Versatile chemistry of six-membered NHC with boranes: bromination at sp3 borane, activation of B–H bond of HBpin, and ring expansion of NHC
Kundu, Gargi; Dixit, Ruchi; Tothadi, Srinu; Vanka, Kumar; Sen, Sakya Singha; Dalton Transactions  (2022) –; doi:10.1039/D2DT01707E

data_7711062
_publ_section_title
;
 Versatile chemistry of six-membered NHC with boranes: bromination at sp3
 borane, activation of B--H bond of HBpin, and ring expansion of NHC
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01707E
_journal_year                    2022
_chemical_formula_moiety         'C36 H53.502 B N2, C36 H55 B N2'
_chemical_formula_sum            'C72 H108.5 B2 N4'
_chemical_formula_weight         1051.75
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-08-06
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-06 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                71.460(3)
_cell_angle_beta                 86.897(3)
_cell_angle_gamma                82.860(3)
_cell_formula_units_Z            2
_cell_length_a                   9.8912(9)
_cell_length_b                   16.5219(14)
_cell_length_c                   20.764(2)
_cell_measurement_reflns_used    9692
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.28
_cell_measurement_theta_min      2.32
_cell_volume                     3191.8(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Apex3 v2019.11-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 97-2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (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_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            143859
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.30
_diffrn_reflns_theta_min         2.07
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.062
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.7067
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0825 before and 0.0480 after correction.
The Ratio of minimum to maximum transmission is 0.9477.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.094
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1157
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.789
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     756
_refine_ls_number_reflns         15829
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0980
_refine_ls_R_factor_gt           0.0820
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0699P)^2^+4.0842P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1904
_refine_ls_wR_factor_ref         0.2004
_reflns_number_gt                13024
_reflns_number_total             15829
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d2dt01707e2.cif
_cod_data_source_block           mo_gk_9bbnexp_0m_a
_cod_original_formula_sum        'C72 H108.50 B2 N4'
_cod_database_code               7711062
_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. Others
 Sof(H43c)=Sof(H43d)=Sof(C68)=Sof(H68a)=Sof(H68b)=Sof(H75a)=Sof(H67c)=
 Sof(H67d)=Sof(C76)=Sof(H76a)=Sof(H76b)=Sof(H74a)=Sof(C53)=Sof(H53a)=Sof(H53b)=
 Sof(C44)=Sof(H44)=1-FVAR(1)
 Sof(H43a)=Sof(H43b)=Sof(C59)=Sof(H59a)=Sof(H59b)=Sof(H75)=Sof(H67a)=Sof(H67b)=
 Sof(C52)=Sof(H52a)=Sof(H52b)=Sof(H74)=Sof(C40)=Sof(H40a)=Sof(H40b)=Sof(C41)=
 Sof(H41a)=Sof(H41b)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C70(H70), C47(H47), C54(H54), C57(H57), C1(H1), C26(H26), C11(H11), C14(H14),
 C29(H29), C33(H33), C23(H23), C75(H75), C75(H75a), C74(H74a), C74(H74)
3.b Secondary CH2 refined with riding coordinates:
 C43(H43c,H43d), C43(H43a,H43b), C68(H68a,H68b), C66(H66a,H66b), C62(H62a,
 H62b), C63(H63a,H63b), C59(H59a,H59b), C36(H36a,H36b), C35(H35a,H35b),
 C34(H34a,H34b), C32(H32a,H32b), C31(H31a,H31b), C30(H30a,H30b), C2(H2a,H2b),
 C3(H3a,H3b), C4(H4a,H4b), C67(H67a,H67b), C67(H67c,H67d), C52(H52a,H52b),
 C76(H76a,H76b), C40(H40a,H40b), C53(H53a,H53b), C41(H41a,H41b)
3.c Aromatic/amide H refined with riding coordinates:
 C50(H50), C49(H49), C65(H65), C45(H45), C69(H69), C58(H58), C8(H8), C7(H7),
 C9(H9), C21(H21), C20(H20), C19(H19), C44(H44)
3.d Idealised Me refined as rotating group:
 C42(H42a,H42b,H42c), C73(H73a,H73b,H73c), C51(H51a,H51b,H51c), C46(H46a,H46b,
 H46c), C61(H61a,H61b,H61c), C60(H60a,H60b,H60c), C56(H56a,H56b,H56c), C55(H55a,
 H55b,H55c), C28(H28a,H28b,H28c), C12(H12a,H12b,H12c), C15(H15a,H15b,H15c),
 C16(H16a,H16b,H16c), C24(H24a,H24b,H24c), C25(H25a,H25b,H25c), C27(H27a,H27b,
 H27c), C13(H13a,H13b,H13c)
;
_olex2_submission_special_instructions 'No special instructions were received'