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_1571931
_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 U, 2(C16 H36 N), C2 H3 N, 0.75[C5H12]'
_chemical_formula_sum            'C45.75 H108 Mo10 N5 O36 U'
_chemical_formula_weight         2501.80
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-01
_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                90
_cell_angle_beta                 92.925(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.7821(5)
_cell_length_b                   15.0682(4)
_cell_length_c                   24.1223(6)
_cell_measurement_reflns_used    24205
_cell_measurement_temperature    100.2(4)
_cell_measurement_theta_max      24.6640
_cell_measurement_theta_min      2.3520
_cell_volume                     7907.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.98a (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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.2(4)
_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 0.998
_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    -11.00  44.00   0.50  180.00    --   -0.14  41.00-123.00  110
  2  \w    -71.00  11.00   0.50  180.00    --   -0.14 -41.00  84.00  164
  3  \w    -13.00  45.00   0.50  180.00    --   -0.14  38.00   0.00  116
  4  \w    -50.00  13.00   0.50  180.00    --   -0.14 -38.00-180.00  126
;
_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      0.0112181000
_diffrn_orient_matrix_UB_12      -0.0183828000
_diffrn_orient_matrix_UB_13      -0.0169198000
_diffrn_orient_matrix_UB_21      0.0230697000
_diffrn_orient_matrix_UB_22      0.0063272000
_diffrn_orient_matrix_UB_23      0.0105249000
_diffrn_orient_matrix_UB_31      -0.0019122000
_diffrn_orient_matrix_UB_32      -0.0316161000
_diffrn_orient_matrix_UB_33      0.0119193000
_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  0.0591
_diffrn_reflns_av_unetI/netI     0.0398
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            77757
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        19.665
_diffrn_reflns_theta_max         21.071
_diffrn_reflns_theta_min         2.214
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Ag) X-ray Source'
_exptl_absorpt_coefficient_mu    7.63857
_exptl_absorpt_correction_T_max  0.614
_exptl_absorpt_correction_T_min  0.280
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.98a (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    2.102
_exptl_crystal_description       block
_exptl_crystal_F_000             4870
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.818
_refine_diff_density_min         -1.713
_refine_diff_density_rms         0.175
_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     1040
_refine_ls_number_reflns         17419
_refine_ls_number_restraints     621
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0450
_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^)+(0.0355P)^2^+79.4581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1141
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12760
_reflns_number_total             17419
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02644f2.cif
_cod_data_source_block           matson003_ag_final
_cod_depositor_comments
'Adding full bibliography for 1571928--1571932.cif.'
_cod_database_code               1571931
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C47H63Mo10N5O36U
_shelx_estimated_absorpt_t_max   0.427
_shelx_estimated_absorpt_t_min   0.303
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29B-C25B
 2.5 with sigma of 0.02
 C35A-C36A
 1.5 with sigma of 0.02
 C34A-C36A
 2.5 with sigma of 0.02
 C23B-C22 \\sim C23A-C22 \\sim C15-C14 \\sim C11-C10 \\sim C19-C18
 with sigma of 0.02
 C24A-C23A \\sim C24B-C23B \\sim C16-C15 \\sim C12-C11 \\sim C19-C20
 with sigma of 0.02
 O17-C4A \\sim O17-C4B \\sim O16-C3 \\sim O15-C2 \\sim O14-C1 \\sim O34-C7
\\sim O33-C6 \\sim O32-C5 \\sim O35-
 C8A
 with sigma of 0.02
 O35-C8A \\sim O35-C8B \\sim O33-C8 \\sim O33-C6
 with sigma of 0.02
 C19-C18 \\sim C11-C10 \\sim C15-C14 \\sim C23B-C22 \\sim C23A-C22
 with sigma of 0.02
 N4-C37A \\sim N4-C33A \\sim N4-C25A \\sim N4-C29A
 with sigma of 0.02
 N4-C25A \\sim N4-C29A \\sim N4-C37A \\sim N4-C33A
 with sigma of 0.02
 N4-C37B \\sim N4-C37A \\sim N4-C29A \\sim N4-C29B \\sim N4-C25A \\sim N4-C33A
 with sigma of 0.02
 C38A-C37A \\sim C38B-C37B \\sim C29B-C30B \\sim C30A-C29A
 with sigma of 0.02
 C31-C30B \\sim C30A-C31 \\sim C38A-C39 \\sim C38B-C39
 with sigma of 0.02
 C30A-C29A \\sim C29B-C30B
 with sigma of 0.02
 C26A-C25A \\sim C29B-C30B \\sim C30A-C29A \\sim C38B-C37B \\sim C38A-C37A
\\sim C34B-C33B \\sim C34A-
 C33A
 with sigma of 0.02
