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_1576611
_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         'C40 H60 Cl1.406 I0.594 Mo2 S4 U Zr, C7 H8'
_chemical_formula_sum            'C47 H68 Cl1.406 I0.594 Mo2 S4 U Zr'
_chemical_formula_weight         1407.69
_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             2025-03-10
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                72.9030(10)
_cell_angle_beta                 81.0160(10)
_cell_angle_gamma                76.5430(10)
_cell_formula_units_Z            2
_cell_length_a                   11.62190(10)
_cell_length_b                   13.15020(10)
_cell_length_c                   17.5967(2)
_cell_measurement_reflns_used    56835
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.5670
_cell_measurement_theta_min      2.6500
_cell_volume                     2488.73(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-015 (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 0.998
_diffrn_measured_fraction_theta_max 0.984
_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    -13.00  28.00   0.50    0.05    --  -47.28  19.00  60.00   82
  2  \w    -53.00  25.00   0.50    0.05    --  -47.28  57.00  60.00  156
  3  \w    -30.00  26.00   0.50    0.05    --  -47.28  38.00 -90.00  112
  4  \w    -13.00  28.00   0.50    0.05    --  -47.28  19.00 150.00   82
  5  \w    -13.00  28.00   0.50    0.05    --  -47.28  19.00 120.00   82
  6  \w    -13.00  28.00   0.50    0.05    --  -47.28  19.00-150.00   82
  7  \w    -30.00  26.00   0.50    0.05    --  -47.28  38.00-180.00  112
  8  \w     42.00 118.00   0.50    0.18    --  113.25 -77.00   0.00  152
  9  \w     42.00 118.00   0.50    0.18    --  113.25 -77.00  90.00  152
 10  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00  90.00   84
 11  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00 150.00   84
 12  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00  30.00   84
 13  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00   0.00   84
 14  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00 -60.00   84
 15  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00 -90.00   84
 16  \w     42.00  84.00   0.50    0.18    --  113.25 -61.00-150.00   84
 17  \w     44.00 111.00   0.50    0.18    --  113.25-125.00 -30.00  134
 18  \w     44.00 111.00   0.50    0.18    --  113.25-125.00 -60.00  134
 19  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00-180.00  128
 20  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00-150.00  128
 21  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00-120.00  128
 22  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00 -90.00  128
 23  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00 -60.00  128
 24  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00 -30.00  128
 25  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00   0.00  128
 26  \w    -13.00  78.00   0.50    0.05    --   47.28 -93.00  42.00  182
 27  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00 120.00  128
 28  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00  90.00  128
 29  \w     42.00 106.00   0.50    0.18    --  113.25 -94.00  60.00  128
 30  \w     42.00 106.00   0.50    0.18    --  113.25 -93.00  42.00  128
 31  \w    100.00 178.00   0.50    0.18    --  113.25  15.00  90.00  156
 32  \w    101.00 178.00   0.50    0.18    --  113.25  45.00 150.00  154
 33  \w    101.00 178.00   0.50    0.18    --  113.25  45.00 150.00  154
 34  \w     97.00 178.00   0.50    0.18    --  113.25  61.00  90.00  162
 35  \w    101.00 178.00   0.50    0.18    --  113.25  30.00 150.00  154
 36  \w     35.00 120.00   0.50    0.05    --   47.28  38.00  30.00  170
 37  \w    101.00 178.00   0.50    0.18    --  113.25  45.00 -90.00  154
 38  \w    101.00 178.00   0.50    0.18    --  113.25  30.00-120.00  154
 39  \w    101.00 178.00   0.50    0.18    --  113.25  30.00-120.00  154
 40  \w    101.00 178.00   0.50    0.18    --  113.25  30.00-150.00  154
 41  \w    100.00 178.00   0.50    0.18    --  113.25  15.00 -30.00  156
 42  \w    100.00 178.00   0.50    0.18    --  113.25  15.00  30.00  156
 43  \w    104.00 178.00   0.50    0.18    --  113.25  93.00 153.00  148
 44  \w    104.00 178.00   0.50    0.18    --  113.25  93.00 153.00  148
 45  \w     95.00 178.00   0.50    0.18    --  113.25 125.00 -90.00  166
 46  \w     95.00 178.00   0.50    0.18    --  113.25 125.00 -90.00  166
 47  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 -60.00  188
 48  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00-150.00  188
 49  \w   -119.00 -32.00   0.50    0.05    --  -47.28 -57.00 -30.00  174
 50  \w   -119.00 -32.00   0.50    0.05    --  -47.28 -57.00-150.00  174
 51  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00  60.00  188
 52  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 120.00  188
 53  \w   -119.00 -25.00   0.50    0.05    --  -47.28 -77.00 150.00  188
 54  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -77.00  37.46  188
 55  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -77.00 120.00  188
 56  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -77.00   0.00  188
 57  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -77.00 -30.00  188
 58  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -77.00 -90.00  188
 59  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -76.00-163.52  188
 60  \w   -163.00 -71.00   0.50    0.18    --  -91.75 -71.00-132.01  184
 61  \w   -163.00 -69.00   0.50    0.18    --  -91.75 -76.00  71.38  188
 62  \w   -163.00 -83.00   0.50    0.18    --  -91.75 -93.00  42.00  160
 63  \w   -163.00 -83.00   0.50    0.18    --  -91.75 -94.00 150.00  160
 64  \w    -58.00 -19.00   0.50    0.18    --  -91.75  61.00 150.00   78
 65  \w    -80.00 -19.00   0.50    0.18    --  -91.75  93.00 153.00  122
 66  \w    -77.00  25.00   0.50    0.05    --  -47.28  93.00 153.00  204
 67  \w    -58.00 -19.00   0.50    0.18    --  -91.75  61.00-180.00   78
;
_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      0.0774787000
_diffrn_orient_matrix_UB_12      0.0736025000
_diffrn_orient_matrix_UB_13      0.0118180000
_diffrn_orient_matrix_UB_21      -0.0214584000
_diffrn_orient_matrix_UB_22      0.0752910000
_diffrn_orient_matrix_UB_23      -0.0841465000
_diffrn_orient_matrix_UB_31      -0.1108196000
_diffrn_orient_matrix_UB_32      0.0674469000
_diffrn_orient_matrix_UB_33      0.0352850000
_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  0.0604
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            84842
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.086
_diffrn_reflns_theta_min         2.639
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    20.133
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38238
_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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.878
_exptl_crystal_description       block
_exptl_crystal_F_000             1371
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.044
_refine_diff_density_max         2.167
_refine_diff_density_min         -2.379
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         10719
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0340
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0326P)^2^+15.0544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0844
_refine_ls_wR_factor_ref         0.0849
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10577
_reflns_number_total             10719
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matlrv38
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_database_code               1576611
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.471
_shelx_estimated_absorpt_t_min   0.160
_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
 U1-Cl1 = U1-Cl2
 2.652 with sigma of 0.02
 U1-I2' = U1-I1'
 3.082 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(I2') = Uanis(Cl2)
Uanis(Cl1) = Uanis(I1')
4. Others
 Sof(I1')=1-FVAR(1)
 Sof(Cl1)=FVAR(1)
 Sof(I2')=1-FVAR(2)
 Sof(Cl2)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C43(H43), C44(H44), C45(H45), C46(H46), C47(H47)
5.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), C36(H36A,
 H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C),
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              47337
_olex2_submission_original_sample_id mATLRV38
_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 1.896
_oxdiff_exptl_absorpt_empirical_full_min 0.653