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_7251342
_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         'C13 H12 Mo N2 O5 S'
_chemical_formula_sum            'C13 H12 Mo N2 O5 S'
_chemical_formula_weight         404.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-08
_audit_creation_method
;
Olex2 1.5-ac7-014
(compiled 2025.02.27 svn.r6f4c0eaf for Rigaku Oxford Diffraction, GUI svn.r7171)
;
_audit_update_record
;
2025-09-18 deposited with the CCDC.	2025-11-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.8458(2)
_cell_length_b                   7.28750(10)
_cell_length_c                   26.5865(3)
_cell_measurement_reflns_used    19073
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.7540
_cell_measurement_theta_min      3.3350
_cell_volume                     2876.36(6)
_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-ac7-014 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.993
_diffrn_measured_fraction_theta_max 0.994
_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    -80.00 -23.00   0.50    0.50    --  -47.69 125.00  60.00  114
  2  \w   -120.00 -95.00   0.50    0.50    --  -47.69-125.00 150.00   50
  3  \w    -63.00  25.00   0.50    0.50    --  -47.69  57.00   0.00  176
  4  \w   -118.00 -90.00   0.50    0.50    --  -47.69 -77.00 -90.00   56
  5  \w    -26.00  28.00   0.50    0.50    --  -47.69  19.00-120.00  108
  6  \w   -116.00 -81.00   0.50    0.50    --  -47.69-125.00  30.00   70
  7  \w   -117.00 -84.00   0.50    0.50    --  -47.69-125.00  90.00   66
  8  \w    -38.00  25.00   0.50    0.50    --  -47.69  38.00 120.00  126
  9  \w     35.00  67.00   0.50    0.50    --   47.69 -99.00 -90.00   64
 10  \w     61.00  89.00   0.50    0.50    --   47.69-125.00-120.00   56
 11  \w   -146.00-120.00   0.50    2.00    --  -91.75 -15.00  60.00   52
 12  \w    131.00 157.00   0.50    2.00    --  113.25  30.00-180.00   52
 13  \w     91.00 117.00   0.50    2.00    --  113.25 -86.00 148.09   52
 14  \w     78.00 106.00   0.50    2.00    --  113.25 -95.00 -60.00   56
 15  \w    103.00 129.00   0.50    2.00    --  113.25  30.00-180.00   52
 16  \w     85.00 111.00   0.50    2.00    --  113.25-125.00 -30.00   52
 17  \w     42.00  84.00   0.50    2.00    --  113.25 -86.00 148.09   84
 18  \w     81.00 107.00   0.50    2.00    --  113.25 -82.00 -42.09   52
 19  \w     45.00  70.00   0.50    2.00    --  113.25 -61.00  60.00   50
 20  \w     42.00  67.00   0.50    2.00    --  113.25 -61.00  30.00   50
 21  \w     81.00 106.00   0.50    2.00    --  113.25 -95.00 120.00   50
 22  \w    101.00 174.00   0.50    2.00    --  113.25  45.00-150.00  146
 23  \w    142.00 168.00   0.50    2.00    --  113.25  61.00  60.00   52
 24  \w    143.00 176.00   0.50    2.00    --  113.25  15.00 120.00   66
 25  \w    103.00 138.00   0.50    2.00    --  113.25  30.00  60.00   70
 26  \w    150.00 177.00   0.50    2.00    --  113.25  30.00  60.00   54
 27  \w     42.00  67.00   0.50    2.00    --  113.25 -61.00-150.00   50
 28  \w     67.00  93.00   0.50    2.00    --  113.25 -95.00 150.00   52
 29  \w     43.00  69.00   0.50    2.00    --  113.25 -95.00 -90.00   52
 30  \w     74.00 100.00   0.50    2.00    --  113.25 -95.00 -90.00   52
 31  \w     42.00  71.00   0.50    2.00    --  113.25 -95.00 120.00   58
 32  \w     80.00 106.00   0.50    2.00    --  113.25 -95.00  30.00   52
 33  \w    112.00 138.00   0.50    2.00    --  113.25 -81.00-103.64   52
 34  \w     91.00 128.00   0.50    2.00    --  113.25  77.00-150.00   74
 35  \w    144.00 176.00   0.50    2.00    --  113.25  30.00 150.00   64
 36  \w    101.00 137.00   0.50    2.00    --  113.25  30.00 150.00   72
 37  \w     70.00 107.00   0.50    2.00    --  113.25-125.00-120.00   74
 38  \w     45.00  71.00   0.50    2.00    --  113.25 -61.00 -60.00   52
