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_7720196
_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         'C76 H88 N12 O20 V4'
_chemical_formula_sum            'C76 H88 N12 O20 V4'
_chemical_formula_weight         1693.34
_chemical_name_systematic
'oxo-n-pentoxo-[N''-(2-oxo-3-methoxybenzylidene)nicotinoylhydrazonato]vanadium(v) polymer form beta'
_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             2025-09-09
_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                87.4190(10)
_cell_angle_beta                 75.757(2)
_cell_angle_gamma                76.5960(10)
_cell_formula_units_Z            1
_cell_length_a                   10.3360(2)
_cell_length_b                   14.3043(2)
_cell_length_c                   15.0552(3)
_cell_measurement_reflns_used    28001
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.6570
_cell_measurement_theta_min      3.0250
_cell_volume                     2098.54(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_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_temperature      293(2)
_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 0.968
_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   -119.00 -77.00   0.50    2.00    --  -46.93 174.00 146.00   84
  2  \w    -68.00 -42.00   0.50    2.00    --  -46.93 174.00 146.00   52
  3  \w    -81.00  -9.00   0.50    2.00    --  -46.93 115.00   5.00  144
  4  \w   -105.00 -80.00   0.50    2.00    --  -46.93-174.00 136.00   50
  5  \w     85.00 115.00   0.50    2.00    --   46.93 174.00 146.00   60
  6  \w     27.00  65.00   0.50    2.00    --   46.93-115.00 -83.00   76
  7  \w   -111.00 -86.00   0.50    8.00    --  -86.25-174.00 136.00   50
  8  \w   -144.00-119.00   0.50    8.00    --  -86.25-115.00 -83.00   50
  9  \w   -104.00 -79.00   0.50    8.00    --  -86.25 174.00 146.00   50
 10  \w    -71.00 -46.00   0.50    8.00    --  -86.25 115.00   5.00   50
 11  \w    101.00 127.00   0.50    8.00    --  106.38 174.00 146.00   52
 12  \w     73.00 146.00   0.50    8.00    --  106.38-174.00 136.00  146
 13  \w     35.00 108.00   0.50    8.00    --  106.38-115.00 -83.00  146
 14  \w    101.00 127.00   0.50    8.00    --  106.38 115.00   5.00   52
 15  \w    -18.00   7.00   0.50    2.00    --   14.00  97.00 -74.27   50
 16  \w    -11.00  14.00   0.50    2.00    --   18.00  91.00 106.53   50
 17  \w     -1.00  24.00   0.50    2.00    --   26.00  87.00 159.73   50
 18  \w      8.00  34.00   0.50    2.00    --   30.00  79.00 -82.40   52
 19  \w     12.00  37.00   0.50    2.00    --   34.00  75.00 129.47   50
 20  \w     12.00  37.00   0.50    2.00    --   34.00  76.00  67.82   50
 21  \w     12.00  37.00   0.50    2.00    --   34.00  77.00 -21.04   50
 22  \w     16.00  44.00   0.50    2.00    --   34.00  73.00 -57.44   56
 23  \w     18.00  43.00   0.50    2.00    --   38.00  70.00-114.65   50
 24  \w     35.00  91.00   0.50    2.00    --   46.93  19.00  60.00  112
 25  \w     96.00 121.00   0.50    2.00    --   46.93  19.00  60.00   50
 26  \w     37.00 112.00   0.50    2.00    --   46.93  19.00 -90.00  150
 27  \w     65.00  90.00   0.50    2.00    --   46.93-174.00 136.00   50
 28  \w     80.00 106.00   0.50    2.00    --   50.00  64.00 139.88   52
 29  \w     34.00  60.00   0.50    2.00    --   50.00  64.00 139.88   52
