From structure to function: tunable electrical and catalytic properties in rare Mo(vi)-thiophene-2-carboxylic acid hydrazone complexes obtained mechanochemically
Pavić, Luka; Miočić, Filip; Razum, Marta; Sarjanović, Josipa; Pisk, Jana; RSC Advances 15 (2025) 46194–46206; doi:10.1039/D5RA07456H

data_7251341
_publ_section_title
;
 From structure to function: tunable electrical and catalytic properties
 in rare Mo(vi)-thiophene-2-carboxylic acid hydrazone complexes obtained
 mechanochemically
;
_journal_issue                   54
_journal_name_full               'RSC Advances'
_journal_page_first              46194
_journal_page_last               46206
_journal_paper_doi               10.1039/D5RA07456H
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C12 H10 Mo N2 O5 S, C3 H6 O'
_chemical_formula_sum            'C15 H16 Mo N2 O6 S'
_chemical_formula_weight         448.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-28
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-18 deposited with the CCDC.	2025-11-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.132(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.74290(10)
_cell_length_b                   10.64170(10)
_cell_length_c                   21.2775(4)
_cell_measurement_reflns_used    14459
_cell_measurement_temperature    298
_cell_measurement_theta_max      78.8450
_cell_measurement_theta_min      4.1560
_cell_volume                     1752.87(4)
_computing_cell_refinement       'CrysAlisPro 1.171.44.114a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.114a 64-bit (release 13-06-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.114a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.986
_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   -116.00 -88.00   0.50    3.00    --  -47.94 -77.00 -90.00   56
  2  \w    -43.00  23.00   0.50    3.00    --  -47.94  38.00   0.00  132
  3  \w    -26.00  25.00   0.50    3.00    --  -47.94  38.00 120.00  102
  4  \w   -120.00 -95.00   0.50    3.00    --  -47.94-125.00-150.00   50
  5  \w   -120.00 -95.00   0.50    3.00    --  -47.94 -77.00 -30.00   50
  6  \w   -122.00 -40.00   0.50    3.00    --  -47.94 -19.00-180.00  164
  7  \w     51.00  79.00   0.50    3.00    --   47.94 -99.00 -60.00   56
  8  \w     -1.00  45.00   0.50    3.00    --   47.94 -99.00 -60.00   92
  9  \w     57.00  95.00   0.50    3.00    --   47.94-125.00  30.00   76
 10  \w     89.00 118.00   0.50    3.00    --   47.94  77.00 120.00   58
 11  \w     90.00 115.00   0.50    3.00    --   47.94  77.00 150.00   50
 12  \w    -69.00 -37.00   0.50   12.00    --  -91.75  61.00-120.00   64
 13  \w    -71.00 -46.00   0.50   12.00    --  -91.75  61.00-150.00   50
 14  \w     78.00 105.00   0.50   12.00    --  113.25 -95.00 120.00   54
 15  \w     43.00  70.00   0.50   12.00    --  113.25 -61.00 120.00   54
 16  \w     68.00 115.00   0.50   12.00    --  113.25   6.00  63.67   94
 17  \w     48.00  76.00   0.50   12.00    --  113.25-125.00 -60.00   56
 18  \w    104.00 137.00   0.50   12.00    --  113.25  61.00  30.00   66
 19  \w     99.00 137.00   0.50   12.00    --  113.25 -79.00  -6.00   76
 20  \w     97.00 139.00   0.50   12.00    --  113.25 -84.00  21.68   84
 21  \w     51.00  99.00   0.50   12.00    --  113.25 -95.00   0.00   96
 22  \w     96.00 160.00   0.50   12.00    --  113.25 125.00  90.00  128
 23  \w     62.00  99.00   0.50   12.00    --  113.25 -95.00 -90.00   74
