Carboxonium derivatives based on closo-dodecaborate anions [1,2-B12H10O2CR]−: synthesis and molecular orbital analysis
Kolbunova, Anastasia V.; Klyukin, Ilya N.; Novikov, Alexander S.; Nelyubin, Alexey V.; Zhdanov, Andrey P.; Kubasov, Alexey S.; Selivanov, Nikita A.; Bykov, Alexander Yu.; Zhizhin, Konstantin Yu.; Kuznetsov, Nikolay T.; New Journal of Chemistry 48 (2024) 8361–8370; doi:10.1039/D4NJ01048E

data_7063175
_publ_section_title
;
 Carboxonium derivatives based on closo-dodecaborate anions
 [1,2-B12H10O2CR]&#x2212;: synthesis and molecular orbital analysis
;
_journal_issue                   18
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              8361
_journal_page_last               8370
_journal_paper_doi               10.1039/D4NJ01048E
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C16 H35 N, C4 H17 B12 O2'
_chemical_formula_sum            'C20 H52 B12 N O2'
_chemical_formula_weight         468.34
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-02-01
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-19 deposited with the CCDC.	2024-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.341(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.3412(9)
_cell_length_b                   21.8620(17)
_cell_length_c                   14.5823(15)
_cell_measurement_reflns_used    5199
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.848
_cell_measurement_theta_min      2.380
_cell_volume                     2965.0(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker SMART APEX II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0571
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            23942
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        24.994
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         1.684
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.058
_exptl_absorpt_correction_T_max  0.7464
_exptl_absorpt_correction_T_min  0.6312
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0946 before and 0.0558 after correction.
The Ratio of minimum to maximum transmission is 0.8457.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.049
_exptl_crystal_description       block
_exptl_crystal_F_000             1020
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.971
_refine_diff_density_min         -0.479
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         5196
_refine_ls_number_restraints     149
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.1382
_refine_ls_R_factor_gt           0.1037