 39  \w     42.00  67.00   0.50    2.00    --  113.25 -61.00   0.00   50
 40  \w     44.00  71.00   0.50    2.00    --  113.25-125.00 -60.00   54
 41  \w     86.00 111.00   0.50    2.00    --  113.25-125.00 -60.00   50
 42  \w    144.00 178.00   0.50    2.00    --  113.25 125.00 -90.00   68
 43  \w    135.00 178.00   0.50    2.00    --  113.25  77.00  60.00   86
 44  \w     51.00 111.00   0.50    2.00    --  113.25-125.00   0.00  120
 45  \w    103.00 136.00   0.50    2.00    --  113.25  61.00-150.00   66
 46  \w    101.00 127.00   0.50    2.00    --  113.25  61.00  60.00   52
 47  \w     99.00 139.00   0.50    2.00    --  113.25 -86.00 -21.53   80
 48  \w     43.00  73.00   0.50    2.00    --  113.25-125.00  90.00   60
 49  \w     82.00 111.00   0.50    2.00    --  113.25-125.00  90.00   58
 50  \w     54.00  79.00   0.50    2.00    --  113.25 -77.00-150.00   50
 51  \w    103.00 128.00   0.50    2.00    --  113.25  30.00 -30.00   50
 52  \w    136.00 177.00   0.50    2.00    --  113.25  30.00 -30.00   82
 53  \w    115.00 174.00   0.50    2.00    --  113.25  77.00 150.00  118
 54  \w    137.00 162.00   0.50    2.00    --  113.25  30.00  30.00   50
 55  \w     57.00  83.00   0.50    2.00    --  113.25 -77.00  60.00   52
 56  \w    122.00 172.00   0.50    2.00    --  113.25  45.00  90.00  100
 57  \w     44.00  70.00   0.50    2.00    --  113.25 -77.00 -30.00   52
 58  \w     46.00  72.00   0.50    2.00    --  113.25 -95.00 -60.00   52
 59  \w    108.00 140.00   0.50    2.00    --  113.25 -87.00-175.10   64
 60  \w    143.00 168.00   0.50    2.00    --  113.25 125.00  60.00   50
 61  \w     56.00  81.00   0.50    2.00    --  113.25 -77.00  90.00   50
 62  \w    102.00 127.00   0.50    2.00    --  113.25  61.00   0.00   50
 63  \w     95.00 132.00   0.50    2.00    --  113.25 125.00  60.00   74
 64  \w    108.00 134.00   0.50    2.00    --  113.25  30.00 -60.00   52
 65  \w     86.00 111.00   0.50    2.00    --  113.25-125.00  30.00   50
 66  \w    130.00 164.00   0.50    2.00    --  113.25 125.00-120.00   68
 67  \w    135.00 160.00   0.50    2.00    --  113.25  61.00   0.00   50
 68  \w     49.00 103.00   0.50    2.00    --  113.25 -77.00 150.00  108
 69  \w     72.00 105.00   0.50    2.00    --  113.25 -95.00-150.00   66
 70  \w     62.00 110.00   0.50    2.00    --  113.25-125.00-180.00   96
 71  \w     86.00 111.00   0.50    2.00    --  113.25-125.00-150.00   50
 72  \w     86.00 111.00   0.50    2.00    --  113.25-125.00 120.00   50
 73  \w     51.00  77.00   0.50    2.00    --  113.25 -82.00  18.11   52
 74  \w    113.00 138.00   0.50    2.00    --  113.25 -82.00  18.11   50
 75  \w     52.00  78.00   0.50    2.00    --  113.25-125.00  30.00   52
 76  \w    140.00 174.00   0.50    2.00    --  113.25  77.00-150.00   68
 77  \w     45.00  70.00   0.50    2.00    --  113.25 -61.00 -90.00   50
 78  \w     43.00  69.00   0.50    2.00    --  113.25 -61.00 150.00   52
 79  \w     78.00 103.00   0.50    2.00    --  113.25 -95.00-120.00   50
 80  \w     72.00  99.00   0.50    2.00    --  113.25 -95.00 -30.00   54
 81  \w     78.00 111.00   0.50    2.00    --  113.25-125.00  60.00   66
 82  \w     98.00 138.00   0.50    2.00    --  113.25  61.00-180.00   80
 83  \w    151.00 176.00   0.50    2.00    --  113.25 125.00-180.00   50
 84  \w     95.00 128.00   0.50    2.00    --  113.25 125.00 -90.00   66
 85  \w    124.00 163.00   0.50    2.00    --  113.25  45.00-120.00   78
 86  \w     95.00 126.00   0.50    2.00    --  113.25  77.00  60.00   62
 87  \w     66.00  92.00   0.50    2.00    --  113.25 -87.00-175.10   52
 88  \w     47.00  72.00   0.50    2.00    --  113.25 -77.00 -60.00   50
 89  \w     57.00  83.00   0.50    2.00    --  113.25 -77.00  30.00   52
 90  \w    121.00 147.00   0.50    2.00    --  113.25  45.00 150.00   52