 30  \w     32.00  67.00   0.50    2.00    --   50.00  66.00  93.04   70
 31  \w     61.00  87.00   0.50    2.00    --   50.00  66.00 -71.58   52
 32  \w     33.00  62.00   0.50    2.00    --   50.00  66.00  11.97   58
 33  \w     32.00  58.00   0.50    2.00    --   50.00  66.00 163.96   52
 34  \w     33.00  58.00   0.50    2.00    --   50.00  66.00 -71.58   50
 35  \w     79.00 117.00   0.50    2.00    --   50.00  66.00  93.04   76
 36  \w     36.00  70.00   0.50    2.00    --   54.00  66.00-177.98   68
 37  \w     40.00  66.00   0.50    2.00    --   54.00  65.00 -33.94   52
 38  \w     83.00 124.00   0.50    2.00    --   54.00  65.00 -33.94   82
 39  \w    107.00 133.00   0.50    2.00    --   62.00  64.00  47.91   52
 40  \w     45.00  71.00   0.50    2.00    --   62.00  64.00  47.91   52
 41  \w     43.00  69.00   0.50    2.00    --   62.00  67.00 -33.68   52
 42  \w     43.00  68.00   0.50    2.00    --   62.00  67.00-108.86   50
 43  \w     43.00  70.00   0.50    2.00    --   62.00  67.00 163.92   54
 44  \w     44.00  82.00   0.50    2.00    --   62.00  67.00-153.46   76
 45  \w     45.00  70.00   0.50    2.00    --   62.00  65.00 -66.19   50
 46  \w     45.00  71.00   0.50    2.00    --   62.00  67.00 -15.09   52
 47  \w     43.00  76.00   0.50    2.00    --   62.00  67.00-139.11   66
 48  \w     43.00  72.00   0.50    2.00    --   62.00  67.00  12.27   58
 49  \w    -75.00 -49.00   0.50    2.00    --  -66.00 -63.00  83.40   52
 50  \w    -74.00 -49.00   0.50    2.00    --  -66.00 -62.00  21.55   50
 51  \w    -78.00 -52.00   0.50    8.00    --  -70.00 -66.00 139.90   52
 52  \w    -77.00 -51.00   0.50    8.00    --  -70.00 -67.00-111.85   52
 53  \w    -85.00 -57.00   0.50    8.00    --  -74.00 -61.00-137.32   56
 54  \w    -82.00 -57.00   0.50    8.00    --  -74.00 -63.00  58.06   50
 55  \w    -85.00 -59.00   0.50    8.00    --  -74.00 -63.00 121.55   52
 56  \w    -87.00 -57.00   0.50    8.00    --  -74.00 -63.00   3.13   60
 57  \w    -83.00 -57.00   0.50    8.00    --  -74.00 -62.00  75.59   52
 58  \w    -86.00 -61.00   0.50    8.00    --  -78.00 -63.00 172.09   50
 59  \w    -92.00 -66.00   0.50    8.00    --  -82.00 -61.00 100.78   52
 60  \w    -94.00 -66.00   0.50    8.00    --  -82.00 -60.00 -90.63   56
 61  \w    -89.00 -64.00   0.50    8.00    --  -82.00 -65.00-159.53   50
 62  \w    -96.00 -65.00   0.50    8.00    --  -82.00 -63.00 -39.23   62
 63  \w    -99.00 -65.00   0.50    8.00    --  -82.00 -62.00 -78.39   68
 64  \w    -97.00 -68.00   0.50    8.00    --  -86.00 -64.00  78.89   58
 65  \w   -120.00 -69.00   0.50    8.00    --  -86.25 -64.00 155.40  102
 66  \w   -158.00-127.00   0.50    8.00    --  -86.25 -64.00 155.40   62
 67  \w    -95.00 -70.00   0.50    8.00    --  -86.25 -60.00 -50.32   50
 68  \w   -158.00-114.00   0.50    8.00    --  -86.25 -60.00 -50.32   88
 69  \w    -95.00 -69.00   0.50    8.00    --  -86.25 -65.00 -53.92   52
 70  \w    -96.00 -71.00   0.50    8.00    --  -86.25 -62.00 -22.15   50
 71  \w    -96.00 -70.00   0.50    8.00    --  -86.25 -64.00  18.49   52
 72  \w    -99.00 -70.00   0.50    8.00    --  -86.25 -61.00  -3.04   58
 73  \w    -95.00 -68.00   0.50    8.00    --  -86.25 -65.00-102.18   54
 74  \w    -94.00 -69.00   0.50    8.00    --  -86.25 -64.00  94.58   50
