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_7718765
_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         '2(C16 H30 N7 Ni O5), 4(C H4 O), 2(Cl), H2 O'
_chemical_formula_sum            'C36 H78 Cl2 N14 Ni2 O15'
_chemical_formula_weight         1135.44
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-11
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-02-12 deposited with the CCDC.	2025-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.30780(10)
_cell_length_b                   13.51830(10)
_cell_length_c                   21.2684(2)
_cell_measurement_reflns_used    30245
_cell_measurement_temperature    99.97(12)
_cell_measurement_theta_max      79.7510
_cell_measurement_theta_min      3.2660
_cell_volume                     5263.72(7)
_computing_cell_refinement       'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.91a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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    -83.00  -9.00   0.50    1.00    --  -42.78 119.00-150.00  148
  2  \w   -117.00 -51.00   0.50    1.00    --  -42.78-158.00 -29.00  132
  3  \w    -37.00  29.00   0.50    1.00    --   42.78 -23.00 -30.00  132
  4  \w    106.00 178.00   0.50    4.00    --  117.50 104.00 -50.00  144
  5  \w     90.00 178.00   0.50    4.00    --  117.50  23.00 134.00  176
  6  \w     46.00 109.00   0.50    4.00    --  117.50-119.00 124.00  126
  7  \w    106.00 178.00   0.50    4.00    --  117.50 104.00 -50.00  144
  8  \w   -117.00 -20.00   0.50    1.00    --  -42.78 -57.00-150.00  194
  9  \w    -27.00  38.00   0.50    1.00    --  -42.78  19.00-180.00  130
 10  \w   -117.00 -20.00   0.50    1.00    --  -42.78 -57.00-150.00  194
 11  \w     44.00  71.00   0.50    4.00    --  117.50 -61.00   0.00   54
 12  \w     44.00 105.00   0.50    4.00    --  117.50 -95.00  30.00  122
 13  \w     44.00 105.00   0.50    4.00    --  117.50 -95.00 -90.00  122
 14  \w     52.00 111.00   0.50    4.00    --  117.50-125.00-150.00  118
 15  \w     54.00  91.00   0.50    4.00    --  117.50 -77.00-150.00   74
 16  \w     44.00  69.00   0.50    4.00    --  117.50 -61.00 -30.00   50
 17  \w    143.00 178.00   0.50    4.00    --  117.50  30.00 -90.00   70
 18  \w     45.00  71.00   0.50    4.00    --  117.50 -77.00-120.00   52
 19  \w     44.00  98.00   0.50    4.00    --  117.50 -95.00-150.00  108
 20  \w     98.00 128.00   0.50    4.00    --  117.50 125.00   0.00   60
 21  \w     44.00  69.00   0.50    4.00    --  117.50 -61.00  60.00   50
 22  \w     49.00  75.00   0.50    4.00    --  117.50 -95.00  60.00   52
 23  \w     45.00  94.00   0.50    4.00    --  117.50 -77.00 150.00   98
 24  \w     89.00 115.00   0.50    4.00    --  117.50  15.00  60.00   52
 25  \w    123.00 174.00   0.50    4.00    --  117.50  15.00  60.00  102
 26  \w     95.00 124.00   0.50    4.00    --  117.50  45.00 -60.00   58
 27  \w    153.00 178.00   0.50    4.00    --  117.50  45.00 -60.00   50
 28  \w     56.00  82.00   0.50    4.00    --  117.50 -85.00  97.47   52
 29  \w     87.00 112.00   0.50    4.00    --  117.50 -85.00  97.47   50
 30  \w     48.00  73.00   0.50    4.00    --  117.50-125.00-150.00   50
 31  \w     50.00  79.00   0.50    4.00    --  117.50 -77.00 -60.00   58
 32  \w     79.00 105.00   0.50    4.00    --  117.50 -95.00-180.00   52
 33  \w     79.00 105.00   0.50    4.00    --  117.50 -95.00   0.00   52
 34  \w     44.00  69.00   0.50    4.00    --  117.50 -61.00 120.00   50
 35  \w     97.00 135.00   0.50    4.00    --  117.50-158.00 -29.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0158277000
_diffrn_orient_matrix_UB_12      0.1099444000
_diffrn_orient_matrix_UB_13      -0.0131425000
_diffrn_orient_matrix_UB_21      0.0199843000
_diffrn_orient_matrix_UB_22      -0.0255666000
_diffrn_orient_matrix_UB_23      -0.0684486000
_diffrn_orient_matrix_UB_31      -0.0802399000
_diffrn_orient_matrix_UB_32      0.0153422000
_diffrn_orient_matrix_UB_33      -0.0196863000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0333
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            43580
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.949
_diffrn_reflns_theta_min         4.157
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.452
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.486
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.91a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.261
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.134
_refine_diff_density_max         0.697
_refine_diff_density_min         -0.535
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.159
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     413
_refine_ls_number_reflns         5694
_refine_ls_number_restraints     50
_refine_ls_restrained_S_all      1.156
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0643P)^2^+20.1737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1815
_refine_ls_wR_factor_ref         0.1818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5567
_reflns_number_total             5694
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00812c2.cif
_cod_data_source_block           PJ1270
_cod_depositor_comments
'Adding full bibliography for 7718760--7718765.cif.'
