Stabilisation and characterisation of a trinuclear uranyl complex by ligand-radical formation.
Singh, Mukesh K.; Sproules, Stephen; Love, Jason B.; Chemical communications (Cambridge, England) 62 (2026) 5660–5664; doi:10.1039/d5cc06420a

data_7135468
_publ_section_title
;
 Stabilisation and characterisation of a trinuclear uranyl complex by
 ligand-radical formation.
;
_journal_issue                   20
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5660
_journal_page_last               5664
_journal_paper_doi               10.1039/d5cc06420a
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C31 H41 Cl6 K N9 O13 U3, C4 H8 O, 2.25[C4H8O]'
_chemical_formula_sum            'C44 H67 Cl6 K N9 O16.25 U3'
_chemical_formula_weight         1947.95
_chemical_name_systematic        MKS-3
_chemical_properties_physical    Air-sensitive,Light-sensitive
_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     iterative
_audit_creation_date             2025-01-11
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-11 deposited with the CCDC.	2026-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                74.253(2)
_cell_angle_beta                 87.805(2)
_cell_angle_gamma                69.205(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9789(3)
_cell_length_b                   14.6991(4)
_cell_length_c                   17.4435(5)
_cell_measurement_reflns_used    23396
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      28.7130
_cell_measurement_theta_min      3.5000
_cell_volume                     3218.28(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.116a 64-bit (release 22-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2792
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.909
_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    -19.00 101.00   1.00   35.00    --   17.00  47.00 140.00  120
  2  \w    -67.00  53.00   1.00   35.00    --   17.00 -47.00  -8.00  120
  3  \w    -42.00  23.00   1.00   35.00    --  -16.45 -77.00  90.00   65
  4  \w    -15.00  30.00   1.00   35.00    --  -16.45 -99.00 -90.00   45
  5  \w   -113.00 -61.00   1.00   35.00    --  -16.45-178.00 120.00   52
  6  \w    -42.00  23.00   1.00   35.00    --  -16.45 -77.00 150.00   65
  7  \w    -42.00  23.00   1.00   35.00    --  -16.45 -77.00  30.00   65
  8  \w    -42.00  56.00   1.00   35.00    --   17.00 -77.00 -90.00   98
  9  \w    -67.00  54.00   1.00   35.00    --   17.00 -57.00  30.00  121
 10  \w     39.00 113.00   1.00   35.00    --   17.00 178.00   0.00   74
 11  \w    -15.00  54.00   1.00   35.00    --   17.00 -99.00-180.00   69
 12  \w    -20.00 101.00   1.00   35.00    --   17.00  38.00   0.00  121
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0510492000
_diffrn_orient_matrix_UB_12      -0.0347776000
_diffrn_orient_matrix_UB_13      0.0100009000
_diffrn_orient_matrix_UB_21      -0.0187009000
_diffrn_orient_matrix_UB_22      -0.0376035000
_diffrn_orient_matrix_UB_23      0.0222782000
_diffrn_orient_matrix_UB_31      -0.0015801000
_diffrn_orient_matrix_UB_32      -0.0161382000
_diffrn_orient_matrix_UB_33      -0.0345841000
_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  0.0578
_diffrn_reflns_av_unetI/netI     0.0561
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.909
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            70525
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.115
_diffrn_reflns_theta_min         3.254
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    7.909
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55633
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.010
_exptl_crystal_description       needle
_exptl_crystal_F_000             1842
_exptl_crystal_preparation
'Overnight reaction of one equivalence of TPymT with one equivalence of potassium graphite and three equivalence of {UO2Cl2(THF)2}, followed by filtration, concentration of filtrate and kept at -20oC for two days, leads to the formation of dark blue colour needle shape crystals.,Magnetic properties'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.164
_refine_diff_density_min         -0.896
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         15702
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0346P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0711
_refine_ls_wR_factor_ref         0.0763
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12339
_reflns_number_total             15702
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc06420a12.cif
_cod_data_source_block           mks-3-abs
_cod_depositor_comments          'Adding full bibliography for 7135468.cif.'
_cod_original_cell_volume        3218.28(15)
_cod_database_code               7135468
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C43 N9 O16 Cl6 K U3 '
_chemical_oxdiff_usercomment     '@120K THF vapour diffusion with hexane'
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.330
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,
 H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B),
  C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              55847
_shelx_hkl_checksum              53506
_shelx_fab_checksum              85198
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id MKS-3
_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 2.131
_oxdiff_exptl_absorpt_empirical_full_min 0.698