 75  \w   -103.00 -70.00   0.50    8.00    --  -86.25 -60.00  27.00   66
 76  \w    -95.00 -69.00   0.50    8.00    --  -86.25 -63.00-147.26   52
 77  \w    -95.00 -70.00   0.50    8.00    --  -86.25 -65.00-122.30   50
 78  \w    -98.00 -70.00   0.50    8.00    --  -86.25 -60.00 118.94   56
 79  \w    -97.00 -69.00   0.50    8.00    --  -86.25 -63.00 -12.01   56
 80  \w   -155.00-129.00   0.50    8.00    --  -86.25 -63.00 -12.01   52
 81  \w    -94.00 -69.00   0.50    8.00    --  -86.25 -63.00   8.21   50
 82  \w    -94.00 -68.00   0.50    8.00    --  -86.25 -66.00 175.09   52
 83  \w   -157.00-124.00   0.50    8.00    --  -86.25 -65.00 -53.92   66
 84  \w    -94.00 -69.00   0.50    8.00    --  -86.25 -64.00  46.03   50
 85  \w    -95.00 -69.00   0.50    8.00    --  -86.25 -64.00  64.28   52
 86  \w   -157.00-101.00   0.50    8.00    --  -86.25 -64.00  64.28  112
 87  \w     89.00 178.00   0.50    8.00    --  106.38  77.00 -90.00  178
 88  \w     34.00 103.00   0.50    8.00    --  106.38 -77.00 120.00  138
 89  \w     37.00 110.00   0.50    8.00    --  106.38-125.00  30.00  146
 90  \w     35.00 106.00   0.50    8.00    --  106.38-125.00-120.00  142
 91  \w     93.00 175.00   0.50    8.00    --  106.38  57.00   0.00  164
 92  \w    146.00 176.00   0.50    8.00    --  106.38  57.00 120.00   60
 93  \w    101.00 142.00   0.50    8.00    --  106.38  57.00 120.00   82
 94  \w     99.00 177.00   0.50    8.00    --  106.38  57.00 -30.00  156
 95  \w     88.00 174.00   0.50    8.00    --  106.38  77.00 -60.00  172
 96  \w    130.00 174.00   0.50    8.00    --  106.38  77.00  30.00   88
 97  \w     88.00 118.00   0.50    8.00    --  106.38  77.00  30.00   60
 98  \w    141.00 166.00   0.50    8.00    --  106.38  19.00 -60.00   50
 99  \w     40.00  66.00   0.50    8.00    --  106.38 -57.00 -30.00   52
100  \w    136.00 177.00   0.50    8.00    --  106.38  57.00  60.00   82
101  \w     96.00 121.00   0.50    8.00    --  106.38  57.00  60.00   50
102  \w     97.00 134.00   0.50    8.00    --  106.38  19.00 -60.00   74
103  \w     97.00 165.00   0.50    8.00    --  106.38  57.00-120.00  136
104  \w     35.00  81.00   0.50    8.00    --  106.38-125.00   0.00   92
105  \w     36.00 103.00   0.50    8.00    --  106.38 -99.00 -60.00  134
106  \w     78.00 104.00   0.50    8.00    --  106.38 -99.00 -90.00   52
107  \w     39.00  64.00   0.50    8.00    --  106.38 -99.00 -90.00   50
108  \w    145.00 170.00   0.50    8.00    --  106.38  19.00  90.00   50
109  \w     92.00 177.00   0.50    8.00    --  106.38  57.00-180.00  170
110  \w     98.00 141.00   0.50    8.00    --  106.38  19.00  90.00   86
111  \w     95.00 174.00   0.50    8.00    --  106.38  77.00  90.00  158
112  \w     92.00 139.00   0.50    8.00    --  106.38  57.00 150.00   94
113  \w     34.00 100.00   0.50    8.00    --  106.38-125.00 120.00  132
114  \w     34.00  96.00   0.50    8.00    --  106.38 -99.00-150.00  124
115  \w     88.00 178.00   0.50    8.00    --  106.38  77.00 150.00  180
116  \w     79.00 105.00   0.50    8.00    --  106.38 -99.00 120.00   52
117  \w     74.00 107.00   0.50    8.00    --  106.38-106.00  91.58   66
118  \w     94.00 155.00   0.50    8.00    --  106.38  57.00-150.00  122
119  \w     94.00 120.00   0.50    8.00    --  106.38  38.00  60.00   52
