Isolable monoatomic monovalent bismuth complexes with a redox non-innocent bis-silylenyl carborane ligand
Xu, Jian; Yao, Shenglai; Postils, Verònica; Matito, Eduard; Lorent, Christian; Driess, Matthias; Chemical Science 16 (2025) 10826–10832; doi:10.1039/D5SC02644J

data_1574673
_publ_section_title
;
 Isolable monoatomic monovalent bismuth complexes with a redox
 non-innocent bis-silylenyl carborane ligand
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              10826
_journal_page_last               10832
_journal_paper_doi               10.1039/D5SC02644J
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C33 H59 B10 Bi N4 Si2, 2(C F3 O3 S), C H2 Cl2'
_chemical_formula_sum            'C36 H61 B10 Bi Cl2 F6 N4 O6 S2 Si2'
_chemical_formula_weight         1268.16
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-27
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-01 deposited with the CCDC.	2025-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.144(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.1469(4)
_cell_length_b                   18.0810(3)
_cell_length_c                   18.3593(4)
_cell_measurement_reflns_used    19361
_cell_measurement_temperature    111.3(6)
_cell_measurement_theta_max      72.1180
_cell_measurement_theta_min      3.3850
_cell_volume                     5306.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      111.15
_diffrn_detector_area_resol_mean 10.5435
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -66.00  39.00   1.00    6.00    --  -41.50  19.00-180.00  105
  2  \w    -44.00  -7.00   1.00    6.00    --  -41.50 125.00-150.00   37
  3  \w   -115.00 -23.00   1.00    6.00    --  -41.50 -38.00   0.00   92
  4  \w    -96.00 -12.00   1.00    6.00    --  -41.50 125.00 120.00   84
  5  \w     32.00  96.00   1.00    6.00    --   41.50-125.00 -30.00   64
  6  \w     54.00 109.00   1.00    7.00    --  103.94-111.00-150.00   55
  7  \w     97.00 124.00   1.00    7.00    --  103.94 -77.00 -60.00   27
  8  \w     43.00 124.00   1.00    7.00    --  103.94 -45.00 -90.00   81
  9  \w     31.00 109.00   1.00    7.00    --  103.94-111.00  90.00   78
 10  \w     47.00  74.00   1.00    7.00    --  103.94-111.00 120.00   27
 11  \w     33.00 158.00   1.00    7.00    --  103.94   0.00-120.00  125
 12  \w     71.00  98.00   1.00    7.00    --  103.94 -94.00 -90.00   27
 13  \w     31.00 116.00   1.00    7.00    --  103.94 -45.00  60.00   85
 14  \w     32.00 127.00   1.00    7.00    --  103.94 -45.00-180.00   95
 15  \w     66.00 108.00   1.00    7.00    --  103.94-111.00   0.00   42
 16  \w     95.00 158.00   1.00    7.00    --  103.94  45.00 -90.00   63
 17  \w    108.00 141.00   1.00    7.00    --  103.94 111.00-150.00   33
 18  \w     66.00 109.00   1.00    7.00    --  103.94-111.00 -90.00   43
 19  \w    117.00 146.00   1.00    7.00    --  103.94 178.00-120.00   29
 20  \w     24.00  49.00   1.00    7.00    --  103.94 -94.00-150.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0906
_diffrn_reflns_av_unetI/netI     0.0689
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            36892
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.874
_diffrn_reflns_theta_min         3.414
_exptl_absorpt_coefficient_mu    9.186
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61545
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.137a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.588
_exptl_crystal_description       block
_exptl_crystal_F_000             2536
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         3.143
_refine_diff_density_min         -2.912
_refine_diff_density_rms         0.233
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     639
_refine_ls_number_reflns         10398
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0799
_refine_ls_R_factor_gt           0.0620
_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^)+(0.1581P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1785
_refine_ls_wR_factor_ref         0.2149
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8214
_reflns_number_total             10398
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02644j2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1574669--1574673.cif.'
_cod_database_code               1574673
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C36) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Bi1) = Uanis(Bi1A)
2. Others
 Sof(Bi1A)=1-FVAR(1)
 Sof(Bi1)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C36(H36A,H36B)
3.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C14(H14), C10(H10), C26(H26), C29(H29), C13(H13), C27(H27),
 C11(H11), C12(H12), C28(H28)
3.c Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C7(H7A,H7B,H7C), C22(H22A,H22B,H22C), C21(H21A,H21B,
 H21C), C5(H5A,H5B,H5C), C33(H33A,H33B,H33C), C6(H6A,H6B,H6C), C20(H20A,H20B,
 H20C), C32(H32A,H32B,H32C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C3(H3A,
 H3B,H3C), C18(H18A,H18B,H18C)
3.d Boron cage BH refined with riding coordinates:
 B7(H7), B4(H4), B9(H9), B10(H10A), B1(H1), B8(H8), B6(H6), B5(H5), B3(H3),
 B2(H2)
;
_shelx_res_checksum              83316
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;