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_1571660
_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         'C22 H42 B20 N2 Rh S2, C F3 O3 S'
_chemical_formula_sum            'C23 H42 B20 F3 N2 O3 Rh S3'
_chemical_formula_weight         866.87
_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
_audit_creation_date             2023-09-14
_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                99.204(4)
_cell_angle_beta                 101.430(4)
_cell_angle_gamma                91.527(4)
_cell_formula_units_Z            2
_cell_length_a                   11.6103(11)
_cell_length_b                   13.1824(13)
_cell_length_c                   13.5411(13)
_cell_measurement_reflns_used    9762
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      52.49
_cell_measurement_theta_min      3.38
_cell_volume                     2001.6(3)
_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      173.0
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_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  0.0284
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            13097
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        51.998
_diffrn_reflns_theta_max         51.998
_diffrn_reflns_theta_min         2.960
_exptl_absorpt_coefficient_mu    3.495
_exptl_absorpt_correction_T_max  0.6146
_exptl_absorpt_correction_T_min  0.4633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1716 before and 0.0692 after correction.
The Ratio of minimum to maximum transmission is 0.7538.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       block
_exptl_crystal_F_000             876
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.717
_refine_diff_density_min         -0.805
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         6632
_refine_ls_number_restraints     135
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0176P)^2^+5.6562P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0906
_refine_ls_wR_factor_ref         0.1036
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5569
_reflns_number_total             6632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01158a2.cif
_cod_data_source_block           ga_230808f_a
_cod_depositor_comments
'Adding full bibliography for 1571656--1571663.cif.'
_cod_database_code               1571660
_shelx_estimated_absorpt_t_max   0.572
_shelx_estimated_absorpt_t_min   0.475
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-H2A = C12-H12A
 1.04 with sigma of 0.05
 N1-H1 = N2-H2
 0.95 with sigma of 0.02
 S3'-C23'
 1.8 with sigma of 0.02
 S3'-O2'
 1.43 with sigma of 0.02
 C23-F2 = C23'-F1' = C23'-F2' = C23'-F3'
 1.32 with sigma of 0.02
 F2-F3 = F1'-F2' = F1'-F3' = F2'-F3'
 2.1 with sigma of 0.03
 S3-F2
 2.6 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
C23 \\sim F2 \\sim C23' \\sim F2': within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.05
Uanis(S3) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(S3') \\sim
Ueq, Uanis(O3') \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(C23') \\sim Ueq, Uanis(F1') \\sim Ueq,
Uanis(F2') \\sim Ueq, Uanis(F3') \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(O2') \\sim Ueq: with sigma of 0.007 and sigma for terminal atoms of 0.014
4. Others
 Sof(S3')=Sof(O2')=Sof(O3')=Sof(C23')=Sof(F1')=Sof(F2')=Sof(F3')=1-FVAR(1)
 Sof(S3)=Sof(O2)=Sof(O3)=Sof(C23)=Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C7(H7A), C8(H8A), C9(H9A)
5.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C)
5.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(H14), B15(H15), B16(H16), B17(H17), B18(H18), B19(H19),
  B20(H20), B21(H21), B22(H22)
;
_shelx_res_checksum              66173
_shelx_shelxl_version_number     2019/2
_olex2_submission_special_instructions 'No special instructions were received'