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_1576608
_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         'C40 H60 Mo2 S8 U Zr, C4 H8 O'
_chemical_formula_sum            'C44 H68 Mo2 O S8 U Zr'
_chemical_formula_weight         1390.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-06-24
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-12-04 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.8060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.77150(10)
_cell_length_b                   11.70870(10)
_cell_length_c                   16.49650(10)
_cell_measurement_reflns_used    56326
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.3080
_cell_measurement_theta_min      2.7260
_cell_volume                     2430.81(3)
_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 2019/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -56.00  26.00   0.50    0.41    --  -47.01  58.00  67.00  164
  2  \w   -119.00 -32.00   0.50    0.41    --  -47.01 -58.00 -72.00  174
  3  \w     32.00 120.00   0.50    0.41    --   47.01  58.00  67.00  176
  4  \w    -24.00  62.00   0.50    0.41    --   47.01 -58.00 -72.00  172
  5  \w   -163.00 -76.00   0.50    1.66    --  -91.75 -58.00 -72.00  174
  6  \w    -56.00 -19.00   0.50    1.66    --  -91.75  58.00  67.00   74
  7  \w     98.00 178.00   0.50    1.66    --  113.25  58.00  67.00  160
  8  \w     42.00  79.00   0.50    1.66    --  113.25 -58.00 -72.00   74
  9  \w   -120.00 -73.00   0.50    0.41    --  -47.01-125.00 120.00   94
 10  \w     -9.00  29.00   0.50    0.41    --  -47.01  19.00-120.00   76
 11  \w    -30.00  26.00   0.50    0.41    --  -47.01  38.00 -90.00  112
 12  \w     -9.00  29.00   0.50    0.41    --  -47.01  19.00-150.00   76
 13  \w     34.00 123.00   0.50    0.41    --   47.01  19.00-120.00  178
 14  \w     34.00  95.00   0.50    0.41    --   47.01-125.00  60.00  122
 15  \w     32.00 120.00   0.50    0.41    --   47.01  57.00 120.00  176
 16  \w   -163.00 -70.00   0.50    1.66    --  -91.75 -75.00-162.17  186
 17  \w   -163.00 -71.00   0.50    1.66    --  -91.75 -71.00 174.67  184
 18  \w   -163.00 -79.00   0.50    1.66    --  -91.75 -45.00-180.00  168
 19  \w   -163.00 -75.00   0.50    1.66    --  -91.75 -61.00-150.00  176
 20  \w    -61.00 -19.00   0.50    1.66    --  -91.75  61.00-120.00   84
 21  \w   -163.00 -75.00   0.50    1.66    --  -91.75 -61.00 150.00  176
 22  \w     91.00 178.00   0.50    1.66    --  113.25  77.00 120.00  174
 23  \w    100.00 178.00   0.50    1.66    --  113.25  15.00   0.00  156
 24  \w     91.00 178.00   0.50    1.66    --  113.25  77.00 120.00  174
 25  \w     42.00  84.00   0.50    1.66    --  113.25 -61.00-150.00   84
 26  \w     91.00 178.00   0.50    1.66    --  113.25  77.00-180.00  174
 27  \w     42.00  84.00   0.50    1.66    --  113.25 -61.00-120.00   84
 28  \w    101.00 178.00   0.50    1.66    --  113.25  30.00 120.00  154
 29  \w     91.00 178.00   0.50    1.66    --  113.25  77.00 150.00  174
 30  \w    101.00 178.00   0.50    1.66    --  113.25  45.00 120.00  154
 31  \w     42.00 106.00   0.50    1.66    --  113.25 -94.00   0.00  128
 32  \w     91.00 178.00   0.50    1.66    --  113.25  77.00-120.00  174
 33  \w     97.00 178.00   0.50    1.66    --  113.25  61.00 -60.00  162
 34  \w    100.00 178.00   0.50    1.66    --  113.25  15.00   0.00  156
 35  \w     42.00  84.00   0.50    1.66    --  113.25 -61.00 -30.00   84
 36  \w     97.00 178.00   0.50    1.66    --  113.25  61.00-180.00  162
 37  \w     42.00 111.00   0.50    1.66    --  113.25-125.00 150.00  138
 38  \w     97.00 178.00   0.50    1.66    --  113.25  61.00-150.00  162
 39  \w     95.00 178.00   0.50    1.66    --  113.25 125.00  90.00  166
 40  \w     42.00 106.00   0.50    1.66    --  113.25 -94.00-150.00  128
 41  \w     95.00 178.00   0.50    1.66    --  113.25 125.00  90.00  166
 42  \w    101.00 178.00   0.50    1.66    --  113.25  45.00 -60.00  154
 43  \w    101.00 178.00   0.50    1.66    --  113.25  30.00-120.00  154
 44  \w    101.00 178.00   0.50    1.66    --  113.25  45.00 -60.00  154