120  \w     41.00  76.00   0.50    8.00    --  106.38 -99.00 120.00   70
;
_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      -0.0455695000
_diffrn_orient_matrix_UB_12      -0.0322385000
_diffrn_orient_matrix_UB_13      -0.0814331000
_diffrn_orient_matrix_UB_21      -0.0848308000
_diffrn_orient_matrix_UB_22      -0.0622064000
_diffrn_orient_matrix_UB_23      0.0647244000
_diffrn_orient_matrix_UB_31      -0.1251805000
_diffrn_orient_matrix_UB_32      0.0857369000
_diffrn_orient_matrix_UB_33      0.0180759000
_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  0.0353
_diffrn_reflns_av_unetI/netI     0.0195
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            65009
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.394
_diffrn_reflns_theta_min         3.176
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.243
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.53a (Rigaku Oxford Diffraction, 2022)
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    1.340
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.240
_refine_diff_density_min         -0.766
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     491
_refine_ls_number_reflns         8627
_refine_ls_number_restraints     126
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0608
_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^)+(0.1512P)^2^+0.4773P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1978
_refine_ls_wR_factor_ref         0.2091
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7142
_reflns_number_total             8627
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt03088a2.cif
_cod_data_source_block           5beta
_cod_depositor_comments
'Adding full bibliography for 7720194--7720204.cif.'
_cod_database_code               7720196
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'V C N O'
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.883
_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
 C15A-O4A
 1.5 with sigma of 0.02
 C15-O4
 1.5 with sigma of 0.02
 H19E-C17A
 3.35 with sigma of 0.02
 H19C-C17
 3.238 with sigma of 0.02
 C15-C16 \\sim C16-C17 \\sim C17-C18 \\sim C18-C19
 with sigma of 0.02
 C15-C17 \\sim C17-C19 \\sim C16-C18
 with sigma of 0.04
 C15A-C16A \\sim C16A-C17A \\sim C17A-C18A \\sim C18A-C19A
 with sigma of 0.02
 C15A-C17A \\sim C17A-C19A \\sim C16A-C18A
 with sigma of 0.04
3. Rigid bond restraints
 C15, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C15A, C16A, C17A, C18A, C19A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C15, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15A, C16A, C17A, C18A, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Free rotating group:
 C15(C16,C17,C18,C19), C15A(C16A,C17A,C18A,C19A)
6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C15A(H15C,
 H15D), C16A(H16C,H16D), C17A(H17C,H17D), C18A(H18C,H18D)
6.c Aromatic/amide H refined with riding coordinates:
 C11A(H11A), C10A(H10A), C10(H10), C13A(H13A), C2(H2), C12A(H12A), C8(H8),
 C2A(H2A), C11(H11), C13(H13), C6(H6), C7(H7), C6A(H6A), C12(H12), C8A(H8A),
 C7A(H7A)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C19(H19A,H19B,H19C), C19A(H19D,
 H19E,H19F)
;
_shelx_res_checksum              85148
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.357
_oxdiff_exptl_absorpt_empirical_full_min 0.774