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1309P)^2^+4.2072P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2612
_refine_ls_wR_factor_ref         0.2904
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3665
_reflns_number_total             5196
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj01048e2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7063172--7063175.cif.'
_cod_database_code               7063175
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.997
_shelx_estimated_absorpt_t_min   0.977
_olex2_refinement_description
;
1. Restrained distances
 B3A-B4A = B3A-B2A = B3A-B1A = B3A-B8A = B3A-B7A
 1.8 with sigma of 0.02
 B9A-B8A = B9A-B12A = B9A-B10A = B9A-B5A = B9A-B4A
 1.8 with sigma of 0.02
 B11A-B7A = B11A-B12A = B11A-B10A = B11A-B6A = B11A-B2A
 1.8 with sigma of 0.02
 B3B-B1B = B3B-B11B = B3B-B2B = B3B-B4B = B3B-B7B
 1.8 with sigma of 0.02
 B10B-B11B = B10B-B2B = B10B-B12B = B10B-B9B = B10B-B6B
 1.8 with sigma of 0.02
 B5B-B1B = B5B-B8B = B5B-B9B = B5B-B4B = B5B-B6B
 1.8 with sigma of 0.02
 B12B-B8B = B12B-B9B = B12B-B10B = B12B-B11B = B12B-B7B
 1.8 with sigma of 0.02
 B4C-B5C = B4C-B1C = B4C-B3C = B4C-B9C = B4C-B8C
 1.8 with sigma of 0.02
 B7C-B11C = B7C-B12C = B7C-B2C = B7C-B3C = B7C-B8C
 1.8 with sigma of 0.02
 B12C-B11C = B12C-B10C = B12C-B9C = B12C-B8C = B12C-B7C
 1.8 with sigma of 0.02
 B10C-B11C = B10C-B12C = B10C-B5C = B10C-B6C = B10C-B9C
 1.8 with sigma of 0.02
 B6C-B11C = B6C-B10C = B6C-B5C = B6C-B2C = B6C-B1C
 1.8 with sigma of 0.02
 B1C-B3C
 1.8 with sigma of 0.02
 B6C-B2C
 1.8 with sigma of 0.02
 B7C-B2C
 1.8 with sigma of 0.02
 O1C-B1C
 1.51 with sigma of 0.02
 O2C-B2C
 1.51 with sigma of 0.02
 C1C-O1C
 1.29 with sigma of 0.01
 O2C-C1C
 1.29 with sigma of 0.01
 O1A-C1A
 1.29 with sigma of 0.01
 O2A-C1A
 1.29 with sigma of 0.01
 C1C-C2C
 1.52 with sigma of 0.02
 C1A-C2A
 1.52 with sigma of 0.02
 C3A-C2A
 1.52 with sigma of 0.02
 C1A-C3A
 2.57 with sigma of 0.02
 C3B-C2B
 1.52 with sigma of 0.02
 C2B-C4B
 2.57 with sigma of 0.02
 C2B-C3B
 1.52 with sigma of 0.01
 C3B-C4B
 1.52 with sigma of 0.01
 C2A-C1A
 1.52 with sigma of 0.01
 C2A-C3A
 1.52 with sigma of 0.01
 C4A-C3A
 1.52 with sigma of 0.01
 C4A-C2A
 2.57 with sigma of 0.02
 C3C-C2C
 1.52 with sigma of 0.01
 C1C-C3C
 2.57 with sigma of 0.02
 C4C-C3C
 1.52 with sigma of 0.01
 C4C-C2C
 2.57 with sigma of 0.02
 C12B-C11B = C12B-C11A
 1.52 with sigma of 0.01
 C10-C11B
 1.52 with sigma of 0.01
 C11B-C12B
 1.52 with sigma of 0.01
 C11A-C12A