 24  \w     85.00 111.00   0.50   12.00    --  113.25-125.00  30.00   52
 25  \w     95.00 140.00   0.50   12.00    --  113.25 125.00-150.00   90
 26  \w     86.00 111.00   0.50   12.00    --  113.25-125.00 -60.00   50
 27  \w    105.00 177.00   0.50   12.00    --  113.25  15.00-150.00  144
 28  \w     67.00  92.00   0.50   12.00    --  113.25 -77.00  30.00   50
 29  \w    106.00 133.00   0.50   12.00    --  113.25  61.00  90.00   54
 30  \w     81.00 106.00   0.50   12.00    --  113.25 -95.00 -30.00   50
 31  \w    129.00 155.00   0.50   12.00    --  113.25 125.00   0.00   52
 32  \w     86.00 111.00   0.50   12.00    --  113.25-125.00-120.00   50
 33  \w     51.00  76.00   0.50   12.00    --  113.25-125.00-120.00   50
 34  \w    139.00 177.00   0.50   12.00    --  113.25   6.00-177.91   76
 35  \w     96.00 136.00   0.50   12.00    --  113.25 -79.00-173.32   80
 36  \w     57.00 111.00   0.50   12.00    --  113.25-125.00 150.00  108
 37  \w    101.00 166.00   0.50   12.00    --  113.25 125.00 150.00  130
 38  \w    101.00 156.00   0.50   12.00    --  113.25  45.00 -60.00  110
 39  \w     97.00 122.00   0.50   12.00    --  113.25  77.00   0.00   50
 40  \w    145.00 177.00   0.50   12.00    --  113.25  77.00   0.00   64
 41  \w    130.00 156.00   0.50   12.00    --  113.25 125.00 -90.00   52
 42  \w     80.00 106.00   0.50   12.00    --  113.25 -95.00-180.00   52
 43  \w    106.00 132.00   0.50   12.00    --  113.25  30.00  90.00   52
 44  \w     69.00 111.00   0.50   12.00    --  113.25-125.00 -30.00   84
 45  \w     81.00 111.00   0.50   12.00    --  113.25-125.00  60.00   60
 46  \w    101.00 163.00   0.50   12.00    --  113.25  45.00 150.00  124
 47  \w     72.00 133.00   0.50   12.00    --  113.25   6.00-177.91  122
 48  \w     43.00  68.00   0.50   12.00    --  113.25-125.00  30.00   50
 49  \w    153.00 178.00   0.50   12.00    --  113.25  15.00 -90.00   50
 50  \w    133.00 165.00   0.50   12.00    --  113.25 125.00 -30.00   64
 51  \w    121.00 150.00   0.50   12.00    --  113.25  15.00 -90.00   58
 52  \w    106.00 131.00   0.50   12.00    --  113.25  30.00 -60.00   50
 53  \w    153.00 178.00   0.50   12.00    --  113.25  30.00 -60.00   50
 54  \w     97.00 178.00   0.50   12.00    --  113.25 125.00-180.00  162
 55  \w     43.00 102.00   0.50   12.00    --  113.25 -95.00-150.00  118
 56  \w     42.00  71.00   0.50   12.00    --  113.25 -61.00 -30.00   58
 57  \w     42.00  67.00   0.50   12.00    --  113.25 -61.00-120.00   50
 58  \w     43.00  68.00   0.50   12.00    --  113.25 -77.00  90.00   50
 59  \w     67.00  92.00   0.50   12.00    --  113.25 -77.00   0.00   50
 60  \w    149.00 177.00   0.50   12.00    --  113.25  61.00  90.00   56
 61  \w     96.00 151.00   0.50   12.00    --  113.25 125.00-120.00  110
 62  \w     50.00  75.00   0.50   12.00    --  113.25 -77.00-150.00   50
 63  \w     56.00  82.00   0.50   12.00    --  113.25 -77.00 -90.00   52
 64  \w     74.00 111.00   0.50   12.00    --  113.25-125.00 120.00   74
 65  \w     59.00 106.00   0.50   12.00    --  113.25 -95.00 150.00   94
 66  \w     80.00 106.00   0.50   12.00    --  113.25 -95.00 -60.00   52
 67  \w     45.00  70.00   0.50   12.00    --  113.25 -95.00  60.00   50
 68  \w     82.00 111.00   0.50   12.00    --  113.25-125.00 -90.00   58
 69  \w     53.00 102.00   0.50   12.00    --  113.25-125.00   0.00   98
 70  \w    104.00 155.00   0.50   12.00    --  113.25  45.00  60.00  102
