
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-01-10 deposited with the CCDC.	2025-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                84.390(2)
_cell_angle_beta                 72.008(2)
_cell_angle_gamma                68.497(2)
_cell_formula_units_Z            1
_cell_length_a                   10.8373(5)
_cell_length_b                   12.1312(7)
_cell_length_c                   13.6657(7)
_cell_measurement_reflns_used    9170
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      32.120
_cell_measurement_theta_min      2.369
_cell_volume                     1589.59(15)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0357
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            80309
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.025
_diffrn_reflns_theta_max         25.025
_diffrn_reflns_theta_min         1.567
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.068
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.6850
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1295 before and 0.0583 after correction.
The Ratio of minimum to maximum transmission is 0.9179.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             596
_exptl_crystal_size_max          0.291
_exptl_crystal_size_mid          0.193
_exptl_crystal_size_min          0.184
_refine_diff_density_max         0.551
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         5618
_refine_ls_number_restraints     84
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0604
_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^)+(0.0702P)^2^+1.2528P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1492
_refine_ls_wR_factor_ref         0.1507
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5340
_reflns_number_total             5618
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02645h3.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1574650--1574657.cif.'
_cod_database_code               1574654
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.988
_shelx_estimated_absorpt_t_min   0.981
_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
 C012-C016 \\sim C0-C5
 with sigma of 0.02
 C012-C017 \\sim C0-C1
 with sigma of 0.02
 C013-C014 \\sim C3-C4
 with sigma of 0.02
 C013-C015 \\sim C3-C2
 with sigma of 0.02
 C014-C016 \\sim C4-C5
 with sigma of 0.02
 C015-C017 \\sim C2-C1
 with sigma of 0.02
 C012-C014 \\sim C0-C4
 with sigma of 0.04
 C012-C015 \\sim C0-C2
 with sigma of 0.04
 C013-C016 \\sim C3-C5
 with sigma of 0.04
 C013-C017 \\sim C3-C1
 with sigma of 0.04
 C014-C015 \\sim C4-C2
 with sigma of 0.04
 C016-C017 \\sim C5-C1
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C012) \\sim Ueq, Uanis(C013) \\sim Ueq, Uanis(C014) \\sim Ueq,
Uanis(C015) \\sim Ueq, Uanis(C016) \\sim Ueq, Uanis(C017) \\sim Ueq, Uanis(C0)
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C3) = Uanis(C013)
Uanis(C4) = Uanis(C014)
Uanis(C5) = Uanis(C016)
Uanis(C0) = Uanis(C012)
Uanis(C1) = Uanis(C017)
Uanis(C2) = Uanis(C015)
4. Others
 Sof(C0)=Sof(H0)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=Sof(C5)=Sof(H5)=1-FVAR(1)
 Sof(C012)=Sof(H012)=Sof(C013)=Sof(H013)=Sof(C014)=Sof(H014)=Sof(C015)=
 Sof(H015)=Sof(C016)=Sof(H016)=Sof(C017)=Sof(H017)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00E(H00E), C00G(H00G), C00I(H00J), C00K(H00K), C00M(H00O),
 C00N(H00P), C00P(H00Q), C00R(H00U), C00S(H00V), C00T(H00W), C00Z(H00),
 C010(H010), C011(H011), C012(H012), C013(H013), C014(H014), C015(H015),
 C016(H016), C017(H017), C0(H0), C1(H1), C2(H2), C3(H3), C4(H4), C5(H5)
5.b Idealised Me refined as rotating group:
 C00F(H00A,H00B,H00C), C00H(H00F,H00H,H00I), C00L(H00L,H00M,H00N), C00Q(H00R,
 H00S,H00T), C00X(H00X,H00Y,H), C00Y(H00Z,HA,HB)
;
_shelx_res_checksum              55692
_olex2_submission_special_instructions 'No special instructions were received'