Nicotinoyl hydrazone-directed vanadium assemblies: metallosupramolecular isomerism, polymorphism, and catalytic oxidation performance.
Topić, Edi; Sarjanović, Josipa; Kuzman, Dino; Cocut, Andrea; Hrenar, Tomica; Pisk, Jana; Vrdoljak, Višnja; Dalton transactions (Cambridge, England : 2003) 55 (2026) 4237–4249; doi:10.1039/d5dt03088a

data_7720197
_publ_section_title
;
 Nicotinoyl hydrazone-directed vanadium assemblies: metallosupramolecular
 isomerism, polymorphism, and catalytic oxidation performance.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4237
_journal_page_last               4249
_journal_paper_doi               10.1039/d5dt03088a
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C68 H72 N12 O20 V4'
_chemical_formula_sum            'C68 H72 N12 O20 V4'
_chemical_formula_weight         1581.13
_chemical_name_systematic
'oxo-n-propoxo-[N''-(2-oxo-3-methoxybenzylidene)nicotinoylhydrazonato]vanadium(v) tetramer'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-09-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-22 deposited with the CCDC.	2026-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                102.8740(10)
_cell_angle_beta                 100.0230(10)
_cell_angle_gamma                108.9320(10)
_cell_formula_units_Z            4
_cell_length_a                   15.7349(2)
_cell_length_b                   19.5409(3)
_cell_length_c                   26.1973(4)
_cell_measurement_reflns_used    49209
_cell_measurement_temperature    173.4(4)
_cell_measurement_theta_max      77.4530
_cell_measurement_theta_min      3.1000
_cell_volume                     7157.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.92a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.4(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.975
_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   -108.00 -58.00   0.50    0.90    --  -46.91-149.00  71.00  100
  2  \w    -94.00 -64.00   0.50    0.90    --  -46.91 149.00 118.00   60
  3  \w    -44.00 -17.00   0.50    0.90    --  -46.91 124.00 -45.00   54
  4  \w     55.00 108.00   0.50    0.90    --   46.91-149.00  71.00  106
  5  \w     34.00  93.00   0.50    0.90    --   46.91-124.00-124.00  118
  6  \w    -88.00 -63.00   0.50    2.10    --  -86.25 149.00 118.00   50
  7  \w   -128.00-103.00   0.50    2.10    --  -86.25-149.00  71.00   50
  8  \w    -73.00 -48.00   0.50    2.10    --  -86.25 124.00 -45.00   50
  9  \w   -101.00 -75.00   0.50    2.10    --  -86.25-124.00-124.00   52
 10  \w     99.00 124.00   0.50    2.10    --  107.75 149.00 118.00   50
 11  \w     72.00 100.00   0.50    2.10    --  107.75-124.00-124.00   56
 12  \w     75.00 129.00   0.50    2.10    --  107.75-149.00  71.00  108
 13  \w    106.00 138.00   0.50    2.10    --  107.75 124.00 -45.00   64
 14  \w    -27.00  19.00   0.50    0.90    --  -46.91  19.00-120.00   92
 15  \w   -118.00 -24.00   0.50    0.90    --  -46.91 -77.00 120.00  188
 16  \w   -118.00 -75.00   0.50    0.90    --  -46.91-125.00-150.00   86
 17  \w    -14.00  12.00   0.50    0.90    --  -46.91  19.00  90.00   52
 18  \w    -25.00  14.00   0.50    0.90    --   46.91 -19.00 -30.00   78
 19  \w    -22.00   6.00   0.50    0.90    --   46.91 -19.00-120.00   56
 20  \w   -121.00 -77.00   0.50    2.10    --  -86.25 -61.00 -60.00   88
 21  \w     35.00  83.00   0.50    2.10    --  107.75 -95.00 -90.00   96
 22  \w    130.00 175.00   0.50    2.10    --  107.75  45.00 -60.00   90
 23  \w     35.00  66.00   0.50    2.10    --  107.75 -61.00-150.00   62
 24  \w     39.00  87.00   0.50    2.10    --  107.75 -77.00 -60.00   96
 25  \w     94.00 169.00   0.50    2.10    --  107.75  15.00-150.00  150
 26  \w     96.00 177.00   0.50    2.10    --  107.75  45.00 -90.00  162
 27  \w     42.00  78.00   0.50    2.10    --  107.75 -77.00 -30.00   72
 28  \w     38.00  70.00   0.50    2.10    --  107.75 -61.00-180.00   64
 29  \w     38.00  66.00   0.50    2.10    --  107.75 -61.00 -60.00   56
 30  \w     98.00 174.00   0.50    2.10    --  107.75  30.00  60.00  152
 31  \w     35.00 112.00   0.50    2.10    --  107.75-125.00 150.00  154
