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_7251340
_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 N2 O2 S'
_chemical_formula_sum            'C12 H10 N2 O2 S'
_chemical_formula_weight         246.28
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-08-26
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7308)
;
_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            4
_cell_length_a                   19.4454(3)
_cell_length_b                   5.36070(10)
_cell_length_c                   10.9087(2)
_cell_measurement_reflns_used    5013
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      78.9380
_cell_measurement_theta_min      6.0970
_cell_volume                     1137.13(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.990
_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     57.00  98.00   0.50    0.08    --  111.50 -95.00-120.00   82
  2  \w     42.00  95.00   0.50    0.08    --  111.50 -95.00 -90.00  106
  3  \w     82.00 110.00   0.50    0.08    --  111.50-125.00  30.00   56
  4  \w     44.00 106.00   0.50    0.08    --  111.50-101.00  50.00  124
  5  \w     44.00 106.00   0.50    0.08    --  111.50 -85.00 142.00  124
  6  \w     43.00  69.00   0.50    0.08    --  111.50 -61.00  60.00   52
  7  \w     41.00  66.00   0.50    0.08    --  111.50 -61.00  30.00   50
  8  \w     48.00 105.00   0.50    0.08    --  111.50 -77.00  60.00  114
  9  \w     42.00  79.00   0.50    0.08    --  111.50 -77.00 150.00   74
 10  \w     42.00  70.00   0.50    0.08    --  111.50 -61.00  90.00   56
 11  \w    139.00 165.00   0.50    0.08    --  111.50  85.00 -98.00   52
 12  \w     94.00 175.00   0.50    0.08    --  111.50  77.00-150.00  162
 13  \w    107.00 132.00   0.50    0.08    --  111.50  61.00-180.00   50
 14  \w    141.00 166.00   0.50    0.08    --  111.50  61.00-180.00   50
 15  \w    122.00 149.00   0.50    0.08    --  111.50  45.00-150.00   54
 16  \w     95.00 143.00   0.50    0.08    --  111.50  77.00-120.00   96
 17  \w     43.00  98.00   0.50    0.05    --   50.15  45.00  58.00  110
 18  \w    107.00 135.00   0.50    0.08    --  111.50  45.00  58.00   56
 19  \w    131.00 174.00   0.50    0.08    --  111.50  61.00 -60.00   86
 20  \w    106.00 131.00   0.50    0.08    --  111.50  15.00-150.00   50
 21  \w    -26.00  15.00   0.50    0.05    --  -50.15  19.00-180.00   82
 22  \w    -50.00 -21.00   0.50    0.08    --  -90.00  45.00   0.00   58
 23  \w    -50.00 -18.00   0.50    0.08    --  -90.00  45.00  58.00   64
 24  \w   -120.00 -95.00   0.50    0.05    --  -50.15 -77.00 -60.00   50
 25  \w   -119.00 -81.00   0.50    0.05    --  -50.15-125.00 -60.00   76
 26  \w   -156.00-130.00   0.50    0.08    --  -90.00-101.00  50.00   52
 27  \w   -119.00 -94.00   0.50    0.05    --  -50.15-125.00 120.00   50
 28  \w   -119.00 -88.00   0.50    0.05    --  -50.15-125.00  60.00   62
;
_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      0.0422964000
_diffrn_orient_matrix_UB_12      0.1160982000
_diffrn_orient_matrix_UB_13      0.0567186000
_diffrn_orient_matrix_UB_21      -0.0123262000
_diffrn_orient_matrix_UB_22      0.0459081000
_diffrn_orient_matrix_UB_23      -0.2681232000
_diffrn_orient_matrix_UB_31      -0.0658420000
_diffrn_orient_matrix_UB_32      0.0659684000
_diffrn_orient_matrix_UB_33      0.0866684000
_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  0.0345
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7899
_diffrn_reflns_point_group_measured_fraction_full 0.895
_diffrn_reflns_point_group_measured_fraction_max 0.868
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.746
_diffrn_reflns_theta_min         4.548
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.466
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68208
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_description       prism
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.125
_refine_diff_density_min         -0.099
_refine_diff_density_rms         0.029
_refine_ls_abs_structure_details
;
 Flack x determined using 751 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(14)
_refine_ls_extinction_coef       0.0043(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     193
_refine_ls_number_reflns         2155
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0419P)^2^+0.0220P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0736
_refine_ls_wR_factor_ref         0.0747
_reflns_Friedel_coverage         0.665
_reflns_Friedel_fraction_full    0.783
_reflns_Friedel_fraction_max     0.732
_reflns_number_gt                2042
_reflns_number_total             2155
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra07456h2.cif
_cod_data_source_block           exp_7482
_cod_database_code               7251340
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O S'
_shelx_estimated_absorpt_t_max   0.791
_shelx_estimated_absorpt_t_min   0.578
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C10B-C11B \\sim C10A-C12B
 with sigma of 0.02
 S2B-C11A \\sim S1A-C12A
 with sigma of 0.02
 C11B-C11A \\sim C12B-C12A
 with sigma of 0.02
 S2B-C8 \\sim S1A-C8
 with sigma of 0.04
 S2B-C10B \\sim S1A-C10A
 with sigma of 0.04
 S2B-C11B \\sim S1A-C12B
 with sigma of 0.04
 C8-C10B \\sim C8-C10A
 with sigma of 0.04
 C10B-C11A \\sim C10A-C12A
 with sigma of 0.04
3. Others
 Sof(C10A)=Sof(H10A)=Sof(C12B)=Sof(H12B)=Sof(C12A)=Sof(H12A)=Sof(S1A)=1-FVAR(1)
 Sof(S2B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C11A)=Sof(H11A)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C7(H7), N1(H1), C3(H3), C6(H6), C4(H4), C10B(H10B), C5(H5), C11B(H11B),
 C11A(H11A), C10A(H10A), C12B(H12B), C12A(H12A)
4.b Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_shelx_res_checksum              72662
_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 1.472
_oxdiff_exptl_absorpt_empirical_full_min 0.793