Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation of a stable U(v) sandwich complex.
Shiels, Dominic; Brennessel, William W.; Crawley, Matthew R.; Matson, Ellen M.; Chemical science 15 (2024) 11072–11083; doi:10.1039/d4sc02644f

data_1571929
_publ_section_title
;
 Leveraging a reduced polyoxomolybdate-alkoxide cluster for the formation
 of a stable U(v) sandwich complex.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              11072
_journal_page_last               11083
_journal_paper_doi               10.1039/d4sc02644f
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C8 H24 Mo10 N2 O36 Th, 2(C16 H36 N), C2 H3 N'
_chemical_formula_sum            'C42 H99 Mo10 N5 O36 Th'
_chemical_formula_weight         2441.70
_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
_audit_creation_date             2024-03-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-08 deposited with the CCDC.	2024-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                87.1760(10)
_cell_angle_beta                 84.0750(10)
_cell_angle_gamma                73.7140(10)
_cell_formula_units_Z            2
_cell_length_a                   12.8161(2)
_cell_length_b                   15.4649(2)
_cell_length_c                   19.9194(3)
_cell_measurement_reflns_used    36004
_cell_measurement_temperature    100.01(16)
_cell_measurement_theta_max      29.1890
_cell_measurement_theta_min      2.5720
_cell_volume                     3768.50(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.101a 64-bit (release 13-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(16)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_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    -21.00  32.00   0.50   45.00    --   -0.14 -99.00 -60.00  106
  2  \w    -23.00  17.00   0.50   45.00    --   -0.14 -99.00  90.00   80
  3  \w    -43.00  11.00   0.50   45.00    --   -0.14 -38.00 150.00  108
  4  \w    -69.00 -41.00   0.50   45.00    --   -0.14 -19.00 -60.00   56
  5  \w    -26.00   4.00   0.50   45.00    --   -0.14 -19.00 -60.00   60
  6  \w     12.00  58.00   0.50   45.00    --   -0.14  38.00 -90.00   92
  7  \w    -18.00  21.00   0.50   45.00    --   -0.14 -77.00 120.00   78
  8  \w    -17.00  62.00   0.50   45.00    --   -0.14   0.00 -30.00  158
;
_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      0.0294149000
_diffrn_orient_matrix_UB_12      -0.0015418000
_diffrn_orient_matrix_UB_13      0.0192093000
_diffrn_orient_matrix_UB_21      -0.0328824000
_diffrn_orient_matrix_UB_22      -0.0003948000
_diffrn_orient_matrix_UB_23      0.0206975000
_diffrn_orient_matrix_UB_31      0.0118108000
_diffrn_orient_matrix_UB_32      -0.0376599000
_diffrn_orient_matrix_UB_33      -0.0004020000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ag K\a'
_diffrn_radiation_wavelength     0.56087
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            86035
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        19.665
_diffrn_reflns_theta_max         25.144
_diffrn_reflns_theta_min         2.329
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Ag) X-ray Source'
_exptl_absorpt_coefficient_mu    7.87606
_exptl_absorpt_correction_T_max  0.476
_exptl_absorpt_correction_T_min  0.124
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.101a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.152
_exptl_crystal_description       block
_exptl_crystal_F_000             2368
_exptl_crystal_size_max          0.416
_exptl_crystal_size_mid          0.324
_exptl_crystal_size_min          0.267
_refine_diff_density_max         1.564
_refine_diff_density_min         -1.645
_refine_diff_density_rms         0.127
_refine_ls_extinction_coef       0.00045(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     939
_refine_ls_number_reflns         27268
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0252
_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^)+(0.0207P)^2^+0.7907P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0507
_refine_ls_wR_factor_ref         0.0530
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22524
_reflns_number_total             27268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02644f2.cif
_cod_data_source_block           matson002_ag_final
_cod_depositor_comments
'Adding full bibliography for 1571928--1571932.cif.'
