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_1571932
_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 Zr, 2(C16 H36 N), C2 H3 N, 0.776(C4 H10 O)'
_chemical_formula_sum            'C45.1 H106.75 Mo10 N5 O36.78 Zr'
_chemical_formula_weight         2358.35
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-02-21
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2024-04-08 deposited with the CCDC.	2024-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.6550(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4037(2)
_cell_length_b                   15.0940(2)
_cell_length_c                   24.2093(3)
_cell_measurement_reflns_used    80810
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.1890
_cell_measurement_theta_min      1.6060
_cell_volume                     7812.84(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))'
_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 0.880
_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     38.00  84.00   0.50    3.10    --   11.01-178.00 120.00   92
  2  \w     38.00  84.00   0.50    3.10    --   11.01-178.00   0.00   92
  3  \w      1.00  48.00   0.50    3.10    --   11.01-109.00-155.00   94
  4  \w    -64.00   8.00   0.50    3.10    --   11.01 -19.00 -60.00  144
  5  \w     -4.00  84.00   0.50    3.10    --   11.01  57.00 -90.00  176
  6  \w    -12.00  58.00   0.50    3.10    --   11.01  77.00  30.00  140
  7  \w    -64.00   8.00   0.50    3.10    --   11.01 -19.00 -90.00  144
  8  \w    -83.00   3.00   0.50    3.10    --  -12.10 -57.00-120.00  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      -0.0180731000
_diffrn_orient_matrix_UB_12      -0.0137081000
_diffrn_orient_matrix_UB_13      -0.0237813000
_diffrn_orient_matrix_UB_21      0.0115493000
_diffrn_orient_matrix_UB_22      -0.0437541000
_diffrn_orient_matrix_UB_23      0.0035320000
_diffrn_orient_matrix_UB_31      -0.0253362000
_diffrn_orient_matrix_UB_32      -0.0102105000
_diffrn_orient_matrix_UB_33      0.0167854000
_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  0.0367
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.880
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            147354
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.880
_diffrn_reflns_theta_full        29.575
_diffrn_reflns_theta_max         33.336
_diffrn_reflns_theta_min         1.590
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.759
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81367
_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            green-blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.005
_exptl_crystal_description       block
_exptl_crystal_F_000             4666
_exptl_crystal_size_max          0.212
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.131
_refine_diff_density_max         1.955
_refine_diff_density_min         -2.111
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1167
_refine_ls_number_reflns         26637
_refine_ls_number_restraints     597
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0553
_refine_ls_R_factor_gt           0.0445
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0216P)^2^+34.6529P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0891
_refine_ls_wR_factor_ref         0.0929
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22504
_reflns_number_total             26637
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02644f2.cif
_cod_data_source_block           matds01mo
_cod_depositor_comments
'Adding full bibliography for 1571928--1571932.cif.'
_cod_original_formula_sum        'C45.10 H106.75 Mo10 N5 O36.78 Zr'
_cod_database_code               1571932
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.802
_shelx_estimated_absorpt_t_min   0.707
_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
 C25-C29 \\sim C25-C33 \\sim C25-C37 \\sim C29-C33 \\sim C29-C37 \\sim C33-C37
\\sim C25A-C29A \\sim C25A-
 C33A \\sim C25A-C37A \\sim C29A-C33A \\sim C29A-C37A \\sim C33A-C37A
 with sigma of 0.04
 N3-C21 \\sim N3-C21A
 with sigma of 0.02
 C17-C18 \\sim C17-C18A
 with sigma of 0.02
 C18-C19 \\sim C18A-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C17-C19 \\sim C17-C19A
 with sigma of 0.04
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 O26-C8 \\sim O26-C8A \\sim O23-C5 \\sim O23-C5A \\sim O24-C6 \\sim O24-C6A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.22A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.22A
O23 \\sim C5 \\sim C5A: within 2A with sigma of 0.008 and sigma for terminal
atoms of 0.016 within 2A
4. Rigid body (RIGU) restrains
 C43, C44, O37, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, C21A, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C37, C38, C39, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N4A, C37A, C38A, C39A, C40A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O26, C8, C8A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{C21, C22, C23, C24} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C21A, C22A, C23A, C24A}
{N4A, C33A, C34A, C35A, C36A, C29A, C30A, C31A, C32A, C25A, C26A, C27A, C28A}
sigma for 1-2: 0.02, 1-3: 0.04
{N4, C29, C30, C31, C32} sigma for 1-2: 0.02, 1-3: 0.04
{N4A, C29A, C30A, C31A, C32A} sigma for 1-2: 0.02, 1-3: 0.04
{N4, C33, C34, C35, C36} sigma for 1-2: 0.02, 1-3: 0.04
{N4A, C33A, C34A, C35A, C36A} sigma for 1-2: 0.02, 1-3: 0.04
{N4, C37, C38, C39, C40} sigma for 1-2: 0.02, 1-3: 0.04
{N4A, C37A, C38A, C39A, C40A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N4, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36}
{C46, C45, O37, C44, C43} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C43, C44, O37, C45, C46}
6. Others
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(1)
 Sof(C21A)=Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=
 Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(2)
 Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C19A)=Sof(H19C)=
 Sof(H19D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(3)
 Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(3)
 Sof(N4A)=Sof(C33A)=Sof(H33C)=Sof(H33D)=Sof(C34A)=Sof(H34C)=Sof(H34D)=
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=
 Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C31A)=
 Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C25A)=
 Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=Sof(H27C)=
 Sof(H27D)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C37A)=Sof(H37C)=
 Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=
 Sof(C40A)=Sof(H40D)=Sof(H40E)=Sof(H40F)=1-FVAR(4)
 Sof(N4)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=
 Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=
 Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=
 Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(4)
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 1-FVAR(5)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(O37)=
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(5)
7.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), C17(H17C,H17D), C18(H18A,H18B), C19(H19A,H19B),
  C18A(H18C,H18D), C19A(H19C,H19D), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,
 H23B), C21A(H21C,H21D), C22A(H22C,H22D), C23A(H23C,H23D), C25(H25A,H25B),
 C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
  C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C37(H37A,H37B), C38(H38A,
 H38B), C39(H39A,H39B), C33A(H33C,H33D), C34A(H34C,H34D), C35A(H35C,H35D),
 C29A(H29C,H29D), C30A(H30C,H30D), C31A(H31C,H31D), C25A(H25C,H25D), C26A(H26C,
 H26D), C27A(H27C,H27D), C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,H39D),
 C44(H44A,H44B), C45(H45A,H45B)
7.b Me refined with riding coordinates:
 C36(H36A,H36B,H36C)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C5A(H5AA,H5AB,
 H5AC), C6A(H6AA,H6AB,H6AC), C8A(H8AA,H8AB,H8AC), C12(H12A,H12B,H12C), C16(H16A,
 H16B,H16C), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C24(H24A,H24B,H24C),
 C24A(H24D,H24E,H24F), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C40(H40A,H40B,
 H40C), C36A(H36D,H36E,H36F), C32A(H32D,H32E,H32F), C28A(H28D,H28E,H28F),
 C40A(H40D,H40E,H40F), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C46(H46A,H46B,
 H46C)
;
_shelx_res_checksum              30001
_shelx_hkl_checksum              99965
_olex2_submission_original_sample_id matds01mo
_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 1.213
_oxdiff_exptl_absorpt_empirical_full_min 0.821