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_1576612
_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         'C52 H70 Mo2 N2 S4 U Zr, 1.5(C7 H8)'
_chemical_formula_sum            'C62.5 H82 Mo2 N2 S4 U Zr'
_chemical_formula_weight         1510.67
_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             2025-05-17
_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                72.4760(10)
_cell_angle_beta                 88.3000(10)
_cell_angle_gamma                67.3040(10)
_cell_formula_units_Z            2
_cell_length_a                   11.1822(2)
_cell_length_b                   13.5657(2)
_cell_length_c                   22.4202(2)
_cell_measurement_reflns_used    64425
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.8420
_cell_measurement_theta_min      2.0800
_cell_volume                     2977.54(8)
_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 0.996
_diffrn_measured_fraction_theta_max 0.976
_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    -78.00  25.00   0.50    0.29    --  -47.28  95.00  71.00  206
  2  \w     -9.00  79.00   0.50    0.29    --   47.28 -95.00 -38.00  176
  3  \w   -163.00 -83.00   0.50    1.16    --  -91.75 -95.00 -38.00  160
  4  \w    -80.00 -19.00   0.50    1.16    --  -91.75  95.00  71.00  122
  5  \w     42.00 106.00   0.50    1.16    --  113.25 -95.00 -38.00  128
  6  \w    105.00 178.00   0.50    1.16    --  113.25  95.00  71.00  146
  7  \w    -58.00  25.00   0.50    0.29    --  -47.28  57.00  30.00  166
  8  \w    -11.00  28.00   0.50    0.29    --  -47.28  19.00 -90.00   78
  9  \w    -11.00  28.00   0.50    0.29    --  -47.28  19.00 150.00   78
 10  \w    -11.00  28.00   0.50    0.29    --  -47.28  19.00  60.00   78
 11  \w    -11.00  28.00   0.50    0.29    --  -47.28  19.00 -30.00   78
 12  \w    -11.00  28.00   0.50    0.29    --  -47.28  19.00 120.00   78
 13  \w    -32.00  26.00   0.50    0.29    --  -47.28  38.00   0.00  116
 14  \w    -58.00  25.00   0.50    0.29    --  -47.28  57.00-120.00  166
 15  \w     34.00  93.00   0.50    0.29    --   47.28-125.00-150.00  118
 16  \w   -163.00 -83.00   0.50    1.16    --  -91.75 -94.00  60.00  160
 17  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00 -30.00   78
 18  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00  60.00  128
 19  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00  60.00  128
 20  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00 150.00   78
 21  \w    101.00 178.00   0.50    1.16    --  113.25  45.00 -30.00  154
 22  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00-180.00  128
 23  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00  90.00   78
 24  \w    101.00 178.00   0.50    1.16    --  113.25  45.00 -30.00  154
 25  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00-120.00  128
 26  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 120.00  128
 27  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00   0.00  128
 28  \w    100.00 178.00   0.50    1.16    --  113.25  15.00 120.00  156
 29  \w     41.00 113.00   0.50    1.16    --  113.25   0.00 -90.00  144
 30  \w     44.00 111.00   0.50    1.16    --  113.25-125.00 -90.00  134
 31  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00-120.00   78
 32  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 -60.00  128
 33  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00 120.00   78
 34  \w     97.00 178.00   0.50    1.16    --  113.25  61.00  30.00  162
 35  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 120.00  128
 36  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00  90.00  128
 37  \w     41.00 113.00   0.50    1.16    --  113.25   0.00 150.00  144
 38  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00  30.00   78
 39  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00  30.00  128
 40  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00 -60.00   78
 41  \w     97.00 178.00   0.50    1.16    --  113.25  61.00-150.00  162
 42  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 150.00  128
 43  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 150.00  128
 44  \w     44.00 111.00   0.50    1.16    --  113.25-125.00  60.00  134
 45  \w     44.00 111.00   0.50    1.16    --  113.25-125.00  60.00  134
 46  \w    101.00 178.00   0.50    1.16    --  113.25  30.00 120.00  154
 47  \w     95.00 178.00   0.50    1.16    --  113.25 125.00  30.00  166
 48  \w     91.00 178.00   0.50    1.16    --  113.25  77.00 120.00  174
 49  \w     44.00 111.00   0.50    1.16    --  113.25-125.00 -60.00  134
 50  \w     42.00 106.00   0.50    1.16    --  113.25 -94.00 -90.00  128
 51  \w     44.00 111.00   0.50    1.16    --  113.25-125.00 120.00  134
 52  \w    101.00 178.00   0.50    1.16    --  113.25  45.00 150.00  154
 53  \w     42.00  81.00   0.50    1.16    --  113.25 -61.00-180.00   78
 54  \w   -119.00 -25.00   0.50    0.29    --  -47.28 -77.00-120.00  188
