Isolation of Ce(iv) centered polyoxoalkoxide sandwich-type complexes allows comparison of metal-oxygen bond covalency.
Shiels, Dominic; Pittalis, Michele; Gunarathna, Nadeeshan; Berlfein, Adriana C.; Brennessel, William W.; Ruggiero, Michael T.; Matson, Ellen M.; Chemical science 16 (2025) 21917–21931; doi:10.1039/d5sc06415e

data_1575984
_publ_section_title
;
 Isolation of Ce(iv) centered polyoxoalkoxide sandwich-type complexes
 allows comparison of metal-oxygen bond covalency.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              21917
_journal_page_last               21931
_journal_paper_doi               10.1039/d5sc06415e
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C8 H24 Ce Mo2 N2 O36 W8, 2(C16 H36 N), 0.5(C4 H10 O), C2 H3 N'
_chemical_formula_sum            'C44 H104 Ce Mo2 N5 O36.5 W8'
_chemical_formula_weight         3090.12
_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             2025-05-16
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-08-21 deposited with the CCDC.	2025-10-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.8090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.8546(2)
_cell_length_b                   15.10070(10)
_cell_length_c                   24.2678(2)
_cell_measurement_reflns_used    76605
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      79.7410
_cell_measurement_theta_min      2.9790
_cell_volume                     7999.23(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_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, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_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 0.978
_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  74.00   0.50    0.43    --   47.28 -85.00-122.00  190
  2  \w    -21.00  74.00   0.50    0.43    --   47.28 -85.00-122.00  190
  3  \w   -163.00 -79.00   0.50    1.74    --  -91.75 -85.00-122.00  168
  4  \w   -163.00 -79.00   0.50    1.74    --  -91.75 -85.00-122.00  168
  5  \w   -118.00 -19.00   0.50    1.74    --  -91.75  85.00  -2.00  198
  6  \w    101.00 178.00   0.50    1.74    --  113.25  85.00  -2.00  154
  7  \w    -14.00  28.00   0.50    0.43    --  -47.28  19.00-150.00   84
  8  \w    -35.00  26.00   0.50    0.43    --  -47.28  38.00 120.00  122
  9  \w    -74.00  25.00   0.50    0.43    --  -47.28  85.00  -2.00  198
 10  \w    -14.00  28.00   0.50    0.43    --  -47.28  19.00   0.00   84
 11  \w    -74.00  25.00   0.50    0.43    --  -47.28  85.00  -2.00  198
 12  \w    -14.00  28.00   0.50    0.43    --  -47.28  19.00 -90.00   84
 13  \w    -14.00  28.00   0.50    0.43    --  -47.28  19.00  90.00   84
 14  \w    -67.00 -19.00   0.50    1.74    --  -91.75  61.00 150.00   96
 15  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00-120.00   74
 16  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00 -60.00   74
 17  \w     97.00 178.00   0.50    1.74    --  113.25  61.00 -60.00  162
 18  \w    101.00 178.00   0.50    1.74    --  113.25  30.00 -90.00  154
 19  \w     42.00 136.00   0.50    1.74    --  113.25 -77.00-180.00  188
 20  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00  60.00   74
 21  \w     42.00 140.00   0.50    1.74    --  113.25 -85.00-122.00  196
 22  \w     41.00 111.00   0.50    1.74    --  113.25   0.00  60.00  140
 23  \w     44.00 111.00   0.50    1.74    --  113.25-125.00-120.00  134
 24  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00 120.00   74
 25  \w     97.00 178.00   0.50    1.74    --  113.25  61.00 -60.00  162
 26  \w     41.00 111.00   0.50    1.74    --  113.25   0.00  60.00  140
 27  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00 -30.00   74
 28  \w     44.00 111.00   0.50    1.74    --  113.25-125.00 -30.00  134
 29  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00   0.00   74
 30  \w    101.00 178.00   0.50    1.74    --  113.25  45.00  90.00  154
 31  \w    101.00 178.00   0.50    1.74    --  113.25  45.00  90.00  154
 32  \w     42.00 106.00   0.50    1.74    --  113.25 -94.00   0.00  128
 33  \w    101.00 178.00   0.50    1.74    --  113.25  45.00 -30.00  154
 34  \w    101.00 178.00   0.50    1.74    --  113.25  45.00 -30.00  154
 35  \w     42.00 136.00   0.50    1.74    --  113.25 -77.00-180.00  188
 36  \w     42.00  79.00   0.50    1.74    --  113.25 -61.00  30.00   74
 37  \w   -119.00 -25.00   0.50    0.43    --  -47.28 -77.00   0.00  188
 38  \w     25.00  52.00   0.50    0.43    --   47.28  77.00 120.00   54
;
_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      -0.0643381000
_diffrn_orient_matrix_UB_12      0.0419811000
_diffrn_orient_matrix_UB_13      -0.0020972000
_diffrn_orient_matrix_UB_21      -0.0253539000
_diffrn_orient_matrix_UB_22      -0.0796814000
_diffrn_orient_matrix_UB_23      -0.0334917000
_diffrn_orient_matrix_UB_31      -0.0142015000
_diffrn_orient_matrix_UB_32      -0.0479239000
_diffrn_orient_matrix_UB_33      0.0539541000
_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  0.0541
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            137249
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.763
_diffrn_reflns_theta_min         3.448
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.067
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66058
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange-blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.566
_exptl_crystal_description       block
_exptl_crystal_F_000             5716
_exptl_crystal_size_max          0.106
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.058
_refine_diff_density_max         2.446
_refine_diff_density_min         -2.797
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1126
_refine_ls_number_reflns         17176
_refine_ls_number_restraints     752
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0181P)^2^+86.7671P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0830
_refine_ls_wR_factor_ref         0.0848
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15797
_reflns_number_total             17176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06415e3.cif
_cod_data_source_block           matds35
_cod_depositor_comments
'Adding full bibliography for 1575982--1575985.cif.'
