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_1574672
_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         'C32 H56 B10 Bi N4 Si2, 2[C7H8]'
_chemical_formula_sum            'C46 H72 B10 Bi N4 Si2'
_chemical_formula_weight         1054.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           63
_space_group_name_Hall           '-C 2c 2'
_space_group_name_H-M_alt        'C m c m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-27
_audit_creation_method
;
Olex2 1.5-beta
(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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.2329(4)
_cell_length_b                   18.6010(4)
_cell_length_c                   13.6308(3)
_cell_measurement_reflns_used    10878
_cell_measurement_temperature    110.07(12)
_cell_measurement_theta_max      72.4760
_cell_measurement_theta_min      2.4070
_cell_volume                     5890.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (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 0.998
_diffrn_measured_fraction_theta_max 0.992
_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     10.00  98.00   1.00    7.00    --   41.62-125.00 120.00   88
  2  \w    -31.00  50.00   1.00    7.00    --   41.62 -57.00-120.00   81
  3  \w      6.00  58.00   1.00    7.00    --   41.62-125.00-150.00   52
  4  \w    100.00 139.00   1.00    8.00    --  103.63  77.00 -90.00   39
  5  \w     90.00 136.00   1.00    8.00    --  103.63 -77.00-180.00   46
  6  \w     30.00  72.00   1.00    8.00    --  103.63 -77.00-180.00   42
  7  \w     83.00 150.00   1.00    8.00    --  103.63  45.00-120.00   67
  8  \w     82.00 122.00   1.00    8.00    --  103.63  77.00 -30.00   40
  9  \w     95.00 148.00   1.00    8.00    --  103.63 111.00 150.00   53
 10  \w     51.00 127.00   1.00    8.00    --  103.63 -61.00 -30.00   76
 11  \w     99.00 147.00   1.00    8.00    --  103.63 111.00 -90.00   48
 12  \w     44.00  70.00   1.00    8.00    --  103.63 -15.00  90.00   26
;
_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  0.0935
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            21230
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.824
_diffrn_reflns_theta_min         3.805
_exptl_absorpt_coefficient_mu    6.487
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       block
_exptl_crystal_F_000             2148
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.404
_refine_diff_density_min         -1.571
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         3118
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0561
_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^)+(0.0781P)^2^+32.9507P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1501
_refine_ls_wR_factor_ref         0.1545
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2807
_reflns_number_total             3118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02644j2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 1574669--1574673.cif.'
_cod_database_code               1574672
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Others
 Fixed Sof: Bi1(0.24) Bi2(0.01)
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C8(H8), C10(H10), C9(H9)
2.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C)
2.c Boron cage BH refined with riding coordinates:
 B4(H4), B2(H2), B3(H3), B1(H1)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 336 electrons were 
found in a volume of 1442\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C6H6] per formula unit 
which account for 336 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              72979
_shelx_fab_checksum              86545
_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
;