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_7718763
_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         'C16 H21 B N4 O5, C H4 O'
_chemical_formula_sum            'C17 H25 B N4 O6'
_chemical_formula_weight         392.22
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-07
_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                   10.25318(6)
_cell_length_b                   10.89893(7)
_cell_length_c                   16.74915(12)
_cell_measurement_reflns_used    13635
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.8630
_cell_measurement_theta_min      4.0550
_cell_volume                     1871.70(2)
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.998
_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     81.00 106.00   0.50    0.60    --  115.25-125.00   0.00   50
  2  \w     79.00 105.00   0.50    0.60    --  115.25 -95.00 -30.00   52
  3  \w     45.00  70.00   0.50    0.60    --  115.25 -95.00 -30.00   50
  4  \w     24.00  61.00   0.50    0.15    --   45.05-110.00-164.00   74
  5  \w     43.00  69.00   0.50    0.60    --  115.25 -95.00-180.00   52
  6  \w     43.00 144.00   0.50    0.60    --  115.25 -84.00  86.00  202
  7  \w     43.00 144.00   0.50    0.60    --  115.25 -84.00  86.00  202
  8  \w     51.00  77.00   0.50    0.60    --  115.25 -77.00  30.00   52
  9  \w     45.00  71.00   0.50    0.60    --  115.25 -61.00 150.00   52
 10  \w     68.00 105.00   0.50    0.60    --  115.25 -77.00 120.00   74
 11  \w     43.00  68.00   0.50    0.60    --  115.25 -61.00  90.00   50
 12  \w     45.00  70.00   0.50    0.60    --  115.25 -61.00  30.00   50
 13  \w     46.00  71.00   0.50    0.60    --  115.25 -61.00 -60.00   50
 14  \w     44.00  70.00   0.50    0.60    --  115.25 -61.00-120.00   52
 15  \w     43.00  68.00   0.50    0.60    --  115.25 -61.00-150.00   50
 16  \w    122.00 177.00   0.50    0.60    --  115.25  15.00  30.00  110
 17  \w     97.00 178.00   0.50    0.60    --  115.25  42.00  70.00  162
 18  \w    107.00 145.00   0.50    0.60    --  115.25  45.00 150.00   76
 19  \w     89.00 126.00   0.50    0.60    --  115.25  77.00   0.00   74
 20  \w    149.00 176.00   0.50    0.60    --  115.25  77.00   0.00   54
 21  \w    138.00 169.00   0.50    0.60    --  115.25  30.00 -60.00   62
 22  \w    105.00 130.00   0.50    0.60    --  115.25  30.00 -60.00   50
 23  \w    103.00 151.00   0.50    0.60    --  115.25  30.00-150.00   96
 24  \w    135.00 178.00   0.50    0.60    --  115.25 125.00-120.00   86
 25  \w    103.00 174.00   0.50    0.60    --  115.25 110.00 -69.00  142
 26  \w     -2.00  26.00   0.50    0.15    --   45.05 -19.00  60.00   56
 27  \w   -115.00 -54.00   0.50    0.15    --  -45.05 -57.00  90.00  122
 28  \w   -167.00 -79.00   0.50    0.60    --  -93.75 -84.00  86.00  176
 29  \w   -168.00 -74.00   0.50    0.60    --  -93.75 -42.00 -82.00  188
 30  \w    -82.00 -23.00   0.50    0.60    --  -93.75 110.00 -69.00  118
 31  \w    -82.00  -1.00   0.50    0.15    --  -45.05 110.00 -69.00  162
;
_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      -0.0783846000
_diffrn_orient_matrix_UB_12      -0.0627134000
_diffrn_orient_matrix_UB_13      0.0669941000
_diffrn_orient_matrix_UB_21      0.0085432000
_diffrn_orient_matrix_UB_22      -0.1230541000
_diffrn_orient_matrix_UB_23      -0.0449932000
_diffrn_orient_matrix_UB_31      0.1279493000
_diffrn_orient_matrix_UB_32      -0.0301113000
_diffrn_orient_matrix_UB_33      0.0440667000
_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  0.0306
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            16509
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.062
_diffrn_reflns_theta_min         4.841
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.877
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.440
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.362
_exptl_crystal_size_mid          0.269
_exptl_crystal_size_min          0.213
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.211
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 1565 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     263
_refine_ls_number_reflns         3925
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0308
_refine_ls_R_factor_gt           0.0305
_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^)+(0.0469P)^2^+0.3929P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0810
_refine_ls_wR_factor_ref         0.0814
_reflns_Friedel_coverage         0.690
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.911
_reflns_number_gt                3871
_reflns_number_total             3925
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00812c2.cif
_cod_data_source_block           pj1267
_cod_depositor_comments
'Adding full bibliography for 7718760--7718765.cif.'
_cod_database_code               7718763
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C17H25BN4O6
_chemical_oxdiff_usercomment     PJ1267
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.742
_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
 At 1.5 times of:
  All C(H,H,H) groups, All N(H) groups, All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
2.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C17(H17A,H17B,H17C)
;
_shelx_res_checksum              4929
_shelx_hkl_checksum              90011
_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.821