 C26A-C27A \\sim C30A-C31 \\sim C31-C30B \\sim C38A-C39 \\sim C38B-C39 \\sim
C35B-C34B \\sim C34A-C35A
 with sigma of 0.02
 N4-C25A \\sim N4-C25B
 with sigma of 0.02
 C25A-C26A \\sim C25B-C26B
 with sigma of 0.02
 C26A-C27A \\sim C26B-C27B
 with sigma of 0.02
 C27A-C28A \\sim C27B-C28B
 with sigma of 0.02
 N4-C26A \\sim N4-C26B
 with sigma of 0.04
 C25A-C27A \\sim C25B-C27B
 with sigma of 0.04
 C26A-C28A \\sim C26B-C28B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C33B) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C29A)
\\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C37B) \\sim Ueq,
Uanis(C29B) \\sim Ueq, Uanis(C25B) \\sim Ueq, Uanis(C26A) \\sim Ueq,
Uanis(C30A) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C34A) \\sim Ueq,
Uanis(C38B) \\sim Ueq, Uanis(C30B) \\sim Ueq, Uanis(C34B) \\sim Ueq,
Uanis(C26B) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C35A) \\sim Ueq, Uanis(C35B) \\sim Ueq, Uanis(C27B) \\sim Ueq,
Uanis(C28A) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C36A)
\\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C28B) \\sim Ueq, : with sigma of 0.1
and sigma for terminal atoms of 0.2
Uanis(C8B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O35) = Uanis(C8B)
4. Rigid body (RIGU) restrains
 C22, C23A, C24A, C23B, C24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O17, C4A, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mo7, Mo9, O25, O27, Mo9A, Mo10, Mo8, Mo9B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C31, C32, C39, C40, C25A, C26A, C27A, C28A, C29A, C30A, C33A, C35A, C37A,
 C38A, C36B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C31, C32, C39, C40, C25A, C26A, C27A, C28A, C29A, C30A, C33A, C35A, C37A,
 C38A, C29B, C30B, C36B, C37B, C38B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C31, C32, C39, C40, C25A, C26A, C27A, C28A, C29A, C30A, C33A, C34A, C35A,
 C36A, C37A, C38A, C29B, C30B, C33B, C34B, C35B, C36B, C37B, C38B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C25A, C26A, C27A, C28A, C25B, C26B, C27B, C28B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O35, C8A, C8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H22C)=Sof(H22D)=Sof(C23B)=Sof(H23C)=Sof(H23D)=Sof(C24B)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(H22A)=Sof(H22B)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=
 Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=1-FVAR(2)
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=FVAR(2)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=1-
 FVAR(3)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 FVAR(3)
 Sof(Mo8)=Sof(Mo9B)=1-FVAR(4)
 Sof(Mo9A)=Sof(Mo10)=FVAR(4)
 Sof(H31C)=Sof(H31D)=Sof(H39C)=Sof(H39D)=Sof(C25B)=Sof(H25C)=Sof(H25D)=
 Sof(C26B)=Sof(H26C)=Sof(H26D)=Sof(C27B)=Sof(H27C)=Sof(H27D)=Sof(C28B)=
 Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=Sof(H29C)=Sof(H29D)=Sof(C30B)=
 Sof(H30C)=Sof(H30D)=Sof(C33B)=Sof(H33C)=Sof(H33D)=Sof(C34B)=Sof(H34A)=
 Sof(H34B)=Sof(C35B)=Sof(H35C)=Sof(H35D)=Sof(C36B)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(C38B)=Sof(H38C)=Sof(H38D)=1-FVAR(5)
 Sof(H31A)=Sof(H31B)=Sof(H39A)=Sof(H39B)=Sof(C25A)=Sof(H25A)=Sof(H25B)=
 Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(C28A)=
 Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(C30A)=
 Sof(H30A)=Sof(H30B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(C34A)=Sof(H34C)=
 Sof(H34D)=Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(C36A)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C38A)=Sof(H38A)=Sof(H38B)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C22(H22C,H22D), C23A(H23A,H23B), C23B(H23C,H23D), C31(H31A,
 H31B), C31(H31C,H31D), C39(H39A,H39B), C39(H39C,H39D), C25A(H25A,H25B),
 C26A(H26A,H26B), C27A(H27A,H27B), C29A(H29A,H29B), C30A(H30A,H30B), C33A(H33A,
 H33B), C34A(H34C,H34D), C35A(H35A,H35B), C37A(H37A,H37B), C38A(H38A,H38B),
 C25B(H25C,H25D), C26B(H26C,H26D), C27B(H27C,H27D), C29B(H29C,H29D), C30B(H30C,
 H30D), C33B(H33C,H33D), C34B(H34A,H34B), C35B(H35C,H35D), C37B(H37C,H37D),
 C38B(H38C,H38D)
6.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C7(H7A,
 H7B,H7C), C4A(H4AA,H4AB,H4AC), C6(H6A,H6B,H6C), C8A(H8AA,H8AB,H8AC), C4B(H4BA,
 H4BB,H4BC), C8(H8A,H8B,H8C), C8B(H8BA,H8BB,H8BC), C12(H12A,H12B,H12C),
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C24A(H24A,H24B,H24C), C24B(H24D,H24E,
 H24F), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C28A(H28A,H28B,H28C),
 C36A(H36D,H36E,H36F), C28B(H28D,H28E,H28F), C36B(H36A,H36B,H36C), C42(H42A,
 H42B,H42C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              7068
_shelx_hkl_checksum              93105
_shelx_fab_checksum              7522
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.880