 55  \w   -119.00 -32.00   0.50    0.29    --  -47.28 -57.00  30.00  174
 56  \w   -119.00 -32.00   0.50    0.29    --  -47.28 -57.00 150.00  174
 57  \w   -119.00 -32.00   0.50    0.29    --  -47.28 -57.00 -90.00  174
 58  \w   -119.00 -25.00   0.50    0.29    --  -47.28 -77.00   0.00  188
 59  \w   -119.00 -25.00   0.50    0.29    --  -47.28 -77.00 120.00  188
 60  \w     25.00 120.00   0.50    0.29    --   47.28  77.00 -60.00  190
 61  \w     25.00 120.00   0.50    0.29    --   47.28  77.00 120.00  190
 62  \w     25.00 120.00   0.50    0.29    --   47.28  77.00  60.00  190
 63  \w     25.00 120.00   0.50    0.29    --   47.28  77.00   0.00  190
 64  \w     25.00 120.00   0.50    0.29    --   47.28  77.00-150.00  190
 65  \w   -163.00 -92.00   0.50    1.16    --  -91.75 -77.00  90.00  142
 66  \w   -163.00 -69.00   0.50    1.16    --  -91.75 -76.00-158.32  188
 67  \w   -163.00 -69.00   0.50    1.16    --  -91.75 -77.00  17.90  188
 68  \w   -163.00 -69.00   0.50    1.16    --  -91.75 -76.00 -87.27  188
 69  \w   -163.00 -69.00   0.50    1.16    --  -91.75 -77.00 -30.00  188
 70  \w    100.00 178.00   0.50    1.16    --  113.25  15.00 -60.00  156
;
_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      -0.0172157000
_diffrn_orient_matrix_UB_12      -0.0722158000
_diffrn_orient_matrix_UB_13      0.0646840000
_diffrn_orient_matrix_UB_21      -0.0683443000
_diffrn_orient_matrix_UB_22      0.1069838000
_diffrn_orient_matrix_UB_23      0.0191175000
_diffrn_orient_matrix_UB_31      -0.1324786000
_diffrn_orient_matrix_UB_32      0.0122673000
_diffrn_orient_matrix_UB_33      -0.0263335000
_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  0.0484
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            94519
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.178
_diffrn_reflns_theta_min         3.647
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.931
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43997
_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    1.685
_exptl_crystal_description       needle
_exptl_crystal_F_000             1502
_exptl_crystal_size_max          0.137
_exptl_crystal_size_mid          0.041
_exptl_crystal_size_min          0.019
_refine_diff_density_max         1.171
_refine_diff_density_min         -1.466
_refine_diff_density_rms         0.101
_refine_ls_extinction_coef       0.000033(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/3 (Sheldrick 2015b)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     773
_refine_ls_number_reflns         12731
_refine_ls_number_restraints     162
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0237
_refine_ls_R_factor_gt           0.0222
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0123P)^2^+8.2095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0523
_refine_ls_wR_factor_ref         0.0529
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12146
_reflns_number_total             12731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matlrv48
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_original_formula_sum        'C62.50 H82 Mo2 N2 S4 U Zr'
_cod_database_code               1576612
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.251
_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. 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
Uanis(C61) \\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 C60, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Same fragment restrains
{C60, C61, C66, C65, C64, C63, C62} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C60, C61, C62, C63, C64, C65, C66}
{C53, C54, C55, C56, C57, C58, C59} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C53A, C54A, C55A, C56A, C57A, C58A, C59A}
{C53, C54, C59, C58, C57, C56, C55} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C53, C54, C55, C56, C57, C58, C59}
5. Others
 Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54A)=Sof(C55A)=Sof(H55A)=
 Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=
 Sof(H59A)=1-FVAR(1)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(C55)=Sof(H55)=Sof(C56)=
 Sof(H56)=Sof(C57)=Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=FVAR(1)
 Fixed Sof: C60(0.5) H60A(0.5) H60B(0.5) H60C(0.5) C61(0.5) C62(0.5) H62(0.5)
 C63(0.5) H63(0.5) C64(0.5) H64(0.5) C65(0.5) H65(0.5) C66(0.5) H66(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C48(H48), C49(H49),
 C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59),
  C55A(H55A), C56A(H56A), C57A(H57A), C58A(H58A), C59A(H59A), C62(H62),
 C63(H63), C64(H64), C65(H65), C66(H66)
6.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), C53(H53A,H53B,H53C), C53A(H53D,H53E,H53F), C60(H60A,H60B,
 H60C)
;
_shelx_res_checksum              54106
_olex2_submission_original_sample_id matlrv48
_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 2.027
_oxdiff_exptl_absorpt_empirical_full_min 0.737