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_1574670
_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         'C80 H144 B20 Bi2 K2 N8 O4 Si4, 2(C4 H8 O)'
_chemical_formula_sum            'C88 H160 B20 Bi2 K2 N8 O6 Si4'
_chemical_formula_weight         2250.95
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-08
_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                70.800(4)
_cell_angle_beta                 86.199(3)
_cell_angle_gamma                84.365(3)
_cell_formula_units_Z            1
_cell_length_a                   10.0567(4)
_cell_length_b                   14.8404(6)
_cell_length_c                   19.9981(8)
_cell_measurement_reflns_used    8997
_cell_measurement_temperature    111.5(6)
_cell_measurement_theta_max      71.7900
_cell_measurement_theta_min      3.1410
_cell_volume                     2803.2(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-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      111.5(6)
_diffrn_detector_area_resol_mean 10.5435
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.966
_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     19.00 106.00   1.00    7.00    --   41.50  38.00-150.00   87
  2  \w    -26.00  69.00   1.00    7.00    --   41.50 -57.00 -60.00   95
  3  \w      8.00  94.00   1.00    7.00    --   41.50-125.00 -60.00   86
  4  \w    -30.00  66.00   1.00    7.00    --   41.50 -38.00  30.00   96
  5  \w     70.00 129.00   1.00    6.00    --  103.63 -61.00  30.00   59
  6  \w     77.00 118.00   1.00    6.00    --  103.63  61.00-180.00   41
  7  \w     32.00  63.00   1.00    6.00    --  103.63 -77.00-180.00   31
  8  \w     32.00 123.00   1.00    6.00    --  103.63 -45.00-180.00   91
  9  \w     28.00 104.00   1.00    6.00    --  103.63-111.00   0.00   76
 10  \w     61.00 109.00   1.00    6.00    --  103.63-111.00-120.00   48
 11  \w     36.00  62.00   1.00    6.00    --  103.63-111.00 150.00   26
 12  \w     74.00 109.00   1.00    6.00    --  103.63-111.00 150.00   35
 13  \w     76.00 158.00   1.00    6.00    --  103.63  61.00   0.00   82
 14  \w    132.00 157.00   1.00    6.00    --  103.63  61.00-180.00   25
 15  \w    103.00 133.00   1.00    6.00    --  103.63 -77.00-180.00   30
 16  \w     15.00 158.00   1.00    6.00    --  103.63   0.00-180.00  143
 17  \w     52.00 121.00   1.00    6.00    --  103.63 -45.00 -30.00   69
 18  \w     42.00 109.00   1.00    6.00    --  103.63-111.00  60.00   67
;
_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  0.0667
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21148
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.691
_diffrn_reflns_theta_min         3.164
_exptl_absorpt_coefficient_mu    7.539
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85827
_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    1.333
_exptl_crystal_description       needle
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.752
_refine_diff_density_min         -2.348
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     642
_refine_ls_number_reflns         10794
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0526
_refine_ls_R_factor_gt           0.0448
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0666P)^2^+2.2903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1134
_refine_ls_wR_factor_ref         0.1207
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9482
_reflns_number_total             10794
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02644j2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 1574669--1574673.cif.'
_cod_database_code               1574670
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.660
_olex2_refinement_description
;
1. Restrained distances
 C42-C43 \\sim C42A-C43
 with sigma of 0.02
 K1-C42 \\sim K1-C42A
 with sigma of 0.04
 K1-C41 \\sim K1-C41A
 with sigma of 0.04
 O3-C42 \\sim O3A-C42A
 with sigma of 0.04
 C44-C41 \\sim C44-C41A
 with sigma of 0.04
 C43-C41 \\sim C43-C41A
 with sigma of 0.04
 K1-O3 \\sim K1-O3A
 with sigma of 0.02
 O3-C41 \\sim O3A-C41A
 with sigma of 0.02
 O3-C44 \\sim O3A-C44
 with sigma of 0.02
 C42-C41 \\sim C42A-C41A
 with sigma of 0.02
 C43-C42 \\sim C43-C42A
 with sigma of 0.02
2. Rigid bond restraints
 C41, C42, C43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C41A, C42A, C43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Rigid body (RIGU) restrains
 C41, O3, C44, C43, C42
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C44, C43, C41A, C42A, O3A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Others
 Sof(H44C)=Sof(H44D)=Sof(H43C)=Sof(H43D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=
 Sof(O3A)=Sof(C42A)=Sof(H42C)=Sof(H42D)=1-FVAR(1)
 Sof(O3)=Sof(H44A)=Sof(H44B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H43A)=Sof(H43B)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C38(H38A,H38B), C40(H40A,H40B), C39(H39A,H39B), C34(H34A,
 H34B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C44(H44A,H44B),
 C44(H44C,H44D), C42(H42A,H42B), C43(H43A,H43B), C43(H43C,H43D), C41(H41A,H41B),
  C41A(H41C,H41D), C42A(H42C,H42D)
5.b Aromatic/amide H refined with riding coordinates:
 C24(H24), C28(H28), C13(H13), C9(H9), C25(H25), C27(H27), C10(H10), C26(H26),
 C12(H12), C11(H11)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C32(H32A,H32B,H32C), C15(H15A,H15B,H15C), C19(H19A,H19B,
 H19C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C30(H30A,H30B,H30C), C17(H17A,H17B,
 H17C), C20(H20A,H20B,H20C), C16(H16A,H16B,H16C), C21(H21A,H21B,H21C), C31(H31A,
 H31B,H31C)
5.d Boron cage BH refined with riding coordinates:
 B3(H3), B4(H4), B1(H1), B5(H5), B2(H2), B6(H6)
;
_shelx_res_checksum              38358
_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
;