Hydrogen evolution reaction evidenced for Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>-thiosemicarbazone coordination complexes.
Buils, Jordi; Calancea, Sergiu; Bouaouni, Yasmine; AlChamandi, Roa; Laurans, Maxime; Cebotari, Diana; Marrot, Jérôme; Frégnaux, Mathieu; Gulea, Aurelian; Segado-Centellas, Mireia; Bo, Carles; Floquet, Sébastien; Dalton transactions (Cambridge, England : 2003) 54 (2025) 10381–10395; doi:10.1039/d5dt00399g

data_7718849
_publ_section_title
;
 Hydrogen evolution reaction evidenced for
 Mo<sub>2</sub>O<sub>2</sub>S<sub>2</sub>-thiosemicarbazone coordination
 complexes.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10381
_journal_page_last               10395
_journal_paper_doi               10.1039/d5dt00399g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C22 H26 Mo2 N6 O6 S4, 2(C3 H7 N O)'
_chemical_formula_sum            'C28 H40 Mo2 N8 O8 S4'
_chemical_formula_weight         936.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-20
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-16 deposited with the CCDC.	2025-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.464(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   40.1819(19)
_cell_length_b                   9.2877(5)
_cell_length_c                   21.7610(9)
_cell_measurement_reflns_used    9911
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      26.98
_cell_measurement_theta_min      2.16
_cell_volume                     7608.6(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX4'
_computing_data_reduction        'Bruker SAINT'
_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      200.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1139
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -52
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            180276
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.377
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.935
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6541
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1580 before and 0.0843 after correction.
The Ratio of minimum to maximum transmission is 0.8774.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.636
_exptl_crystal_description       needle
_exptl_crystal_F_000             3808
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.456
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     495
_refine_ls_number_reflns         8713
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0302
_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^)+(0.0236P)^2^+15.8422P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0632
_refine_ls_wR_factor_ref         0.0743
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6835
_reflns_number_total             8713
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00399g2.cif
_cod_data_source_block           yb002dyn_0m_a
_cod_depositor_comments          'Adding full bibliography for 7718849.cif.'
_cod_database_code               7718849
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.767
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1D1-C2D1
 1.4 with sigma of 0.02
 N1D1-C3D1
 -1.5 with sigma of 0.02
3. Others
 Fixed Sof: C1D1(0.5) H1D1(0.5) N1D1(0.5) C2D1(0.5) H2DA(0.5) H2DB(0.5)
 H2DC(0.5) C3D1(0.5) H3DA(0.5) H3DB(0.5) H3DC(0.5) C1D2(0.5) H1D2(0.5)
 N1D2(0.5) C2D2(0.5) H2DD(0.5) H2DE(0.5) H2DF(0.5) C3D2(0.5) H3DD(0.5)
 H3DE(0.5) H3DF(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C13A(H13A,H13B), C14A(H14A,H14B), C13B(H13C,H13D), C14B(H14C,H14D)
4.b Aromatic/amide H refined with riding coordinates:
 C5A(H5A), C7A(H7A), C8A(H8A), C9A(H9A), C5B(H5B), C7B(H7B), C8B(H8B),
 C9B(H9B), C1C(H1C), C1D1(H1D1), C1D2(H1D2)
4.c X=CH2 refined with riding coordinates:
 N1A(H1AA,H1AB), N1B(H1BA,H1BB)
4.d Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C16B(H16D,H16E,H16F), C2C(H2CA,H2CB,H2CC), C3C(H3CA,
 H3CB,H3CC), C2D1(H2DA,H2DB,H2DC), C3D1(H3DA,H3DB,H3DC), C2D2(H2DD,H2DE,H2DF),
 C3D2(H3DD,H3DE,H3DF)
;
_shelx_res_checksum              6982
_shelx_hkl_checksum              62429
_olex2_submission_special_instructions 'No special instructions were received'