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_1576610
_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_formula_moiety         'C60 H90 K2 Mo4 S8 Zr2, C6 D6'
_chemical_formula_sum            'C66 H90 D6 K2 Mo4 S8 Zr2'
_chemical_formula_weight         1796.34
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-05-18
_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                89.584(2)
_cell_angle_beta                 79.031(2)
_cell_angle_gamma                66.672(2)
_cell_formula_units_Z            1
_cell_length_a                   10.9927(2)
_cell_length_b                   11.2521(3)
_cell_length_c                   16.3898(3)
_cell_measurement_reflns_used    29749
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.4340
_cell_measurement_theta_min      2.7390
_cell_volume                     1822.32(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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 2019/3 (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 0.992
_diffrn_measured_fraction_theta_max 0.962
_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   -118.00 -52.00   0.50    0.55    --  -46.53-156.00 -29.00  132
  2  \w    -83.00  -9.00   0.50    0.55    --  -46.53 120.00-148.00  148
  3  \w   -107.00 -29.00   0.50    0.55    --  -46.53 156.00   7.00  156
  4  \w     31.00  90.00   0.50    0.55    --   46.53-120.00 126.00  118
  5  \w     50.00 113.00   0.50    0.55    --   46.53-156.00 -29.00  126
  6  \w    -84.00 -22.00   0.50    2.21    --  -91.75 120.00-148.00  124
  7  \w   -161.00 -77.00   0.50    2.21    --  -91.75-120.00 126.00  168
  8  \w   -107.00 -29.00   0.50    2.21    --  -91.75 156.00   7.00  156
  9  \w   -144.00 -52.00   0.50    2.21    --  -91.75-156.00 -29.00  184
 10  \w     50.00 133.00   0.50    2.21    --  113.25-156.00 -29.00  166
 11  \w     98.00 178.00   0.50    2.21    --  113.25 120.00-148.00  160
 12  \w     44.00 109.00   0.50    2.21    --  113.25-120.00 126.00  130
 13  \w     74.00 161.00   0.50    2.21    --  113.25 156.00   7.00  174
 14  \w    -58.00  26.00   0.50    0.55    --  -46.53  57.00-150.00  168
 15  \w    -11.00  29.00   0.50    0.55    --  -46.53  19.00 120.00   80
 16  \w    -32.00  26.00   0.50    0.55    --  -46.53  38.00 -60.00  116
 17  \w    -11.00  29.00   0.50    0.55    --  -46.53  19.00-150.00   80
 18  \w    -11.00  29.00   0.50    0.55    --  -46.53  19.00 -30.00   80
 19  \w   -118.00 -24.00   0.50    0.55    --  -46.53 -77.00   0.00  188
 20  \w    -58.00  26.00   0.50    0.55    --  -46.53  57.00-150.00  168
 21  \w    -11.00  29.00   0.50    0.55    --  -46.53  19.00 -90.00   80
 22  \w   -163.00 -73.00   0.50    2.21    --  -91.75 -66.00-160.36  180
 23  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00   0.00   78
 24  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00-120.00   78
 25  \w     41.00 113.00   0.50    2.21    --  113.25   0.00 120.00  144
 26  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00 120.00  128
 27  \w     95.00 178.00   0.50    2.21    --  113.25 125.00 -30.00  166
 28  \w    101.00 178.00   0.50    2.21    --  113.25  45.00 -60.00  154
 29  \w     44.00 111.00   0.50    2.21    --  113.25-125.00-120.00  134
 30  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00  60.00   78
 31  \w     95.00 178.00   0.50    2.21    --  113.25 125.00 -60.00  166
 32  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00 120.00   78
 33  \w     44.00 111.00   0.50    2.21    --  113.25-125.00 -90.00  134
 34  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00  30.00  128
 35  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00  30.00  128
 36  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00  30.00   78
 37  \w     44.00 111.00   0.50    2.21    --  113.25-125.00   0.00  134
 38  \w     97.00 178.00   0.50    2.21    --  113.25  61.00 -90.00  162
 39  \w     44.00 111.00   0.50    2.21    --  113.25-125.00-150.00  134
 40  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00 -60.00  128
 41  \w     97.00 178.00   0.50    2.21    --  113.25  61.00 120.00  162
 42  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00   0.00  128
 43  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00   0.00  128
 44  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00  90.00  128
 45  \w     44.00 111.00   0.50    2.21    --  113.25-125.00 -60.00  134
