Formation and reactivity of a unique M⋯C-H interaction stabilized by carborane cages.
Liu, Xin-Ran; Cui, Peng-Fei; García-Rodeja, Yago; Solà, Miquel; Jin, Guo-Xin; Chemical science 15 (2024) 9274–9280; doi:10.1039/d4sc01158a

data_1571662
_publ_section_title
;
 Formation and reactivity of a unique M&#x22ef;C-H interaction stabilized
 by carborane cages.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              9274
_journal_page_last               9280
_journal_paper_doi               10.1039/d4sc01158a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C15 H39 B30 N3 S3, C H2 Cl2'
_chemical_formula_sum            'C17 H43 B30 Cl4 N3 S3'
_chemical_formula_weight         851.82
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-10-11
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2023-10-25 deposited with the CCDC.	2024-05-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.9098(9)
_cell_length_b                   25.502(2)
_cell_length_c                   31.388(3)
_cell_measurement_reflns_used    9965
_cell_measurement_temperature    193(2)
_cell_measurement_theta_max      55.90
_cell_measurement_theta_min      3.25
_cell_volume                     8732.8(13)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      193.0
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1447
_diffrn_reflns_av_unetI/netI     0.1490
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            32746
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        53.499
_diffrn_reflns_theta_max         53.499
_diffrn_reflns_theta_min         3.255
_exptl_absorpt_coefficient_mu    2.586
_exptl_absorpt_correction_T_max  0.7510
_exptl_absorpt_correction_T_min  0.4735
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1836 before and 0.1002 after correction.
The Ratio of minimum to maximum transmission is 0.6305.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             3456
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.386
_refine_diff_density_min         -0.570
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     639
_refine_ls_number_reflns         7801
_refine_ls_number_restraints     212
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.2144
_refine_ls_R_factor_gt           0.1440
_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^)+(0.1739P)^2^+62.8878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3770
_refine_ls_wR_factor_ref         0.4114
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4023
_reflns_number_total             7801
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01158a2.cif
_cod_data_source_block           platon_sq
_cod_depositor_comments
'Adding full bibliography for 1571656--1571663.cif.'
_cod_original_cell_volume        8732.6(12)
_cod_database_code               1571662
_shelx_estimated_absorpt_t_max   0.747
_shelx_estimated_absorpt_t_min   0.482
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
2. Restrained distances
 C2-H2A = C10-H10A = C12-H12A
 1.04 with sigma of 0.05
 N2-H2 = N3-H3A
 0.88 with sigma of 0.02
 C13-Cl2
 1.74 with sigma of 0.03
 B27'-C12
 1.71 with sigma of 0.02
 C11-B23 = C11-B24 = C12-B31 = B31'-C12 = B26'-C12
 1.71 with sigma of 0.02
 B26-B31 = B27-B31 = B32'-B31' = B32'-B27'
 1.76 with sigma of 0.02
 B32-B29 = B32-B31 = B23-B28 = B28-B24 = B24-B29
 1.76 with sigma of 0.02
 B26'-B30' = B31'-B26' = B27-B28 = B28-B29 = B32-B27
 1.76 with sigma of 0.02
 B32'-B28' = B32'-B29' = B23'-B27' = B25'-B30'
 1.76 with sigma of 0.02
 B27'-B28' = B29'-B30' = B30'-B31' = B31'-B27'
 1.76 with sigma of 0.02
3. Restrained planarity
 B27', B28', B29', B30', B31'
 with sigma of 0.02
 B27, B28, B29, B30, B31
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
B27 \\sim B27': within 2A with sigma of 0.02 and sigma for terminal atoms of
0.05
Uanis(B29) \\sim Ueq, Uanis(B30') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(B31') \\sim Ueq, Uanis(B32') \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(Cl2)
\\sim Ueq, Uanis(C13') \\sim Ueq, Uanis(Cl2') \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C6') \\sim Ueq, Uanis(S3') \\sim Ueq, Uanis(B23') \\sim Ueq, Uanis(B24')
\\sim Ueq, Uanis(B25') \\sim Ueq, Uanis(B26') \\sim Ueq, Uanis(B27') \\sim Ueq,
Uanis(B28') \\sim Ueq, Uanis(B29') \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C6) \\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(B23) \\sim Ueq, Uanis(B24)
\\sim Ueq, Uanis(B25) \\sim Ueq, Uanis(B26) \\sim Ueq, Uanis(B27) \\sim Ueq,
Uanis(B28) \\sim Ueq, Uanis(B30) \\sim Ueq, Uanis(B31) \\sim Ueq, Uanis(B32)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Others
 Sof(S3')=Sof(C6')=Sof(B23')=Sof(H23')=Sof(B24')=Sof(H24')=Sof(B25')=Sof(H25')=
 Sof(B26')=Sof(H26')=Sof(B27')=Sof(H27')=Sof(B28')=Sof(H28')=Sof(B29')=
 Sof(H29')=Sof(B30')=Sof(H30')=Sof(B31')=Sof(H31')=Sof(B32')=Sof(H32')=1-FVAR(1)
 Sof(S3)=Sof(C6)=Sof(B23)=Sof(H23)=Sof(B24)=Sof(H24)=Sof(B25)=Sof(H25)=
 Sof(B26)=Sof(H26)=Sof(B27)=Sof(H27)=Sof(B28)=Sof(H28)=Sof(B29)=Sof(H29)=
 Sof(B30)=Sof(H30)=Sof(B31)=Sof(H31)=Sof(B32)=Sof(H32)=FVAR(1)
 Sof(C13')=Sof(H13C)=Sof(H13D)=Sof(Cl2')=1-FVAR(2)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(Cl2)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C13'(H13C,H13D)
6.b Aromatic/amide H refined with riding coordinates:
 C18(H18), C14(H14), C16(H16)
6.c Boron cage BH refined with riding coordinates:
 B3(H3), B4(H4), B5(H5), B6(H6), B7(H7), B8(H8), B9(H9), B10(H10), B11(H11),
 B12(H12), B13(H13), B14(H14A), B15(H15), B16(H16A), B17(H17), B18(H18A),
 B19(H19), B20(H20), B21(H21), B22(H22), B23(H23), B24(H24), B25(H25), B26(H26),
  B27(H27), B28(H28), B29(H29), B30(H30), B31(H31), B32(H32), B23'(H23'),
 B24'(H24'), B25'(H25'), B26'(H26'), B27'(H27'), B28'(H28'), B29'(H29'),
 B30'(H30'), B31'(H31'), B32'(H32')
;
_shelx_res_checksum              83978
_shelx_fab_checksum              78417
_shelx_shelxl_version_number     2019/2
_olex2_submission_special_instructions 'No special instructions were received'