_cod_database_code               1571929
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C42 H100Mo10 N5 O36 Th'
_shelx_estimated_absorpt_t_max   0.256
_shelx_estimated_absorpt_t_min   0.158
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 Mo10-O20 \\sim Mo9-O20
 with sigma of 0.02
 N4-C37B \\sim N4-C37A \\sim N4-C25 \\sim N4-C29 \\sim N4-C33
 with sigma of 0.02
 Mo10-O31B \\sim Mo9-O31A
 with sigma of 0.02
 Mo10-O27 \\sim Mo9-O27
 with sigma of 0.02
 Mo9B-O30B \\sim Mo9A-O30A
 with sigma of 0.02
 Mo10-O26 \\sim Mo9-O26
 with sigma of 0.02
 O20-O31B \\sim O20-O31A
 with sigma of 0.04
 Mo10-O25B \\sim Mo9-O25A
 with sigma of 0.02
 O27-O31B \\sim O27-O31A
 with sigma of 0.04
 O27-O30B \\sim O27-O30A
 with sigma of 0.04
 Mo10-O35 \\sim Mo9-O35
 with sigma of 0.02
 O26-O31B \\sim O26-O31A
 with sigma of 0.04
 Mo9B-O27 \\sim Mo9A-O27
 with sigma of 0.02
 O25B-O31B \\sim O25A-O31A
 with sigma of 0.04
 Mo9B-O19 \\sim Mo9A-O19
 with sigma of 0.02
 O19-O30B \\sim O19-O30A
 with sigma of 0.04
 O25B-O30B \\sim O25A-O30A
 with sigma of 0.04
 Mo9B-O25B \\sim Mo9A-O25A
 with sigma of 0.02
 Mo9B-O24 \\sim Mo9A-O24
 with sigma of 0.02
 Mo9B-O30B \\sim Mo9A-O30A \\sim Mo9-O31A \\sim Mo10-O31B
 with sigma of 0.02
 Mo9B-O34 \\sim Mo9A-O34
 with sigma of 0.02
 O35-O31B \\sim O35-O31A
 with sigma of 0.04
 Mo10-Mo9B \\sim Mo9-Mo9A
 with sigma of 0.04
 O24-O30B \\sim O24-O30A
 with sigma of 0.04
 O34-O30B \\sim O34-O30A
 with sigma of 0.04
 O20-O25B \\sim O20-O25A
 with sigma of 0.04
 O27-O25B \\sim O27-O25A
 with sigma of 0.04
 O26-O25B \\sim O26-O25A
 with sigma of 0.04
 O19-O25B \\sim O19-O25A
 with sigma of 0.04
 O25B-O35 \\sim O25A-O35
 with sigma of 0.04
 O25B-O24 \\sim O25A-O24
 with sigma of 0.04
 O25B-O34 \\sim O25A-O34
 with sigma of 0.04
 Mo10-O25B \\sim Mo9-O25A \\sim Mo9A-O25A \\sim Mo9B-O25B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C37B) \\sim Ueq, Uanis(C37A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 C37B, C37A, C38B, C38A, C39A, C39B, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O30A, O30B, Mo9A, Mo9B, O25A, O25B, Mo9, Mo10, O31A, O31B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H40D)=Sof(H40E)=Sof(H40F)=Sof(C38B)=Sof(H38C)=Sof(H38D)=Sof(C39B)=
 Sof(H39C)=Sof(H39D)=Sof(C37B)=Sof(H37C)=Sof(H37D)=1-FVAR(1)
 Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C38A)=
 Sof(H38A)=Sof(H38B)=Sof(C39A)=Sof(H39A)=Sof(H39B)=FVAR(1)
 Sof(O31A)=Sof(Mo9)=Sof(O25A)=Sof(Mo9A)=Sof(O30A)=1-FVAR(2)
 Sof(Mo10)=Sof(Mo9B)=Sof(O25B)=Sof(O31B)=Sof(O30B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C21(H21A,H21B), C13(H13A,H13B), C18(H18A,H18B), C30(H30A,
 H30B), C9(H9A,H9B), C26(H26A,H26B), C27(H27A,H27B), C25(H25A,H25B), C14(H14A,
 H14B), C23(H23A,H23B), C17(H17A,H17B), C11(H11A,H11B), C10(H10A,H10B),
 C15(H15A,H15B), C33(H33A,H33B), C29(H29A,H29B), C31(H31A,H31B), C22(H22A,H22B),
  C34(H34A,H34B), C35(H35A,H35B), C37A(H37A,H37B), C38A(H38A,H38B), C39A(H39A,
 H39B), C38B(H38C,H38D), C39B(H39C,H39D), C37B(H37C,H37D)
6.b Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C40(H40A,H40B,H40C), C40(H40D,H40E,H40F),
 C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C32(H32A,H32B,H32C), C20(H20A,H20B,H20C),
 C42(H42A,H42B,H42C), C28(H28A,H28B,H28C), C2(H2A,H2B,H2C), C1(H1A,H1B,H1C),
 C24(H24A,H24B,H24C), C7(H7A,H7B,H7C), C12(H12A,H12B,H12C), C5(H5A,H5B,H5C),
 C36(H36A,H36B,H36C), C16(H16A,H16B,H16C)
;
_shelx_res_checksum              11867
_shelx_hkl_checksum              95039
_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 1.290
_oxdiff_exptl_absorpt_empirical_full_min 0.773