Synthesis and characterization of a low-valent uranium complex supported by a redox-active molybdenum oxide metalloligand.
Valerio, Leyla R.; Patra, Kamaless; Shiels, Dominic; Brennessel, William W.; Matson, Ellen M.; Chemical communications (Cambridge, England)  (2025) –; doi:10.1039/d5cc05531h

data_7135182
_publ_section_title
;
 Synthesis and characterization of a low-valent uranium complex supported
 by a redox-active molybdenum oxide metalloligand.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d5cc05531h
_journal_year                    2025
_chemical_formula_moiety         'C40 H60 Cl Mo2 O4 U'
_chemical_formula_sum            'C40 H60 Cl Mo2 O4 U'
_chemical_formula_weight         1070.24
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-04
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-09-18 deposited with the CCDC.	2025-11-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.24570(10)
_cell_length_b                   16.29880(10)
_cell_length_c                   13.52220(10)
_cell_measurement_reflns_used    20763
_cell_measurement_temperature    272.99(10)
_cell_measurement_theta_max      79.2120
_cell_measurement_theta_min      2.7400
_cell_volume                     4021.27(4)
_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, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      272.99(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 0.981
_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     34.00 120.00   0.50    1.38    --   47.40  51.00-147.00  172
  2  \w    -46.00 -19.00   0.50    5.53    --  -91.75  51.00-147.00   54
  3  \w   -163.00 -70.00   0.50    5.53    --  -91.75 -75.00 -73.00  186
  4  \w    -81.00 -19.00   0.50    5.53    --  -91.75 105.00 -60.00  124
  5  \w     42.00 107.00   0.50    5.53    --  113.25-105.00-160.00  130
  6  \w     42.00  69.00   0.50    5.53    --  113.25 -51.00  66.00   54
  7  \w    -30.00  26.00   0.50    1.38    --  -47.40  38.00 -30.00  112
  8  \w     -9.00  28.00   0.50    1.38    --  -47.40  19.00-150.00   74
  9  \w     -9.00  28.00   0.50    1.38    --  -47.40  19.00  60.00   74
 10  \w   -119.00 -73.00   0.50    1.38    --  -47.40-125.00   0.00   92
 11  \w     -9.00  28.00   0.50    1.38    --  -47.40  19.00  30.00   74
 12  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00  90.00   84
 13  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00 -60.00   84
 14  \w     42.00 111.00   0.50    5.53    --  113.25-125.00  30.00  138
 15  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00   0.00   84
 16  \w     42.00 111.00   0.50    5.53    --  113.25-125.00  30.00  138
 17  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00 120.00   84
 18  \w    101.00 178.00   0.50    5.53    --  113.25  45.00  90.00  154
 19  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00-180.00   84
 20  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00 -30.00   84
 21  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00  30.00   84
 22  \w     42.00  84.00   0.50    5.53    --  113.25 -61.00-150.00   84
 23  \w   -119.00 -32.00   0.50    1.38    --  -47.40 -57.00 -30.00  174
 24  \w   -119.00 -40.00   0.50    1.38    --  -47.40 -57.00 120.00  158
 25  \w   -120.00 -34.00   0.50    1.38    --  -47.40 -38.00  30.00  172
;
_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      0.0289842000
_diffrn_orient_matrix_UB_12      0.0765410000
_diffrn_orient_matrix_UB_13      -0.0541373000
_diffrn_orient_matrix_UB_21      0.0759968000
_diffrn_orient_matrix_UB_22      -0.0131559000
_diffrn_orient_matrix_UB_23      0.0470785000
_diffrn_orient_matrix_UB_31      0.0226729000
_diffrn_orient_matrix_UB_32      -0.0538514000
_diffrn_orient_matrix_UB_33      -0.0885156000
_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  0.0348
_diffrn_reflns_av_unetI/netI     0.0195
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            36197
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.394
_diffrn_reflns_theta_min         4.069
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.138
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45566
_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    1.768
