Tuning Reactivity at Uranium through Heterometal Substitution in a Redox-active Thiomolybdate Metalloligand
Valerio, Leyla R.; Dopp, Claire M.; Brennessel, William W.; Matson, Ellen; Chemical Science  (2026) –; doi:10.1039/D5SC09711H

data_1576609
_publ_section_title
;
 Tuning reactivity at uranium through heterometal substitution in a
 redox-active thiomolybdate metalloligand.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              7496
_journal_page_last               7508
_journal_paper_doi               10.1039/d5sc09711h
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H30 Mo2 S4'
_chemical_formula_sum            'C20 H30 Mo2 S4'
_chemical_formula_weight         590.56
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-10-10
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-12-08 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.5596(2)
_cell_length_b                   23.5596(2)
_cell_length_c                   8.20240(10)
_cell_measurement_reflns_used    23715
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.0670
_cell_measurement_theta_min      2.6490
_cell_volume                     4552.78(8)
_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-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2025/1 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_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 0.991
_diffrn_measured_fraction_theta_max 0.980
_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    -92.00 -17.00   0.50    0.94    --  -47.03 133.00  44.00  150
  2  \w    -25.00   7.00   0.50    0.94    --   47.03  -1.00 123.00   64
  3  \w     42.00 178.00   0.50    3.77    --  113.25   1.00 -56.00  272
  4  \w     89.00 178.00   0.50    3.77    --  113.25 135.00 -46.00  178
  5  \w    -14.00  28.00   0.50    0.94    --  -47.03  19.00-180.00   84
  6  \w    -14.00  28.00   0.50    0.94    --  -47.03  19.00-150.00   84
  7  \w    -14.00  28.00   0.50    0.94    --  -47.03  19.00 -30.00   84
  8  \w     42.00 111.00   0.50    3.77    --  113.25-125.00-150.00  138
  9  \w     42.00 111.00   0.50    3.77    --  113.25-125.00-180.00  138
 10  \w     42.00 111.00   0.50    3.77    --  113.25-125.00-150.00  138
 11  \w     42.00 108.00   0.50    3.77    --  113.25-106.00 -32.75  132
 12  \w     95.00 178.00   0.50    3.77    --  113.25 125.00-150.00  166
 13  \w     42.00  79.00   0.50    3.77    --  113.25 -61.00 120.00   74
 14  \w    -14.00  28.00   0.50    0.94    --  -47.03  19.00 -90.00   84
 15  \w     24.00 120.00   0.50    0.94    --   47.03  77.00  60.00  192
 16  \w     32.00 120.00   0.50    0.94    --   47.03  57.00-180.00  176
 17  \w     42.00  79.00   0.50    3.77    --  113.25 -61.00-150.00   74
 18  \w     41.00 111.00   0.50    3.77    --  113.25   0.00 150.00  140
 19  \w     41.00 111.00   0.50    3.77    --  113.25   0.00  90.00  140
 20  \w     42.00  69.00   0.50    3.77    --  113.25 -61.00 -30.00   54
 21  \w    101.00 178.00   0.50    3.77    --  113.25  30.00 150.00  154
 22  \w    108.00 133.00   0.50    3.77    --  113.25 137.00-137.00   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      0.0643185000
_diffrn_orient_matrix_UB_12      -0.0119661000
_diffrn_orient_matrix_UB_13      0.0027474000
_diffrn_orient_matrix_UB_21      0.0119622000
_diffrn_orient_matrix_UB_22      0.0642474000
_diffrn_orient_matrix_UB_23      0.0022046000
_diffrn_orient_matrix_UB_31      -0.0010584000
_diffrn_orient_matrix_UB_32      -0.0005012000
_diffrn_orient_matrix_UB_33      0.1877876000
_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  0.0388
_diffrn_reflns_av_unetI/netI     0.0219
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            38415
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         79.862
_diffrn_reflns_theta_min         2.652
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.458
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52396
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.114a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.723
_exptl_crystal_description       needle
_exptl_crystal_F_000             2384
_exptl_crystal_size_max          0.201
_exptl_crystal_size_mid          0.035
_exptl_crystal_size_min          0.019
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 1960 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.017(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         4816
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0232
_refine_ls_R_factor_gt           0.0220
_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^)+(0.0272P)^2^+6.3223P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0560
_refine_ls_wR_factor_ref         0.0565
_reflns_Friedel_coverage         0.762
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                4647
_reflns_number_total             4816
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matlrv63
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_original_cell_volume        4552.78(10)
_cod_database_code               1576609
_shelx_shelxl_version_number     2025/1
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.189
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name MATLRV63.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              98793
_olex2_submission_original_sample_id matlrv63
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.548
_oxdiff_exptl_absorpt_empirical_full_min 0.754