 91  \w     56.00  81.00   0.50    2.00    --  113.25 -81.00-103.64   50
 92  \w    105.00 133.00   0.50    2.00    --  113.25  61.00 120.00   56
 93  \w    141.00 175.00   0.50    2.00    --  113.25  61.00 120.00   68
 94  \w     49.00  74.00   0.50    2.00    --  113.25 -86.00 -21.53   50
 95  \w     51.00  77.00   0.50    2.00    --  113.25 -82.00 -42.09   52
 96  \w     83.00 108.00   0.50    2.00    --  113.25-108.00 100.28   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      0.0036400000
_diffrn_orient_matrix_UB_12      -0.0340356000
_diffrn_orient_matrix_UB_13      0.0571584000
_diffrn_orient_matrix_UB_21      0.0733968000
_diffrn_orient_matrix_UB_22      0.1482697000
_diffrn_orient_matrix_UB_23      0.0051570000
_diffrn_orient_matrix_UB_31      -0.0732654000
_diffrn_orient_matrix_UB_32      0.1467711000
_diffrn_orient_matrix_UB_33      0.0080278000
_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  0.0491
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            51664
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.131
_diffrn_reflns_theta_min         3.325
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.071
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.487
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.867
_exptl_crystal_description       needle
_exptl_crystal_F_000             1616
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.417
_refine_diff_density_min         -0.906
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     196
_refine_ls_number_reflns         3112
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0363
_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^)+(0.0422P)^2^+10.0631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0941
_refine_ls_wR_factor_ref         0.0946
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3035
_reflns_number_total             3112
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra07456h2.cif
_cod_data_source_block           exp_8612
_cod_database_code               7251342
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C Mo S N H O'
_cell_oxdiff_angle_alpha         89.9881(11)
_cell_oxdiff_angle_beta          89.9847(11)
_cell_oxdiff_angle_gamma         90.0143(12)
_cell_oxdiff_length_a            14.8460(2)
_cell_oxdiff_length_b            7.28789(10)
_cell_oxdiff_length_c            26.5848(3)
_cell_oxdiff_measurement_reflns_used 19073
_cell_oxdiff_volume              2876.36(7)
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.154
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name exp_8612.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) groups
2. Restrained distances
 C10B-C9 \\sim C10A-C9
 with sigma of 0.02
 C10B-C11B \\sim C10A-C11A
 with sigma of 0.02
 C9-C11B \\sim C9-C11A
 with sigma of 0.04
 S1B-C12B \\sim S1A-C12A
 with sigma of 0.02
 S1B-C9 \\sim S1A-C9
 with sigma of 0.02
 S1B-C11B \\sim S1A-C11A
 with sigma of 0.04
 C10B-C12B \\sim C10A-C12A
 with sigma of 0.04
 C12B-C11B \\sim C12A-C11A
 with sigma of 0.02
 C9-C12B \\sim C9-C12A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(S1B) = Uanis(C12B) = Uanis(C11B) = Uanis(C10B)
Uanis(S1B) = Uanis(C10A) = Uanis(C12B) = Uanis(C11A) = Uanis(C12A) =
Uanis(C11B) = Uanis(C10B) = Uanis(S1A)
4. Others
 Sof(S1A)=Sof(C12A)=Sof(H12A)=Sof(C11A)=Sof(H11A)=Sof(C10A)=Sof(H10A)=1-FVAR(1)
 Sof(C10B)=Sof(H10B)=Sof(S1B)=Sof(C12B)=Sof(H12B)=Sof(C11B)=Sof(H11B)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C10B(H10B), C7(H7), C6(H6), C3(H3), C5(H5A), C12B(H12B), C11B(H11B), C4(H4),
 C12A(H12A), C11A(H11A), C10A(H10A)
5.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C)
5.c Idealised tetrahedral OH refined as rotating group:
 O5(H5)
;
_shelx_res_checksum              91174
_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 3.159
_oxdiff_exptl_absorpt_empirical_full_min 0.653