_cod_database_code               7718765
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C36H78Cl2N14Ni2O15
_chemical_oxdiff_usercomment     PJ1270
_shelx_estimated_absorpt_t_max   0.735
_shelx_estimated_absorpt_t_min   0.567
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All Cl(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups, All O(H,H)
  groups
2. Restrained distances
 N4-O5 \\sim N4A-O5A
 with sigma of 0.02
 N4A-C5A \\sim N4-C5
 with sigma of 0.02
 C5-C8 \\sim C5A-C8A
 with sigma of 0.02
 C5-C2 \\sim C5A-C2A
 with sigma of 0.02
 N3-O4 \\sim N3A-O4A
 with sigma of 0.02
 O5-Ni1 \\sim O5A-Ni1A
 with sigma of 0.02
 O4-Ni1 \\sim O4A-Ni1A
 with sigma of 0.02
 O3-Ni1 \\sim O3A-Ni1A
 with sigma of 0.02
 C7-N4 \\sim C7A-N4A
 with sigma of 0.02
 C7-N3 \\sim C7A-N3A
 with sigma of 0.02
 C6-N3 \\sim C6A-N3A
 with sigma of 0.02
 C9-C6 \\sim C9A-C6A
 with sigma of 0.02
 N2-C5 \\sim N2A-C5A
 with sigma of 0.02
 N2-C6 \\sim N2A-C6A
 with sigma of 0.02
 N2-O3 \\sim N2A-O3A
 with sigma of 0.02
 C6-C3 \\sim C6A-C3A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3A
 with sigma of 0.02
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 N1-C1 \\sim N1A-C1A
 with sigma of 0.02
 C1-C4 \\sim C1A-C4A
 with sigma of 0.02
 C7-C4 \\sim C7A-C4A
 with sigma of 0.02
 N1-O1 \\sim N1A-O1A
 with sigma of 0.02
 N1-O2 \\sim N1A-O2A
 with sigma of 0.02
 C10-C7 \\sim C10A-C7A
 with sigma of 0.02
 C18-O7 \\sim C18-O7A
 with sigma of 0.02
 O1-O2 \\sim O1A-O2A
 with sigma of 0.02
 O1A-C1A \\sim O2A-C1A
 with sigma of 0.02
 C10-C4 \\sim C10A-C4A
 with sigma of 0.02
 C9-C3 \\sim C9A-C3A
 with sigma of 0.02
 N2A-C9A \\sim N3A-C9A
 with sigma of 0.02
 C8-C2 \\sim C8A-C2A
 with sigma of 0.02
 N4-N3 \\sim N4A-N3A
 with sigma of 0.02
 N4-N2 \\sim N4A-N2A
 with sigma of 0.02
 N3-N2 \\sim N3A-N2A
 with sigma of 0.02
 O3-O4 \\sim O3A-O4A
 with sigma of 0.02
 O3-O5 \\sim O3A-O5A
 with sigma of 0.02
 O4-O5 \\sim O4A-O5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O7) \\sim Ueq, Uanis(O7A) \\sim Ueq: with sigma of 0.04 and sigma for
terminal atoms of 0.02
Uanis(N4) = Uanis(N4A)
Uanis(O5) = Uanis(O5A)
Uanis(C5) = Uanis(C5A)
Uanis(C8) = Uanis(C8A)
Uanis(C2) = Uanis(C2A)
Uanis(O4) = Uanis(O4A)
Uanis(Ni1) = Uanis(Ni1A)
Uanis(N3) = Uanis(N3A)
Uanis(C7) = Uanis(C7A)
Uanis(C9) = Uanis(C9A)
Uanis(C6) = Uanis(C6A)
Uanis(N2) = Uanis(N2A)
Uanis(O3) = Uanis(O3A)
Uanis(C3) = Uanis(C3A)
Uanis(C1) = Uanis(C1A)
Uanis(N1) = Uanis(N1A)
Uanis(C4) = Uanis(C4A)
Uanis(O1) = Uanis(O1A)
Uanis(O2) = Uanis(O2A)
Uanis(C10) = Uanis(C10A)
Uanis(O7) = Uanis(O7A)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl1) = Uanis(Cl1B)
Uanis(Cl1B) = Uanis(Cl1A)
4. Others
 1*[Sof(Cl1)]+1*[Sof(Cl1A)]+1*[Sof(Cl1B)]=1 with esd of 0.0001
 Sof(Ni1A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(N1A)=Sof(N2A)=
 Sof(N3A)=Sof(N4A)=Sof(C1A)=Sof(C2A)=Sof(H2C)=Sof(H2D)=Sof(C3A)=Sof(H3C)=
 Sof(H3D)=Sof(C4A)=Sof(H4C)=Sof(H4D)=Sof(C5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=
 Sof(H8D)=Sof(H8E)=Sof(H8F)=Sof(C9A)=Sof(H9D)=Sof(H9E)=Sof(H9F)=Sof(C10A)=
 Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(Ni1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(N1)=Sof(N2)=Sof(N3)=
 Sof(N4)=Sof(C1)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 FVAR(1)
 Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(O7A)=Sof(H7B)=1-FVAR(3)
 Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(O7)=Sof(H7A)=FVAR(3)
 Fixed Sof: O8(0.5) H1(0.5) H2(0.5)
5.a Free rotating group:
 O8(H1,H2)
5.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C16(H16A,H16B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C2A(H2C,H2D),
 C3A(H3C,H3D), C4A(H4C,H4D)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C18(H18D,H18E,H18F), C8(H8A,H8B,
 H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C8A(H8D,H8E,H8F), C9A(H9D,H9E,H9F),
  C10A(H10D,H10E,H10F)
5.d Idealised tetrahedral OH refined as rotating group:
 O6(H6A), O7(H7A), O7A(H7B)
;
_shelx_res_checksum              39984
_shelx_hkl_checksum              28769
_platon_squeeze_void_probe_radius 1.20
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.824