 45  \w     95.00 178.00   0.50    1.66    --  113.25 125.00 150.00  166
 46  \w     97.00 178.00   0.50    1.66    --  113.25  61.00 150.00  162
 47  \w     42.00  84.00   0.50    1.66    --  113.25 -61.00   0.00   84
 48  \w    101.00 178.00   0.50    1.66    --  113.25  30.00  60.00  154
 49  \w     95.00 178.00   0.50    1.66    --  113.25 125.00 -60.00  166
 50  \w    101.00 178.00   0.50    1.66    --  113.25  30.00  30.00  154
 51  \w     42.00  84.00   0.50    1.66    --  113.25 -61.00-180.00   84
 52  \w     97.00 178.00   0.50    1.66    --  113.25  61.00 -30.00  162
 53  \w    -30.00  26.00   0.50    0.41    --  -47.01  38.00 150.00  112
 54  \w   -120.00 -34.00   0.50    0.41    --  -47.01 -38.00   0.00  172
 55  \w   -120.00 -34.00   0.50    0.41    --  -47.01 -38.00 120.00  172
 56  \w     24.00 120.00   0.50    0.41    --   47.01  77.00-150.00  192
 57  \w     24.00 120.00   0.50    0.41    --   47.01  77.00 -90.00  192
 58  \w     24.00 120.00   0.50    0.41    --   47.01  77.00 150.00  192
 59  \w     24.00 120.00   0.50    0.41    --   47.01  77.00-120.00  192
 60  \w     24.00 120.00   0.50    0.41    --   47.01  77.00  90.00  192
 61  \w     24.00 120.00   0.50    0.41    --   47.01  77.00 -30.00  192
 62  \w     24.00 120.00   0.50    0.41    --   47.01  77.00   0.00  192
 63  \w   -163.00-125.00   0.50    1.66    --  -91.75 -77.00 109.85   76
 64  \w   -163.00 -69.00   0.50    1.66    --  -91.75 -77.00 -90.00  188
 65  \w   -163.00 -70.00   0.50    1.66    --  -91.75 -74.00  35.40  186
 66  \w     42.00 111.00   0.50    1.66    --  113.25-125.00-180.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            68579
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.020
_diffrn_reflns_theta_min         2.718
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.559
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27056
_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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.900
_exptl_crystal_description       needle
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.037
_exptl_crystal_size_min          0.015
_refine_diff_density_max         1.752
_refine_diff_density_min         -1.069
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Flack x determined using 4602 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.028(2)
_refine_ls_extinction_coef       0.00008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         10311
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0233
_refine_ls_R_factor_gt           0.0226
_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^)+(0.0350P)^2^+3.3482P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0586
_refine_ls_wR_factor_ref         0.0589
_reflns_Friedel_coverage         0.878
_reflns_Friedel_fraction_full    0.992
_reflns_Friedel_fraction_max     0.957
_reflns_number_gt                10114
_reflns_number_total             10311
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matlrv52
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_database_code               1576608
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.768
_shelx_estimated_absorpt_t_min   0.151
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 1.2A
All non-hydrogen atoms have similar U: within 0.4A with sigma of 0.002 and
sigma for terminal atoms of 0.004 within 0.4A
3. Same fragment restrains
{O1, C41, C42, C43, C44} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1A, C41A, C42A, C43A, C44A}
{O1, C44, C43, C42, C41} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, C41, C42, C43, C44}
4. Others
 Sof(O1A)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42C)=Sof(H42D)=
 Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=1-FVAR(1)
 Sof(O1)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=
 Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B), C41A(H41C,
 H41D), C42A(H42C,H42D), C43A(H43C,H43D), C44A(H44C,H44D)
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)
;
_shelx_res_checksum              46082
_olex2_submission_original_sample_id matlrv52
_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
;