_cod_original_formula_sum        'C44 H104 Ce Mo2 N5 O36.50 W8'
_cod_database_code               1575984
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.293
_shelx_estimated_absorpt_t_min   0.155
_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
 N4-C25 = N4-C29 = N4-C33 = N4-C37 = N4A-C25A = N4A-C29A = N4A-C33A = N4A-C37A
 1.54 with sigma of 0.01
 C25-C26 = C26-C27 = C27-C28 = C29-C30 = C30-C31 = C31-C32 = C33-C34 = C34-C35
 = C35-C36 = C37-C38 = C38-C39 = C39-C40 = C25A-C26A = C26A-C27A = C27A-C28A =
 C29A-C30A = C30A-C31A = C31A-C32A = C33A-C34A = C34A-C35A = C35A-C36A = C37A-
 C38A = C38A-C39A = C39A-C40A
 1.52 with sigma of 0.02
 O13-C3 \\sim O13-C3A
 with sigma of 0.02
 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
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(C27) \\sim Ueq, Uanis(C27A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C32) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C21, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39,
  C40, N4A, C29A, C30A, C31A, C32A, C25A, C26A, C27A, C28A, C33A, C34A, C35A,
 C36A, C37A, C38A, C39A, C40A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C41, C42, O37, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C17, C18A, C19A, C20A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C17, C18, C19, C20}
{N4, C29, C30, C31, C32} 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
{N4, C37, C38, C39, C40} sigma for 1-2: 0.02, 1-3: 0.04
{N4A, C25A, C26A, C27A, C28A} 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
{N4A, C33A, C34A, C35A, C36A} 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}
{C21, C22A, C23A, C24A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C21, C22, C23, C24}
{C44, C43, O37, C42, C41} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C41, C42, O37, C43, C44}
6. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(1)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(1)
 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(2)
 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(2)
 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(3)
 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(3)
 Sof(N4A)=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(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(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)
 Fixed Sof: C41(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C42(0.5) H42A(0.5)
 H42B(0.5) O37(0.5) C43(0.5) H43A(0.5) H43B(0.5) C44(0.5) H44A(0.5) H44B(0.5)
 H44C(0.5)
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), C21(H21C,H21D), C22(H22A,
 H22B), C23(H23A,H23B), 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), C29A(H29C,H29D), C30A(H30C,H30D), C31A(H31C,H31D),
 C25A(H25C,H25D), C26A(H26C,H26D), C27A(H27C,H27D), C33A(H33C,H33D), C34A(H34C,
 H34D), C35A(H35C,H35D), C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,H39D),
 C42(H42A,H42B), C43(H43A,H43B)
7.b Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C3A(H3AA,H3AB,H3AC), C28(H28A,H28B,H28C), C32(H32A,H32B,
 H32C), C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C32A(H32D,H32E,H32F),
 C28A(H28D,H28E,H28F), C36A(H36D,H36E,H36F), C40A(H40D,H40E,H40F), C41(H41A,
 H41B,H41C), C44(H44A,H44B,H44C)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C16(H16A,H16B,
 H16C), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C24(H24A,H24B,H24C),
 C24A(H24D,H24E,H24F), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              81998
_olex2_submission_original_sample_id matds35
_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 1.491
_oxdiff_exptl_absorpt_empirical_full_min 0.764