 1.52 with sigma of 0.01
 O1B-B1B \\sim O1B-B4C
 with sigma of 0.02
 O2B-B2B \\sim O2B-B1C
 with sigma of 0.02
 B11B-O2C \\sim B2C-O2C
 with sigma of 0.02
 B2B-O1C \\sim B1C-O1C
 with sigma of 0.02
 O1B-B6B \\sim O1B-B5C
 with sigma of 0.04
 O1B-B2B \\sim O1B-B1C
 with sigma of 0.04
 O1B-B3B \\sim O1B-B3C
 with sigma of 0.04
 O1B-B5B \\sim O1B-B9C
 with sigma of 0.04
 O1B-B4B \\sim O1B-B8C
 with sigma of 0.04
 B12B-B8B \\sim B11C-B12C
 with sigma of 0.04
 B12B-B9B \\sim B11C-B10C
 with sigma of 0.04
 B12B-B6B \\sim B11C-B5C
 with sigma of 0.04
 B12B-B10B \\sim B11C-B6C
 with sigma of 0.04
 B12B-B11B \\sim B11C-B2C
 with sigma of 0.04
 B12B-B2B \\sim B11C-B1C
 with sigma of 0.04
 B12B-B3B \\sim B11C-B3C
 with sigma of 0.04
 B12B-O2C \\sim B11C-O2C
 with sigma of 0.04
 B12B-B5B \\sim B11C-B9C
 with sigma of 0.04
 B12B-B4B \\sim B11C-B8C
 with sigma of 0.04
 B12B-B7B \\sim B11C-B7C
 with sigma of 0.04
 B8B-B9B \\sim B12C-B10C
 with sigma of 0.04
 B8B-B6B \\sim B12C-B5C
 with sigma of 0.04
 B8B-B1B \\sim B12C-B4C
 with sigma of 0.04
 B8B-B10B \\sim B12C-B6C
 with sigma of 0.04
 B8B-B11B \\sim B12C-B2C
 with sigma of 0.04
 B8B-B3B \\sim B12C-B3C
 with sigma of 0.04
 B8B-B5B \\sim B12C-B9C
 with sigma of 0.04
 B8B-B4B \\sim B12C-B8C
 with sigma of 0.04
 B8B-B7B \\sim B12C-B7C
 with sigma of 0.04
 B9B-B6B \\sim B10C-B5C
 with sigma of 0.04
 B9B-B1B \\sim B10C-B4C
 with sigma of 0.04
 B9B-B10B \\sim B10C-B6C
 with sigma of 0.04
 B9B-B11B \\sim B10C-B2C
 with sigma of 0.04
 B9B-B2B \\sim B10C-B1C
 with sigma of 0.04
 B9B-B5B \\sim B10C-B9C
 with sigma of 0.04
 B9B-B4B \\sim B10C-B8C
 with sigma of 0.04
 B9B-B7B \\sim B10C-B7C
 with sigma of 0.04
 B6B-B1B \\sim B5C-B4C
 with sigma of 0.04
 B6B-O2B \\sim B5C-O2B
 with sigma of 0.04
 B6B-B10B \\sim B5C-B6C
 with sigma of 0.04
 B6B-B11B \\sim B5C-B2C
 with sigma of 0.04
 B6B-B2B \\sim B5C-B1C
 with sigma of 0.04
 B6B-B3B \\sim B5C-B3C
 with sigma of 0.04
 B6B-O1C \\sim B5C-O1C
 with sigma of 0.04
 B6B-B5B \\sim B5C-B9C
 with sigma of 0.04
 B6B-B4B \\sim B5C-B8C
 with sigma of 0.04
 B1B-O2B \\sim B4C-O2B
 with sigma of 0.04
 B1B-B10B \\sim B4C-B6C
 with sigma of 0.04
 B1B-B11B \\sim B4C-B2C
 with sigma of 0.04
 B1B-B2B \\sim B4C-B1C
 with sigma of 0.04
 B1B-B3B \\sim B4C-B3C
 with sigma of 0.04
 B1B-O1C \\sim B4C-O1C
 with sigma of 0.04
 B1B-B5B \\sim B4C-B9C
 with sigma of 0.04
 B1B-B4B \\sim B4C-B8C
 with sigma of 0.04
 B1B-B7B \\sim B4C-B7C
 with sigma of 0.04
 O2B-B10B \\sim O2B-B6C
 with sigma of 0.04
 O2B-B11B \\sim O2B-B2C
