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_7718761
_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         'C10 H18 N4 O5, 0.5[CHCl3]'
_chemical_formula_sum            'C10.5 H18.5 Cl1.5 N4 O5'
_chemical_formula_weight         333.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-12-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-14 deposited with the CCDC.	2025-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.915(5)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   20.5159(18)
_cell_length_b                   11.1570(9)
_cell_length_c                   25.254(2)
_cell_measurement_reflns_used    6076
_cell_measurement_temperature    296
_cell_measurement_theta_max      30.46
_cell_measurement_theta_min      2.19
_cell_volume                     5725.5(8)
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.998
_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  0.0867
_diffrn_reflns_av_unetI/netI     0.0743
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            23107
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.004
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.388
_exptl_absorpt_correction_T_max  0.3368
_exptl_absorpt_correction_T_min  0.2304
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1488 before and 0.0922 after correction.
The Ratio of minimum to maximum transmission is 0.6841.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.550
_exptl_crystal_description       prism
_exptl_crystal_F_000             2800
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.374
_refine_diff_density_min         -0.534
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     401
_refine_ls_number_reflns         5030
_refine_ls_number_restraints     40
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.1266
_refine_ls_R_factor_gt           0.1017
_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^)+(0.0811P)^2^+107.2245P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2565
_refine_ls_wR_factor_ref         0.2730
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3759
_reflns_number_total             5030
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00812c2.cif
_cod_data_source_block           pj389
_cod_depositor_comments
'Adding full bibliography for 7718760--7718765.cif.'
_cod_original_cell_volume        5725.6(9)
_cod_original_formula_sum        'C10.50 H18.50 Cl1.50 N4 O5'
_cod_database_code               7718761
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.926
_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, All O(H) groups
2. Restrained distances
 O5'-N4 \\sim O5-N4
 with sigma of 0.02
 O4-N4 \\sim O4'-N4
 with sigma of 0.02
 O5A'-N4A \\sim O5A-N4A
 with sigma of 0.02
 O4A'-N4A \\sim O4A-N4A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O5A') \\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O5')
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C9) \\sim Ueq, Uanis(C9A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O4) = Uanis(O4')
Uanis(O5) = Uanis(O5')
Uanis(O4A') = Uanis(O4A)
Uanis(O5A) = Uanis(O5A')
4. Others
 Sof(O4)=Sof(O5)=1-FVAR(1)
 Sof(O4')=Sof(O5')=FVAR(1)
 Sof(O4A')=Sof(O5A')=1-FVAR(2)
 Sof(O4A)=Sof(O5A)=FVAR(2)
5.a Riding coordinates:
 O2(H2), O3(H3), O1A(H1A), O2A(H2AA)
5.b Ternary CH refined with riding coordinates:
 C1S(H1S)
5.c Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C5(H5A,H5B), C8(H8A,H8B), C2A(H2AB,H2AC), C5A(H5AA,H5AB),
 C8A(H8AA,H8AB)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C4A(H4AA,H4AB,H4AC),
 C7A(H7AA,H7AB,H7AC), C10A(H10D,H10E,H10F)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3A(H3A)
;
_shelx_res_checksum              67834
_shelx_hkl_checksum              43643
_olex2_submission_special_instructions 'No special instructions were received'