 32  \w     47.00  96.00   0.50    2.10    --  107.75 -77.00 -90.00   98
 33  \w     96.00 178.00   0.50    2.10    --  107.75  15.00  30.00  164
 34  \w    113.00 172.00   0.50    2.10    --  107.75 125.00-180.00  118
 35  \w     57.00 112.00   0.50    2.10    --  107.75-125.00-150.00  110
 36  \w     78.00 107.00   0.50    2.10    --  107.75-108.00-107.33   58
 37  \w    102.00 128.00   0.50    2.10    --  107.75 125.00-150.00   52
 38  \w    142.00 175.00   0.50    2.10    --  107.75 125.00-150.00   66
 39  \w     77.00 112.00   0.50    2.10    --  107.75-125.00   0.00   70
 40  \w     70.00 108.00   0.50    2.10    --  107.75-109.00  33.72   76
 41  \w    105.00 145.00   0.50    2.10    --  107.75  30.00 150.00   80
 42  \w    153.00 178.00   0.50    2.10    --  107.75  30.00 150.00   50
 43  \w     45.00  70.00   0.50    2.10    --  107.75 -61.00   0.00   50
 44  \w     45.00  97.00   0.50    2.10    --  107.75 -95.00  60.00  104
 45  \w    100.00 126.00   0.50    2.10    --  107.75  15.00-120.00   52
 46  \w     83.00 112.00   0.50    2.10    --  107.75-125.00 120.00   58
 47  \w     48.00  73.00   0.50    2.10    --  107.75-108.00-107.33   50
 48  \w    140.00 174.00   0.50    2.10    --  107.75  15.00-120.00   68
 49  \w     62.00 119.00   0.50    2.10    --  107.75-134.00-156.50  114
 50  \w     37.00  62.00   0.50    2.10    --  107.75 -61.00 -30.00   50
 51  \w     76.00 118.00   0.50    2.10    --  107.75-133.00 -49.05   84
 52  \w     40.00  89.00   0.50    2.10    --  107.75 -77.00-180.00   98
 53  \w     94.00 162.00   0.50    2.10    --  107.75  15.00 -30.00  136
 54  \w     53.00  79.00   0.50    2.10    --  107.75-125.00  60.00   52
 55  \w     87.00 112.00   0.50    2.10    --  107.75-125.00  60.00   50
 56  \w    104.00 151.00   0.50    2.10    --  107.75  45.00  90.00   94
 57  \w     59.00  84.00   0.50    2.10    --  107.75 -77.00 120.00   50
 58  \w     52.00  77.00   0.50    2.10    --  107.75-110.00-154.45   50
 59  \w     57.00 111.00   0.50    2.10    --  107.75-125.00 -30.00  108
 60  \w     53.00 111.00   0.50    2.10    --  107.75-125.00-180.00  116
 61  \w     36.00  68.00   0.50    2.10    --  107.75 -61.00  60.00   64
 62  \w     69.00  94.00   0.50    2.10    --  107.75 -77.00   0.00   50
 63  \w     44.00 112.00   0.50    2.10    --  107.75-125.00 -90.00  136
 64  \w     46.00  71.00   0.50    2.10    --  107.75 -61.00  90.00   50
;
_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      0.0533518000
_diffrn_orient_matrix_UB_12      -0.0537344000
_diffrn_orient_matrix_UB_13      -0.0049763000
_diffrn_orient_matrix_UB_21      0.0404477000
_diffrn_orient_matrix_UB_22      0.0275510000
_diffrn_orient_matrix_UB_23      0.0621658000
_diffrn_orient_matrix_UB_31      -0.0839907000
_diffrn_orient_matrix_UB_32      -0.0631370000
_diffrn_orient_matrix_UB_33      0.0053922000
_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  0.1043
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            126447
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.267
_diffrn_reflns_theta_min         3.124
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.935
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.116
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.92a (Rigaku Oxford Diffraction, 2020)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3264
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.978
_refine_diff_density_min         -0.753
_refine_diff_density_rms         0.184
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1889
_refine_ls_number_reflns         29938
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.1618
_refine_ls_R_factor_gt           0.1521
_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^)+(0.0956P)^2^+181.7927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4032
_refine_ls_wR_factor_ref         0.4076
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25122
_reflns_number_total             29938
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt03088a2.cif
_cod_data_source_block           3t
_cod_depositor_comments
'Adding full bibliography for 7720194--7720204.cif.'
