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_1575515
_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         'C62 H123 N O Sb2 Si8'
_chemical_formula_sum            'C62 H123 N O Sb2 Si8'
_chemical_formula_weight         1366.83
_chemical_name_systematic        MB037
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-01 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.9310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8015(6)
_cell_length_b                   12.3747(4)
_cell_length_c                   34.4746(12)
_cell_measurement_reflns_used    9774
_cell_measurement_temperature    103.00
_cell_measurement_theta_max      27.613
_cell_measurement_theta_min      2.412
_cell_volume                     7456.6(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      103.00
_diffrn_detector                 'Bruker Photon100 detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0677
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            206446
_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         28.000
_diffrn_reflns_theta_min         2.040
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.888
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.6756
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1005 before and 0.0664 after correction.
The Ratio of minimum to maximum transmission is 0.9053.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       plate
_exptl_crystal_F_000             2896
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.312
_refine_diff_density_min         -1.734
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.316
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     942
_refine_ls_number_reflns         18010
_refine_ls_number_restraints     539
_refine_ls_restrained_S_all      1.305
_refine_ls_R_factor_all          0.0685
_refine_ls_R_factor_gt           0.0642
_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^)+42.5292P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1347
_refine_ls_wR_factor_ref         0.1364
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16800
_reflns_number_total             18010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03416g3.cif
_cod_data_source_block           2d
_cod_depositor_comments
'Adding full bibliography for 1575509--1575515.cif.'
_cod_database_code               1575515
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.808
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C55S-C49 = C56S-C55S
 1.5 with sigma of 0.01
 C60-C59
 1.5 with sigma of 0.01
 O1-C60
 1.42 with sigma of 0.01
 C55-C49 = C55S-C49 = C50-C49 = C50S-C49 = C54-C49 = C54S-C49 = C56-C55 = C54S-
 C53S = C53S-C52S = C58-C51 = C58S-C56S = C51S-C50S = C51-C50 = C54-C53
 1.5 with sigma of 0.01
 N1-C49 \\sim N1S-C49
 with sigma of 0.001
 Sb2-N1 \\sim Sb2S-N1S \\sim Sb1-N1 \\sim Sb1S-N1S
 with sigma of 0.001
 Sb2-Sb1 \\sim Sb2S-Sb1S
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C14 \\sim C15 \\sim C15S \\sim C16 \\sim C16S \\sim C17 \\sim C17S: within 2A
with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C49 \\sim C50 \\sim C50S \\sim C51 \\sim C51S \\sim C52 \\sim C52S \\sim C53
\\sim C54 \\sim C54S \\sim C55 \\sim C55S \\sim C56 \\sim C56S \\sim C57 \\sim
C57S \\sim C58 \\sim C58S \\sim C53S: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
N1 \\sim N1S: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
Sb1 \\sim Sb1S \\sim Sb2S \\sim Sb2: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
C40 \\sim C39 \\sim C44 \\sim C39S \\sim C41 \\sim C38S \\sim C38 \\sim C41S
\\sim C40S: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
N1 \\sim N1S \\sim C49 \\sim C55 \\sim C54S \\sim C54 \\sim C55S \\sim C50
\\sim C50S: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
4. Rigid body (RIGU) restrains
 C62, C61, O1, C60, C59
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C32S)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33S)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C34S)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(1)
 Sof(C35S)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36S)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37S)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(2)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
 Sof(Sb1S)=Sof(Sb2S)=Sof(N1S)=1-FVAR(3)
 Sof(Sb1)=Sof(Sb2)=Sof(N1)=FVAR(3)
 Sof(C50S)=Sof(H50C)=Sof(H50D)=Sof(C51S)=Sof(H51S)=Sof(C52S)=Sof(H52C)=
 Sof(H52D)=Sof(C54S)=Sof(H54C)=Sof(H54D)=Sof(C55S)=Sof(H55C)=Sof(H55D)=
 Sof(C56S)=Sof(H56S)=Sof(C57S)=Sof(H57C)=Sof(H57D)=Sof(C58S)=Sof(H58C)=
 Sof(H58D)=Sof(C53S)=Sof(H53S)=1-FVAR(4)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=
 FVAR(4)
 Sof(C38S)=Sof(C39S)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40S)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=Sof(C41S)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(5)
 Sof(C38)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(5)
 Sof(C15S)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16S)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17S)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(6)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C18(H18), C31(H31), C42(H42), C51(H51), C51S(H51S), C53(H53),
 C56(H56), C56S(H56S), C53S(H53S)
6.b Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C50S(H50C,H50D), C52(H52A,H52B), C52S(H52C,H52D), C54(H54A,
 H54B), C54S(H54C,H54D), C55(H55A,H55B), C55S(H55C,H55D), C57(H57A,H57B),
 C57S(H57C,H57D), C58(H58A,H58B), C58S(H58C,H58D), C60(H60A,H60B), C61(H61A,
 H61B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C27(H27), C29(H29)
6.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C15S(H15D,H15E,
 H15F), C16(H16A,H16B,H16C), C16S(H16D,H16E,H16F), C17(H17A,H17B,H17C),
 C17S(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), C32(H32A,
 H32B,H32C), C32S(H32D,H32E,H32F), C33(H33A,H33B,H33C), C33S(H33D,H33E,H33F),
 C34(H34A,H34B,H34C), C34S(H34D,H34E,H34F), C35(H35A,H35B,H35C), C35S(H35D,H35E,
 H35F), C36(H36A,H36B,H36C), C36S(H36D,H36E,H36F), C37(H37A,H37B,H37C),
 C37S(H37D,H37E,H37F), C39(H39A,H39B,H39C), C39S(H39D,H39E,H39F), C40(H40A,H40B,
 H40C), C40S(H40D,H40E,H40F), C41(H41A,H41B,H41C), C41S(H41D,H41E,H41F),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C59(H59A,H59B,H59C), C62(H62A,
 H62B,H62C)
;
_shelx_res_checksum              8865
_olex2_submission_special_instructions 'No special instructions were received'