 with sigma of 0.04
 O2B-B3B \\sim O2B-B3C
 with sigma of 0.04
 B10B-B11B \\sim B6C-B2C
 with sigma of 0.04
 B10B-B2B \\sim B6C-B1C
 with sigma of 0.04
 B10B-B3B \\sim B6C-B3C
 with sigma of 0.04
 B10B-O2C \\sim B6C-O2C
 with sigma of 0.04
 B10B-O1C \\sim B6C-O1C
 with sigma of 0.04
 B10B-B5B \\sim B6C-B9C
 with sigma of 0.04
 B10B-B7B \\sim B6C-B7C
 with sigma of 0.04
 B11B-B2B \\sim B2C-B1C
 with sigma of 0.04
 B11B-B3B \\sim B2C-B3C
 with sigma of 0.04
 B11B-O1C \\sim B2C-O1C
 with sigma of 0.04
 B11B-B4B \\sim B2C-B8C
 with sigma of 0.04
 B11B-B7B \\sim B2C-B7C
 with sigma of 0.04
 B2B-B3B \\sim B1C-B3C
 with sigma of 0.04
 B2B-O2C \\sim B1C-O2C
 with sigma of 0.04
 B2B-B5B \\sim B1C-B9C
 with sigma of 0.04
 B2B-B4B \\sim B1C-B8C
 with sigma of 0.04
 B2B-B7B \\sim B1C-B7C
 with sigma of 0.04
 B3B-O2C \\sim B3C-O2C
 with sigma of 0.04
 B3B-O1C \\sim B3C-O1C
 with sigma of 0.04
 B3B-B5B \\sim B3C-B9C
 with sigma of 0.04
 B3B-B4B \\sim B3C-B8C
 with sigma of 0.04
 B3B-B7B \\sim B3C-B7C
 with sigma of 0.04
 O2C-B7B \\sim O2C-B7C
 with sigma of 0.04
 B5B-B4B \\sim B9C-B8C
 with sigma of 0.04
 B5B-B7B \\sim B9C-B7C
 with sigma of 0.04
 B4B-B7B \\sim B8C-B7C
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
Uanis(B12B) = Uanis(B8B) = Uanis(B9B) = Uanis(B6B) = Uanis(B1B) = Uanis(B10B) =
Uanis(B11B) = Uanis(B3B) = Uanis(B5B) = Uanis(B4B) = Uanis(B7B) = Uanis(B2B)
Uanis(B9A) = Uanis(B8A) = Uanis(B7A) = Uanis(B11A) = Uanis(B12A) = Uanis(B10A)
= Uanis(B5A) = Uanis(B4A) = Uanis(B6A) = Uanis(B2A) = Uanis(B1A) = Uanis(B3A)
Uanis(B11C) = Uanis(B12C) = Uanis(B10C) = Uanis(B5C) = Uanis(B4C) = Uanis(B6C)
= Uanis(B2C) = Uanis(B1C) = Uanis(B3C) = Uanis(B9C) = Uanis(B8C) = Uanis(B7C)
Uanis(B9A) = Uanis(B5B) = Uanis(B9C)
Uanis(O2C) = Uanis(O2A) = Uanis(O1C) = Uanis(O1A) = Uanis(O2B) = Uanis(O1B)
Uanis(C1C) = Uanis(C1A)
Uanis(C2C) = Uanis(C2A)
Uanis(C3A) = Uanis(C4A)
Uanis(C3C) = Uanis(C4C)
Uanis(C3C) = Uanis(C3A)
Uanis(C3A) = Uanis(C2A)
Uanis(C2A) = Uanis(C1A)
Uanis(C4B) = Uanis(C3B)
Uanis(C12B) = Uanis(C12A)
Uanis(C11A) = Uanis(C11B)
3. Others
 Fixed Sof: H10B(0.55) H10C(0.55) H00C(0.45) H00D(0.45) C11B(0.55) H11D(0.55)
 H11E(0.55) C12B(0.55) H12D(0.55) H12E(0.55) H12F(0.55) H00I(0.5) H00J(0.5)
 C14B(0.4) H14D(0.4) H14E(0.4) C15B(0.4) H15C(0.4) H15D(0.4) C16B(0.4)
 H16A(0.4) H16B(0.4) H16C(0.4) C17B(0.5) H17C(0.5) H17D(0.5) C18B(0.5)
 H18D(0.5) H18E(0.5) C19B(0.5) H19A(0.5) H19B(0.5) C20B(0.5) H20A(0.5)
 H20B(0.5) H20C(0.5) O1B(0.55) O2B(0.55) C1B(0.55) C2B(0.55) H2BA(0.55)