 71  \w    150.00 175.00   0.50   12.00    --  113.25   6.00  63.67   50
 72  \w    107.00 132.00   0.50   12.00    --  113.25  30.00 150.00   50
 73  \w     54.00  80.00   0.50   12.00    --  113.25 -79.00-173.32   52
 74  \w    137.00 162.00   0.50   12.00    --  113.25 125.00  60.00   50
 75  \w     42.00  68.00   0.50   12.00    --  113.25 -84.00  21.68   52
 76  \w     44.00  69.00   0.50   12.00    --  113.25 -81.00  80.71   50
 77  \w    113.00 138.00   0.50   12.00    --  113.25 -81.00  80.71   50
 78  \w     70.00 109.00   0.50   12.00    --  113.25-113.00 -24.76   78
;
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            29131
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.981
_diffrn_reflns_theta_min         4.156
_exptl_absorpt_coefficient_mu    7.553
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.576
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.114a (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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       needle
_exptl_crystal_F_000             904
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetone'
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.411
_refine_diff_density_min         -0.672
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3761
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0318
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0506P)^2^+0.6995P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0885
_refine_ls_wR_factor_ref         0.0910
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3279
_reflns_number_total             3761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra07456h2.cif
_cod_data_source_block           exp_8574
_cod_database_code               7251341
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C15 N2 O5 S Mo H17'
_cell_oxdiff_angle_alpha         90.0013(13)
_cell_oxdiff_angle_beta          91.1058(19)
_cell_oxdiff_angle_gamma         90.0224(15)
_cell_oxdiff_length_a            7.7447(2)
_cell_oxdiff_length_b            10.64254(14)
_cell_oxdiff_length_c            21.2704(4)
_cell_oxdiff_measurement_reflns_used 14459
_cell_oxdiff_volume              1752.86(6)
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.218
_diffrn_oxdiff_measurement_exp_name exp_8574.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C9-S1A \\sim C9-S1A
 with sigma of 0.02
 C9-C10A \\sim C9-C10B
 with sigma of 0.02
 S1A-C12A \\sim S1A-C12A
 with sigma of 0.02
 C10A-C12A \\sim C10B-C12A
 with sigma of 0.04
 C10A-C11A \\sim C10B-C11B
 with sigma of 0.02
 S1A-C11A \\sim S1A-C11B
 with sigma of 0.04
 C9-C12A \\sim C9-C12A
 with sigma of 0.04
 C12A-C11A \\sim C12A-C11B
 with sigma of 0.02
 C9-C11A \\sim C9-C11B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C10A) = Uanis(S1A) = Uanis(C11A) = Uanis(C12A) = Uanis(C12A) =
Uanis(C11B) = Uanis(C10B) = Uanis(S1A)
4. Others
 Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=Sof(S1B)=1-FVAR(1)
 Sof(S1A)=Sof(C10A)=Sof(H10A)=Sof(C12A)=Sof(H12A)=Sof(C11A)=Sof(H11A)=FVAR(1)
5.a Rotating group:
 O5(H5A,H5B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C4(H4), C6(H6), C5(H5), C10A(H10A), C12A(H12A), C11A(H11A),
 C10B(H10B), C11B(H11B), C12B(H12B)
5.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              10729
_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 2.384
_oxdiff_exptl_absorpt_empirical_full_min 0.361