Transition metal-mediated B(4)-H hydroxylation/halogenation of o-carboranes bearing a 2-pyridylsulfenyl ligand.
Guo, Shu-Ting; Cui, Peng-Fei; Yuan, Run-Ze; Jin, Guo-Xin; Chemical communications (Cambridge, England) 57 (2021) 2412–2415; doi:10.1039/d0cc08290b

data_7127877
_publ_section_title
;
 Transition metal-mediated B(4)-H hydroxylation/halogenation of
 o-carboranes bearing a 2-pyridylsulfenyl ligand.
;
_journal_issue                   19
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              2412
_journal_page_last               2415
_journal_paper_doi               10.1039/d0cc08290b
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety         'C17 H29 B9 N Rh S, C H Cl3'
_chemical_formula_sum            'C18 H30 B9 Cl3 N Rh S'
_chemical_formula_weight         599.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-18 deposited with the CCDC.	2021-01-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.623(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.1460(7)
_cell_length_b                   9.4000(4)
_cell_length_c                   16.8416(7)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      59.29
_cell_measurement_theta_min      4.53
_cell_volume                     2690.41(19)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173.02
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0650
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            14358
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         58.454
_diffrn_reflns_theta_min         4.527
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.724
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.4531
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1435 before and 0.0883 after correction.
The Ratio of minimum to maximum transmission is 0.6028.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.479
_exptl_crystal_description       sheet
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.644
_refine_diff_density_min         -0.890
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         3069
_refine_ls_number_restraints     62
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0360
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0620P)^2^+1.3415P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0905
_refine_ls_wR_factor_ref         0.0921
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2905
_reflns_number_total             3069
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc08290b2.cif
_cod_data_source_block           ga_200826g_a
_cod_depositor_comments
'Adding full bibliography for 7127874--7127881.cif.'
_cod_database_code               7127877
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.847
_shelx_estimated_absorpt_t_min   0.394
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{B6, C2'}
{B5, B5'}
{B4, B4'}
{B3, B3'}
{B2, B2'}
{B1, B1'}
{C3, N1}
{C4, C4'}
{C5, C5'}
3. Restrained distances
 B6-H6
 1.14 with sigma of 0.1
 C3-H3A = C4-H4A = C5-H5A
 1.08 with sigma of 0.1
 C12-Cl2 = C12'-Cl1' = C12'-Cl2' = C12'-Cl3'
 1.72 with sigma of 0.03
4. Uiso/Uaniso restraints and constraints
C12 \\sim C12': within 2A with sigma of 0.02 and sigma for terminal atoms of
0.05
Uanis(C12) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3)
\\sim Ueq, Uanis(C12') \\sim Ueq, Uanis(Cl1') \\sim Ueq, Uanis(Cl2') \\sim Ueq,
Uanis(Cl3') \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(B6) = Uanis(C2')
Uanis(B5) = Uanis(B5')
Uanis(B4) = Uanis(B4')
Uanis(B3) = Uanis(B3')
Uanis(B2) = Uanis(B2')
Uanis(B1) = Uanis(B1')
Uanis(C3) = Uanis(N1)
Uanis(C4) = Uanis(C4')
Uanis(C5) = Uanis(C5')
5. Others
 Sof(C12')=Sof(Cl1')=Sof(Cl2')=Sof(Cl3')=0.5*(1-FVAR(2))
 Sof(C12)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=0.5*FVAR(2)
 Fixed Sof: B1(0.25) B2(0.25) B3(0.5) B4(0.5) B5(0.5) B6(0.5) B1'(0.25)
 B2'(0.25) B3'(0.5) B4'(0.5) B5'(0.5) C2'(0.5) C3(0.5) C4(0.5) C5(0.25) N1(0.5)
 C4'(0.5) C5'(0.25) H11A(0.5) H11B(0.5) H11C(0.5) H3A(0.5) H12(0.5)
6.a Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              88049
_olex2_submission_special_instructions 'No special instructions were received'