Azadistibiridines and stabilised-iminobismuthane: reactivity of small inorganic rings in heavy main group chemistry.
Palui, Prasenjit; Bollenbeck, Matthias; Meleschko, Daniel; Brehm, Philipp; Gomila, Rosa M.; Schnakenburg, Gregor; Frontera, Antonio; Bismuto, Alessandro; Chemical science 16 (2025) 16894–16903; doi:10.1039/d5sc03416g

data_1575514
_publ_section_title
;
 Azadistibiridines and stabilised-iminobismuthane: reactivity of small
 inorganic rings in heavy main group chemistry.
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              16894
_journal_page_last               16903
_journal_paper_doi               10.1039/d5sc03416g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(C31 H56 Bi N O2 S Si4)'
_chemical_formula_sum            'C62 H112 Bi2 N2 O4 S2 Si8'
_chemical_formula_weight         1656.33
_chemical_name_systematic        MBO68
_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             2024-08-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-04-01 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.583(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.3099(10)
_cell_length_b                   13.9032(4)
_cell_length_c                   28.5661(12)
_cell_measurement_reflns_used    30828
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.09
_cell_measurement_theta_min      1.64
_cell_volume                     7730.8(6)
_computing_cell_refinement       'X-Area Recipe 2.0.2 (STOE, 2024)'
_computing_data_collection       'X-Area WinXpose 2.0.29.0 (STOE, 2023)'
_computing_data_reduction
;
X-Area Integrate 2.5.18.0 (STOE, 2024)
X-Area LANA 2.8.4 (STOE, 2024)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 6.67
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1052
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            95660
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         2.137
_diffrn_source                   'Anton Paar Primux50'
_exptl_absorpt_coefficient_mu    4.765
_exptl_absorpt_correction_T_max  0.5967
_exptl_absorpt_correction_T_min  0.4015
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Afterwards a spherical absorption correction was performed within STOE LANA.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3360
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.652
_refine_diff_density_min         -1.112
_refine_diff_density_rms         0.204
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     794
_refine_ls_number_reflns         15180
_refine_ls_number_restraints     668
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1007
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0092P)^2^+155.9660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1116
_refine_ls_wR_factor_ref         0.1319
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11035
_reflns_number_total             15180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03416g3.cif
_cod_data_source_block           4a
_cod_depositor_comments
'Adding full bibliography for 1575509--1575515.cif.'
_cod_database_code               1575514
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.702
_shelx_estimated_absorpt_t_min   0.647
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14'-C15' \\sim C14'-C16' \\sim C14'-C17' \\sim C14'-C15" \\sim C14'-C16"
\\sim C14'-C17"
 with sigma of 0.001
 C15'-C16' \\sim C16'-C17' \\sim C17'-C15'
 with sigma of 0.001
 C15"-C16" \\sim C16"-C17" \\sim C17"-C15"
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Bi" \\sim Bi': within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Uanis(Bi') \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Bi") \\sim Ueq, Uanis(Bi') \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C15")=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16")=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17")=Sof(H17A)=Sof(H17B)=Sof(H17C)=1-FVAR(1)
 Sof(C15')=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16')=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17')=Sof(H17D)=Sof(H17E)=Sof(H17F)=FVAR(1)
 Sof(Bi")=1-FVAR(2)
 Sof(Bi')=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C18(H18), C7'(H7'), C18'(H18')
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C26(H26), C27(H27), C29(H29), C30(H30), C3'(H3'), C5'(H5'),
 C26'(H26'), C27'(H27'), C29'(H29'), C30'(H30')
6.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10D,H10E,H10F), C11(H11D,H11E,H11F),
 C12(H12D,H12E,H12F), C13(H13D,H13E,H13F), C15(H15G,H15H,H15I), C16(H16G,H16H,
 H16I), C17(H17G,H17H,H17I), C19(H19D,H19E,H19F), C20(H20D,H20E,H20F), C21(H21D,
 H21E,H21F), C22(H22D,H22E,H22F), C23(H23D,H23E,H23F), C24(H24D,H24E,H24F),
 C31(H31D,H31E,H31F), C8'(H8'A,H8'B,H8'C), C9'(H9'A,H9'B,H9'C), C10'(H10A,H10B,
 H10C), C11'(H11A,H11B,H11C), C12'(H12A,H12B,H12C), C13'(H13A,H13B,H13C),
 C15"(H15A,H15B,H15C), C15'(H15D,H15E,H15F), C16"(H16A,H16B,H16C), C16'(H16D,
 H16E,H16F), C17"(H17A,H17B,H17C), C17'(H17D,H17E,H17F), C19'(H19A,H19B,H19C),
 C20'(H20A,H20B,H20C), C21'(H21A,H21B,H21C), C22'(H22A,H22B,H22C), C23'(H23A,
 H23B,H23C), C24'(H24A,H24B,H24C), C31'(H31A,H31B,H31C)
;
_shelx_res_checksum              90931
_olex2_submission_special_instructions 'No special instructions were received'