High-valent oxovanadium metallosupramolecular species as catalysts for the oxidation of benzyl alcohol derivatives.
Topić, Edi; Sarjanović, Josipa; Musija, Danijela; Mandarić, Mirna; Hrenar, Tomica; Pisk, Jana; Vrdoljak, Višnja; RSC advances 15 (2025) 3547–3561; doi:10.1039/d4ra09073j

data_7249905
_publ_section_title
;
 High-valent oxovanadium metallosupramolecular species as catalysts for
 the oxidation of benzyl alcohol derivatives.
;
_journal_issue                   5
_journal_name_full               'RSC advances'
_journal_page_first              3547
_journal_page_last               3561
_journal_paper_doi               10.1039/d4ra09073j
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C28.84 H23 N6 O8 V2, 1.507(C), 0.5[C2H6O]'
_chemical_formula_sum            'C31.34 H26 N6 O8.5 V2'
_chemical_formula_weight         724.60
_chemical_name_systematic
'[N'-(2-oxobenzylidene)isonicotinoylhydrazonato](ethoxo)oxovanadium(v) ethanol solvate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           73
_space_group_name_Hall           '-I 2b 2c'
_space_group_name_H-M_alt        'I b c a'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-02-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-07-03 deposited with the CCDC.	2025-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   20.6605(9)
_cell_length_b                   22.3137(8)
_cell_length_c                   29.1125(15)
_cell_measurement_reflns_used    12733
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      77.4210
_cell_measurement_theta_min      3.0480
_cell_volume                     13421.2(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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   -105.00 -68.00   0.50    5.02    --  -47.97-133.00-118.00   74
  2  \w    -87.00 -35.00   0.50    5.02    --  -47.97 133.00 -50.00  104
  3  \w   -118.00 -69.00   0.50    5.02    --  -47.97-137.00  63.00   98
  4  \w    -93.00 -56.00   0.50    5.02    --  -47.97 137.00 126.00   74
  5  \w     47.00  73.00   0.50    5.02    --   47.97-137.00  63.00   52
  6  \w     40.00  72.00   0.50    5.02    --   47.97-133.00-118.00   64
  7  \w   -112.00 -87.00   0.50   20.07    --  -91.75-137.00  63.00   50
  8  \w    -88.00 -55.00   0.50   20.07    --  -91.75 137.00 126.00   66
  9  \w    -93.00 -68.00   0.50   20.07    --  -91.75-133.00-118.00   50
 10  \w   -146.00-111.00   0.50   20.07    --  -91.75-133.00-118.00   70
 11  \w     88.00 145.00   0.50   20.07    --  107.59 137.00 126.00  114
 12  \w     91.00 154.00   0.50   20.07    --  107.59 133.00 -50.00  126
 13  \w     86.00 118.00   0.50   20.07    --  107.59-137.00  63.00   64
 14  \w     84.00 117.00   0.50   20.07    --  107.59-133.00-118.00   66
 15  \w   -120.00 -88.00   0.50    5.02    --  -47.97 -77.00-180.00   64
 16  \w   -121.00 -96.00   0.50    5.02    --  -47.97 -77.00  30.00   50
 17  \w   -119.00 -89.00   0.50    5.02    --  -47.97 -77.00 120.00   60
 18  \w   -116.00 -87.00   0.50    5.02    --  -47.97-125.00  90.00   58
 19  \w    -24.00  15.00   0.50    5.02    --  -47.97  19.00  60.00   78
 20  \w   -121.00 -96.00   0.50    5.02    --  -47.97 -77.00 -90.00   50
 21  \w     89.00 121.00   0.50    5.02    --   47.97  77.00-150.00   64
 22  \w     89.00 115.00   0.50    5.02    --   47.97  77.00 120.00   52
 23  \w     90.00 116.00   0.50    5.02    --   47.97  77.00 150.00   52
 24  \w     88.00 113.00   0.50    5.02    --   47.97  77.00-180.00   50
 25  \w    -53.00 -26.00   0.50   20.07    --  -91.75  57.00 120.00   54
 26  \w   -151.00 -93.00   0.50   20.07    --  -91.75 -99.00-150.00  116
 27  \w   -140.00 -92.00   0.50   20.07    --  -91.75 -99.00  90.00   96
 28  \w    -85.00 -36.00   0.50   20.07    --  -91.75 125.00   0.00   98