_exptl_crystal_description       needle
_exptl_crystal_F_000             2100
_exptl_crystal_size_max          0.131
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.029
_refine_diff_density_max         1.491
_refine_diff_density_min         -1.082
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     427
_refine_ls_number_reflns         4473
_refine_ls_number_restraints     504
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0291
_refine_ls_R_factor_gt           0.0264
_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^)+(0.0254P)^2^+10.0845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0640
_refine_ls_wR_factor_ref         0.0654
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4152
_reflns_number_total             4473
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05531h2.cif
_cod_data_source_block           matlrv59
_cod_database_code               7135182
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         UMo2O4ClC40H60
_shelx_estimated_absorpt_t_max   0.636
_shelx_estimated_absorpt_t_min   0.212
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name MATLRV59.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1-C6 \\sim C2-C7 \\sim C3-C8 \\sim C4-C9 \\sim C5-C10 \\sim C1A-C6A \\sim
C2A-C7A \\sim C3A-C8A \\sim C4A-
 C9A \\sim C5A-C10A
 with sigma of 0.02
 C11-C16 \\sim C12-C17 \\sim C13-C18 \\sim C14-C19 \\sim C15-C20
 with sigma of 0.02
 C21-C26 \\sim C22-C27 \\sim C23-C28 \\sim C24-C29 \\sim C25-C30
 with sigma of 0.02
3. 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(C9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. 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
 C11, C12, C13, C14, C15, C16, C17, C18, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C22, C23, C24, C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C2, C3, C4, C5, C1} sigma for 1-2: 0.02, 1-3: 0.04
{C5, C4, C3, C2, C1} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1, C2, C3, C4, C5}
{C1, C2, C3, C4, C5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1A, C2A, C3A, C4A, C5A}
{C22, C23, C24, C25, C21} sigma for 1-2: 0.02, 1-3: 0.04
{C25, C24, C23, C22, C21} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C21, C22, C23, C24, C25}
{C17, C18, C19, C20, C16} sigma for 1-2: 0.02, 1-3: 0.04
{C20, C19, C18, C17, C16} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C16, C17, C18, C19, C20}
{C27, C28, C29, C30, C26} sigma for 1-2: 0.02, 1-3: 0.04
{C30, C29, C28, C27, C26} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C26, C27, C28, C29, C30}
{C12, C13, C14, C15, C11} sigma for 1-2: 0.02, 1-3: 0.04
{C15, C14, C13, C12, C11} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C11, C12, C13, C14, C15}
{C6, C7, C8, C9, C10} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C6A, C7A, C8A, C9A, C10A}
{C7, C8, C9, C10, C6} sigma for 1-2: 0.02, 1-3: 0.04
{C8, C9, C10, C6, C7} sigma for 1-2: 0.02, 1-3: 0.04
{C10, C9, C8, C7, C6} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C6, C7, C8, C9, C10}
6. Others
 Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=
 Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=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)
 Fixed Sof: C21(0.5) C22(0.5) C23(0.5) C24(0.5) C25(0.5) C26(0.5) H26A(0.5)
 H26B(0.5) H26C(0.5) C27(0.5) H27A(0.5) H27B(0.5) H27C(0.5) C28(0.5) H28A(0.5)
 H28B(0.5) H28C(0.5) C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5)
 H30B(0.5) H30C(0.5) C11(0.5) C12(0.5) C13(0.5) C14(0.5) C15(0.5) C16(0.5)
 H16A(0.5) H16B(0.5) H16C(0.5) C17(0.5) H17A(0.5) H17B(0.5) H17C(0.5) C18(0.5)
 H18A(0.5) H18B(0.5) H18C(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C20(0.5)
 H20A(0.5) H20B(0.5) H20C(0.5)
7.a 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), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC),
 C9A(H9AA,H9AB,H9AC), C10A(H10D,H10E,H10F), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C20(H20A,H20B,H20C)
;
_shelx_res_checksum              50288
_olex2_submission_original_sample_id matlrv59
_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 2.043
_oxdiff_exptl_absorpt_empirical_full_min 0.810