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_1576613
_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         'C30 H45 I2 Mo2 S4 U, 2.5(C6 H6)'
_chemical_formula_sum            'C45 H60 I2 Mo2 S4 U'
_chemical_formula_weight         1412.88
_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             2024-05-13
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2025-12-08 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                67.289(2)
_cell_angle_beta                 88.2090(10)
_cell_angle_gamma                74.7910(10)
_cell_formula_units_Z            4
_cell_length_a                   14.2943(2)
_cell_length_b                   18.0623(3)
_cell_length_c                   21.4605(3)
_cell_measurement_reflns_used    78223
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.3360
_cell_measurement_theta_min      1.6610
_cell_volume                     4916.92(15)
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.875
_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     -3.00  83.00   0.50    2.35    --   10.99  53.00  50.00  172
  2  \w    -61.00  25.00   0.50    2.35    --   10.99 -53.00 -94.00  172
  3  \w    -26.00  60.00   0.50    2.35    --  -12.24  53.00  50.00  172
  4  \w    -23.00  44.00   0.50    2.35    --   10.99 -99.00 -90.00  134
  5  \w     38.00  84.00   0.50    2.35    --   10.99-178.00-150.00   92
  6  \w     38.00  84.00   0.50    2.35    --   10.99-178.00  30.00   92
  7  \w     38.00  84.00   0.50    2.35    --   10.99-178.00-120.00   92
  8  \w    -84.00   3.00   0.50    2.35    --  -12.24 -57.00 120.00  174
  9  \w    -84.00   3.00   0.50    2.35    --  -12.24 -57.00   0.00  174
 10  \w    -84.00  11.00   0.50    2.35    --  -12.24 -77.00-120.00  190
 11  \w     38.00  84.00   0.50    2.35    --   10.99-178.00  90.00   92
 12  \w    -25.00  61.00   0.50    2.35    --  -12.24  37.00 150.00  172
 13  \w    -85.00 -38.00   0.50    2.35    --  -12.24 -37.00-150.00   94
 14  \w    -35.00  61.00   0.50    2.35    --  -12.24  77.00 -30.00  192
;
_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      -0.0402129000
_diffrn_orient_matrix_UB_12      0.0057118000
_diffrn_orient_matrix_UB_13      -0.0215240000
_diffrn_orient_matrix_UB_21      0.0119064000
_diffrn_orient_matrix_UB_22      -0.0436464000
_diffrn_orient_matrix_UB_23      0.0087317000
_diffrn_orient_matrix_UB_31      -0.0300311000
_diffrn_orient_matrix_UB_32      -0.0043312000
_diffrn_orient_matrix_UB_33      0.0274267000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0389
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.875
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            180230
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.875
_diffrn_reflns_theta_full        29.575
_diffrn_reflns_theta_max         33.444
_diffrn_reflns_theta_min         1.481
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.243
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56896
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.104a (Rigaku Oxford Diffraction, 2023)
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    1.909
_exptl_crystal_description       block
_exptl_crystal_F_000             2704
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.182
_exptl_crystal_size_min          0.105
_refine_diff_density_max         1.003
_refine_diff_density_min         -0.967
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1181
_refine_ls_number_reflns         33605
_refine_ls_number_restraints     381
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0278
_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^)+(0.0156P)^2^+1.6353P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0479
_refine_ls_wR_factor_ref         0.0501
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27612
_reflns_number_total             33605
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09711h2.cif
_cod_data_source_block           matcd01mo
_cod_depositor_comments
'Adding full bibliography for 1576608--1576613.cif.'
_cod_database_code               1576613
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.609
_shelx_estimated_absorpt_t_min   0.349
_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 0.01 and sigma
for terminal atoms of 0.02 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(C7') \\sim Ueq, Uanis(C9') \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
3. Rigid body (RIGU) restrains
 C1', C2', C3', C4', C5', C6', C7', C8', C9', C10'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{C85, C86, C87, C88, C89, C90} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C85', C86', C87', C88', C89', C90'}
{C86, C87, C88, C89, C90, C85} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C85, C86, C87, C88, C89, C90}
5. Others
 Sof(C1')=Sof(C2')=Sof(C3')=Sof(C4')=Sof(C5')=Sof(C6')=Sof(H6'A)=Sof(H6'B)=
 Sof(H6'C)=Sof(C7')=Sof(H7'A)=Sof(H7'B)=Sof(H7'C)=Sof(C8')=Sof(H8'A)=Sof(H8'B)=
 Sof(H8'C)=Sof(C9')=Sof(H9'A)=Sof(H9'B)=Sof(H9'C)=Sof(C10')=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=1-FVAR(1)
 Sof(C1)=Sof(C2)=Sof(C3)=Sof(C4)=Sof(C5)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=
 Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Sof(C85')=Sof(H85')=Sof(C86')=Sof(H86')=Sof(C87')=Sof(H87')=Sof(C88')=
 Sof(H88')=Sof(C89')=Sof(H89')=Sof(C90')=Sof(H90')=0.5*(1-FVAR(3))
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=
 Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90)=0.5*FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C67(H67),
 C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75),
  C76(H76), C77(H77), C78(H78), C79(H79), C80(H80), C81(H81), C82(H82),
 C83(H83), C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90),
  C85'(H85'), C86'(H86'), C87'(H87'), C88'(H88'), C89'(H89'), C90'(H90'),
 C91(H91), C92(H92), C93(H93)
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), C6'(H6'A,H6'B,H6'C), C7'(H7'A,H7'B,H7'C), C8'(H8'A,H8'B,H8'C),
 C9'(H9'A,H9'B,H9'C), C10'(H10D,H10E,H10F), 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), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C)
;
_shelx_res_checksum              84819
_olex2_submission_original_sample_id matcd01mo
_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 1.769
_oxdiff_exptl_absorpt_empirical_full_min 0.724