Transition metal(IV) complexes of nitro-substituted 2,4,9-triazaadamantane-based tris-hydroxylamines: evidence for nitrogen α-effect on stabilization of higher oxidation states.
Pospelov, Evgeny V.; Sinyushin, Kirill I.; Golovanov, Ivan S.; Lesnikov, Vladislav K.; Frolov, Kirill V.; Nelyubina, Yulia V.; Sukhorukov, Alexey Yu; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9530–9541; doi:10.1039/d5dt00812c

data_7718764
_publ_section_title
;
 Transition metal(IV) complexes of nitro-substituted
 2,4,9-triazaadamantane-based tris-hydroxylamines: evidence for nitrogen
 &#x3b1;-effect on stabilization of higher oxidation states.
;
_journal_issue                   24
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9530
_journal_page_last               9541
_journal_paper_doi               10.1039/d5dt00812c
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C19 H32 B K N4 O8'
_chemical_formula_sum            'C19 H32 B K N4 O8'
_chemical_formula_weight         494.39
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-26 deposited with the CCDC.	2025-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.970(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9221(3)
_cell_length_b                   12.6921(4)
_cell_length_c                   23.3835(6)
_cell_measurement_reflns_used    4231
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      29.62
_cell_measurement_theta_min      2.38
_cell_volume                     2622.37(14)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0884
_diffrn_reflns_av_unetI/netI     0.0680
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            29325
_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         26.999
_diffrn_reflns_theta_min         2.350
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.249
_exptl_absorpt_correction_T_max  0.4330
_exptl_absorpt_correction_T_min  0.3310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1311 before and 0.0711 after correction.
The Ratio of minimum to maximum transmission is 0.7644.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       prism
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.607
_refine_diff_density_min         -0.362
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         5723
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0523
_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^)+(0.0555P)^2^+1.8358P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1230
_refine_ls_wR_factor_ref         0.1417
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4014
_reflns_number_total             5723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00812c2.cif
_cod_data_source_block           PJ388
_cod_depositor_comments
'Adding full bibliography for 7718760--7718765.cif.'
_cod_database_code               7718764
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.940
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O3S-C3S \\sim O3S-C3S'
 with sigma of 0.02
 O2S-C2S' \\sim O2S-C2S
 with sigma of 0.02
 O2S'-C2S' \\sim O2S-C2S
 with sigma of 0.02
 O3S'-C3S' \\sim O3S-C3S
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O3S') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2S) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O2S) = Uanis(O2S')
Uanis(C2S') = Uanis(C2S)
Uanis(C3S) = Uanis(C3S')
Uanis(O3S') = Uanis(O3S)
4. Others
 Sof(O3S')=Sof(C3S')=Sof(H3SD)=Sof(H3SE)=Sof(H3SF)=1-FVAR(1)
 Sof(O3S)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=FVAR(1)
 Sof(O2S')=Sof(C2S')=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=1-FVAR(2)
 Sof(O2S)=Sof(C2S)=Sof(H2SD)=Sof(H2SE)=Sof(H2SF)=FVAR(2)
5.a Riding coordinates:
 O2S(H2S'), O3S(H3S)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C8(H8A,H8B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C2S'(H2SA,H2SB,H2SC),
 C2S(H2SD,H2SE,H2SF), C3S(H3SA,H3SB,H3SC), C3S'(H3SD,H3SE,H3SF), C1S(H1SA,H1SB,
 H1SC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38603
_shelx_hkl_checksum              34496
_shelx_fab_checksum              50680
_olex2_submission_special_instructions 'No special instructions were received'