 H2BB(0.55) C3B(0.55) H3BA(0.55) H3BB(0.55) C4B(0.55) H4BA(0.55) H4BB(0.55)
 H4BC(0.55) B1B(0.55) B2B(0.55) B3B(0.55) H3B(0.55) B4B(0.55) H4BD(0.55)
 B5B(0.55) H5BA(0.55) B6B(0.55) H6BA(0.55) B7B(0.55) H7BA(0.55) B8B(0.55)
 H8BA(0.55) B9B(0.55) H9BA(0.55) B10B(0.55) H10D(0.55) B11B(0.55) H11F(0.55)
 B12B(0.55) H12G(0.55) O1A(0.35) O2A(0.35) O1C(0.1) O2C(0.1) C4A(0.35)
 H14A(0.35) H14B(0.35) H14C(0.35) C14A(0.6) H00R(0.6) H00S(0.6) C16A(0.6)
 H00X(0.6) H00Y(0.6) HD(0.6) C18A(0.5) H2A(0.5) H2B(0.5) C3C(0.1) H17A(0.1)
 H17B(0.1) C11A(0.45) H15A(0.45) H15B(0.45) C4C(0.1) H25A(0.1) H25B(0.1)
 H25C(0.1) C1A(0.35) C12A(0.45) H18A(0.45) H18B(0.45) H18C(0.45) C1C(0.1)
 C15A(0.6) H00T(0.6) H00U(0.6) C2A(0.35) H11B(0.35) H11C(0.35) C17A(0.5)
 H4A(0.5) H4B(0.5) C2C(0.1) H12A(0.1) H12B(0.1) C19A(0.5) H1A(0.5) H1B(0.5)
 C3A(0.35) H13A(0.35) H13B(0.35) C20A(0.5) H00Z(0.5) HE(0.5) HF(0.5) B1A(0.35)
 B9A(0.35) H9AA(0.35) B7A(0.35) H7AB(0.35) B1C(0.1) B11A(0.35) H11A(0.35)
 B2A(0.35) B8A(0.35) H8AA(0.35) B2C(0.1) B10A(0.35) H10A(0.35) B3A(0.35)
 H3A(0.35) B12A(0.35) H12C(0.35) B3C(0.1) H9CA(0.1) B7C(0.1) H10(0.1) B4A(0.35)
 H4AA(0.35) B8C(0.1) H9(0.1) B4C(0.1) H0AA(0.1) B9C(0.1) H8(0.1) B5A(0.35)
 H5AA(0.35) B10C(0.1) H4C(0.1) B5C(0.1) H5C(0.1) B11C(0.1) H2C(0.1) B6A(0.35)
 H6AB(0.35) B6C(0.1) H8C(0.1) B12C(0.1) H3C(0.1)
4.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B), C10(H10B,H10C), C10(H00C,
 H00D), C11B(H11D,H11E), C13(H00I,H00J), C14B(H14D,H14E), C15B(H15C,H15D),
 C17B(H17C,H17D), C18B(H18D,H18E), C19B(H19A,H19B), C2B(H2BA,H2BB), C3B(H3BA,
 H3BB), C14A(H00R,H00S), C18A(H2A,H2B), C3C(H17A,H17B), C11A(H15A,H15B),
 C15A(H00T,H00U), C2A(H11B,H11C), C17A(H4A,H4B), C2C(H12A,H12B), C19A(H1A,H1B),
 C3A(H13A,H13B)
4.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8D), C12B(H12D,H12E,H12F), C16B(H16A,H16B,H16C), C20B(H20A,H20B,
 H20C), C4B(H4BA,H4BB,H4BC), C4A(H14A,H14B,H14C), C16A(H00X,H00Y,HD), C4C(H25A,
 H25B,H25C), C12A(H18A,H18B,H18C), C20A(H00Z,HE,HF)
4.c Boron cage BH refined with riding coordinates:
 B3B(H3B), B4B(H4BD), B5B(H5BA), B6B(H6BA), B7B(H7BA), B8B(H8BA), B9B(H9BA),
 B10B(H10D), B11B(H11F), B12B(H12G), B9A(H9AA), B7A(H7AB), B11A(H11A),
 B8A(H8AA), B10A(H10A), B3A(H3A), B12A(H12C), B3C(H9CA), B7C(H10), B4A(H4AA),
 B8C(H9), B4C(H0AA), B9C(H8), B5A(H5AA), B10C(H4C), B5C(H5C), B11C(H2C),
 B6A(H6AB), B6C(H8C), B12C(H3C)
;
_shelx_res_checksum              84683
_shelx_hkl_checksum              56767
_olex2_submission_special_instructions 'No special instructions were received'