 29  \w   -157.00 -98.00   0.50   20.07    --  -91.75 -57.00 -30.00  118
 30  \w   -133.00-102.00   0.50   20.07    --  -91.75 -99.00 120.00   62
 31  \w    -59.00 -33.00   0.50   20.07    --  -91.75  57.00 150.00   52
 32  \w   -159.00 -81.00   0.50   20.07    --  -91.75 -57.00 -60.00  156
 33  \w    -63.00 -20.00   0.50   20.07    --  -91.75  57.00 -90.00   86
 34  \w    -81.00 -56.00   0.50   20.07    --  -91.75 133.00 -50.00   50
 35  \w    -47.00 -21.00   0.50   20.07    --  -91.75  57.00 -30.00   52
 36  \w   -127.00 -86.00   0.50   20.07    --  -91.75-125.00 -60.00   82
 37  \w     82.00 111.00   0.50   20.07    --  107.59-125.00   0.00   58
 38  \w     43.00  99.00   0.50   20.07    --  107.59-125.00 -60.00  112
 39  \w     39.00 100.00   0.50   20.07    --  107.59 -99.00  90.00  122
 40  \w     36.00  62.00   0.50   20.07    --  107.59 -57.00-150.00   52
 41  \w     69.00 111.00   0.50   20.07    --  107.59-125.00  90.00   84
 42  \w     39.00  66.00   0.50   20.07    --  107.59 -57.00  90.00   54
 43  \w     39.00  64.00   0.50   20.07    --  107.59-125.00  90.00   50
 44  \w     95.00 165.00   0.50   20.07    --  107.59 125.00 -30.00  140
 45  \w     97.00 166.00   0.50   20.07    --  107.59  38.00 120.00  138
 46  \w     37.00  99.00   0.50   20.07    --  107.59 -99.00 -60.00  124
 47  \w     77.00 110.00   0.50   20.07    --  107.59-125.00 -90.00   66
 48  \w     56.00 109.00   0.50   20.07    --  107.59-112.00   0.73  106
 49  \w     40.00  65.00   0.50   20.07    --  107.59 -57.00 -60.00   50
 50  \w     35.00  60.00   0.50   20.07    --  107.59 -57.00 -90.00   50
 51  \w     51.00 108.00   0.50   20.07    --  107.59-125.00-180.00  114
 52  \w     35.00  66.00   0.50   20.07    --  107.59 -57.00 120.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1228
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            86108
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.432
_diffrn_reflns_theta_min         3.962
_exptl_absorpt_coefficient_mu    5.181
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.434
_exptl_crystal_description       plate
_exptl_crystal_F_000             5921
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.581
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         6996
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0949
_refine_ls_R_factor_gt           0.0577
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0868P)^2^+7.4950P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1471
_refine_ls_wR_factor_ref         0.1696
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4346
_reflns_number_total             6996
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra09073j2.cif
_cod_data_source_block           exp_5521
_cod_original_formula_sum        'C31.34 H26 N6 O8.50 V2'
_cod_database_code               7249905
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.288
_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. Uiso/Uaniso restraints and constraints
O4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
3.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
3.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C3(H3), C4A(H4A), C4(H4), C3A(H3A), C6(H6), C5A(H5A), C6A(H6A),
 C13(H13), C10(H10), C5(H5), C7A(H7A), C12(H12), C11(H11), C13A(H13A),
 C10A(H10A), C12A(H12A), C11A(H11A)
3.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 228 electrons were 
found in a volume of 1888\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.5[C2H6O] per Asymmetric Unit 
which account for 208 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              57749
_shelx_hkl_checksum              71846
_shelx_fab_checksum              6306
_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
- Detector area scaling
;