_cod_original_cell_volume        7157.79(19)
_cod_database_code               7720197
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'V2 N6 O10 C34'
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.638
_shelx_estimated_absorpt_t_min   0.285
_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. Restrained distances
 C15H-C16H
 1.5 with sigma of 0.02
 H17X-H16O
 2.1 with sigma of 0.02
3. Rigid bond restraints
 O4E, C15E, C16E, C17E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C15G(H15I,H15J), C15B(H15A,H15B), C16G(H16I,H16J), C15A(H15C,H15D), C15C(H15E,
 H15F), C16A(H16A,H16B), C16B(H16C,H16D), C15F(H15K,H15L), C15E(H15M,H15N),
 C16F(H16K,H16L), C15D(H15G,H15H), C16E(H16M,H16N), C16C(H16E,H16F), C15H(H15O,
 H15P), C16D(H16G,H16H), C16H(H16O,H16P)
4.b Aromatic/amide H refined with riding coordinates:
 C10F(H10F), C12H(H12H), C2G(H2G), C10G(H10G), C2F(H2F), C2E(H2E), C8E(H8E),
 C10H(H10H), C6F(H6F), C2H(H2H), C10E(H10E), C13F(H13F), C6H(H6H), C2A(H2A),
 C10D(H10D), C2B(H2B), C11E(H11E), C13H(H13H), C12F(H12F), C10C(H10C),
 C12C(H12C), C8G(H8G), C6E(H6E), C10A(H10A), C13C(H13C), C11A(H11A), C2D(H2D),
 C11C(H11C), C13A(H13A), C8B(H8B), C10B(H10B), C7B(H7B), C13D(H13D), C11H(H11H),
  C12D(H12D), C7F(H7F), C6B(H6B), C6G(H6G), C13E(H13E), C8F(H8F), C12E(H12E),
 C12A(H12A), C12G(H12G), C11D(H11D), C11F(H11F), C7C(H7C), C7G(H7G), C2C(H2C),
 C7H(H7H), C8A(H8A), C7E(H7E), C13B(H13B), C8H(H8H), C6C(H6C), C7A(H7A),
 C13G(H13G), C11G(H11G), C6A(H6A), C8C(H8C), C11B(H11B), C12B(H12B), C8D(H8D),
 C6D(H6D), C7D(H7D)
4.c Idealised Me refined as rotating group:
 C14G(H14M,H14N,H14O), C14E(H14P,H14Q,H14R), C14A(H14A,H14B,H14C), C14B(H14D,
 H14E,H14F), C17G(H17M,H17N,H17O), C17E(H17P,H17Q,H17R), C17F(H17S,H17T,H17U),
 C17A(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C14D(H14G,H14H,H14I), C14F(H14S,
 H14T,H14U), C14H(H14V,H14W,H14X), C14C(H14J,H14K,H14L), C17H(H17V,H17W,H17X),
 C17C(H17G,H17H,H17I), C17D(H17J,H17K,H17L)
;
_shelx_res_checksum              37122
_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 2.180
_oxdiff_exptl_absorpt_empirical_full_min 0.556