 46  \w    100.00 178.00   0.50    2.21    --  113.25  15.00   0.00  156
 47  \w    100.00 178.00   0.50    2.21    --  113.25  15.00  90.00  156
 48  \w     91.00 178.00   0.50    2.21    --  113.25  77.00   0.00  174
 49  \w     91.00 178.00   0.50    2.21    --  113.25  77.00   0.00  174
 50  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00-150.00  128
 51  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00 150.00  128
 52  \w     97.00 178.00   0.50    2.21    --  113.25  61.00 120.00  162
 53  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00 -90.00   78
 54  \w     42.00 106.00   0.50    2.21    --  113.25 -94.00 -30.00  128
 55  \w     44.00 111.00   0.50    2.21    --  113.25-125.00  90.00  134
 56  \w    101.00 178.00   0.50    2.21    --  113.25  45.00-180.00  154
 57  \w     42.00  81.00   0.50    2.21    --  113.25 -61.00 -30.00   78
 58  \w   -118.00 -24.00   0.50    0.55    --  -46.53 -77.00 120.00  188
 59  \w   -118.00 -32.00   0.50    0.55    --  -46.53 -57.00 150.00  172
 60  \w   -118.00 -24.00   0.50    0.55    --  -46.53 -77.00-120.00  188
 61  \w   -118.00 -24.00   0.50    0.55    --  -46.53 -77.00  60.00  188
 62  \w   -118.00 -30.00   0.50    0.55    --  -46.53 -62.00 -91.12  176
 63  \w     24.00 119.00   0.50    0.55    --   46.53  77.00-180.00  190
 64  \w     34.00 120.00   0.50    0.55    --   46.53  38.00 -60.00  172
 65  \w     24.00 119.00   0.50    0.55    --   46.53  77.00-120.00  190
 66  \w     34.00 120.00   0.50    0.55    --   46.53  38.00  90.00  172
 67  \w     34.00 120.00   0.50    0.55    --   46.53  38.00 150.00  172
 68  \w     32.00 119.00   0.50    0.55    --   46.53  57.00 -30.00  174
 69  \w   -163.00 -81.00   0.50    2.21    --  -91.75 -72.00  96.19  164
 70  \w   -163.00 -69.00   0.50    2.21    --  -91.75 -77.00 150.00  188
 71  \w   -163.00 -73.00   0.50    2.21    --  -91.75 -66.00-116.27  180
;
_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      0.0650080000
_diffrn_orient_matrix_UB_12      -0.0183821000
_diffrn_orient_matrix_UB_13      -0.0935155000
_diffrn_orient_matrix_UB_21      0.1322760000
_diffrn_orient_matrix_UB_22      -0.1028907000
_diffrn_orient_matrix_UB_23      0.0183556000
_diffrn_orient_matrix_UB_31      -0.0508192000
_diffrn_orient_matrix_UB_32      -0.1069333000
_diffrn_orient_matrix_UB_33      -0.0117274000
_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  0.0508
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            50864
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.360
_diffrn_reflns_theta_min         2.754
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.170
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39699
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green-brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.637
_exptl_crystal_description       plate
_exptl_crystal_F_000             906
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.104
_exptl_crystal_size_min          0.023
_refine_diff_density_max         1.480
_refine_diff_density_min         -1.408
_refine_diff_density_rms         0.134
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     385
_refine_ls_number_reflns         7682
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.134
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0519
_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^)+(0.0321P)^2^+15.3361P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1222
_refine_ls_wR_factor_ref         0.1242
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7148
_reflns_number_total             7682
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matlrv45
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_database_code               1576610
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.783
_shelx_estimated_absorpt_t_min   0.193
_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
2. Restrained distances
 C31-C32 = C31-C33_$2 = C32-C33 = C33-C31_$2
 1.39 with sigma of 0.01
3.a Aromatic/amide H refined with riding coordinates:
 C31(D31), C32(D32), C33(D33)
3.b 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), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              80448
_olex2_submission_original_sample_id matlrv45
_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 2.100
_oxdiff_exptl_absorpt_empirical_full_min 0.612