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_1575982
_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 Mo10 N2 O36, 2(C16 H36 N), C2 H3 N, 0.5(C4 H10 O)'
_chemical_formula_sum            'C44 H104 Ce Mo10 N5 O36.5'
_chemical_formula_weight         2386.84
_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             2025-05-15
_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                 92.8717(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.78196(10)
_cell_length_b                   15.03091(7)
_cell_length_c                   24.10430(13)
_cell_measurement_reflns_used    70182
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      80.0230
_cell_measurement_theta_min      3.0280
_cell_volume                     7881.90(7)
_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      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 0.986
_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    -55.00  25.00   0.50    0.43    --  -47.28  59.00 172.00  160
  2  \w   -119.00 -32.00   0.50    0.43    --  -47.28 -59.00  32.00  174
  3  \w    -24.00  63.00   0.50    0.43    --   47.28 -59.00  32.00  174
  4  \w     32.00 120.00   0.50    0.43    --   47.28  59.00 172.00  176
  5  \w   -163.00 -76.00   0.50    1.73    --  -91.75 -59.00  32.00  174
  6  \w    -55.00 -19.00   0.50    1.73    --  -91.75  59.00 172.00   72
  7  \w     98.00 178.00   0.50    1.73    --  113.25  59.00 172.00  160
  8  \w     42.00  81.00   0.50    1.73    --  113.25 -59.00  32.00   78
  9  \w    -13.00  28.00   0.50    0.43    --  -47.28  19.00 -60.00   82
 10  \w    -13.00  28.00   0.50    0.43    --  -47.28  19.00 -30.00   82
 11  \w     34.00  93.00   0.50    0.43    --   47.28-125.00-150.00  118
 12  \w    -58.00 -19.00   0.50    1.73    --  -91.75  61.00 -60.00   78
 13  \w    -58.00 -19.00   0.50    1.73    --  -91.75  61.00   0.00   78
 14  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00-150.00   84
 15  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00  60.00   84
 16  \w     42.00 118.00   0.50    1.73    --  113.25 -77.00 120.00  152
 17  \w    100.00 178.00   0.50    1.73    --  113.25  15.00 -30.00  156
 18  \w     44.00 111.00   0.50    1.73    --  113.25-125.00  60.00  134
 19  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00 -90.00   84
 20  \w     42.00 106.00   0.50    1.73    --  113.25 -94.00  90.00  128
 21  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00   0.00   84
 22  \w    101.00 178.00   0.50    1.73    --  113.25  45.00  60.00  154
 23  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00 120.00   84
 24  \w     97.00 178.00   0.50    1.73    --  113.25  61.00 120.00  162
 25  \w    101.00 178.00   0.50    1.73    --  113.25  45.00  60.00  154
 26  \w     42.00  84.00   0.50    1.73    --  113.25 -61.00-180.00   84
 27  \w    101.00 178.00   0.50    1.73    --  113.25  30.00-120.00  154
 28  \w     42.00 118.00   0.50    1.73    --  113.25 -77.00-180.00  152
 29  \w     42.00 118.00   0.50    1.73    --  113.25 -77.00-180.00  152
 30  \w     42.00 106.00   0.50    1.73    --  113.25 -94.00 -90.00  128
 31  \w    101.00 178.00   0.50    1.73    --  113.25  30.00 -90.00  154
 32  \w    -13.00  28.00   0.50    0.43    --  -47.28  19.00  60.00   82
 33  \w     32.00 120.00   0.50    0.43    --   47.28  57.00   0.00  176
 34  \w     25.00 120.00   0.50    0.43    --   47.28  77.00  90.00  190
 35  \w     25.00 120.00   0.50    0.43    --   47.28  77.00  30.00  190
 36  \w     25.00 120.00   0.50    0.43    --   47.28  77.00 -90.00  190
 37  \w     25.00 120.00   0.50    0.43    --   47.28  77.00-150.00  190
 38  \w    101.00 178.00   0.50    1.73    --  113.25  45.00  90.00  154
 39  \w    101.00 178.00   0.50    1.73    --  113.25  45.00   0.00  154
;
_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      0.0013322000
_diffrn_orient_matrix_UB_12      0.0152147000
_diffrn_orient_matrix_UB_13      0.0632565000
_diffrn_orient_matrix_UB_21      0.0516507000
_diffrn_orient_matrix_UB_22      -0.0695008000
_diffrn_orient_matrix_UB_23      0.0079637000
_diffrn_orient_matrix_UB_31      0.0484127000
_diffrn_orient_matrix_UB_32      0.0737956000
_diffrn_orient_matrix_UB_33      -0.0055204000
_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  0.0463
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            134413
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.125
_diffrn_reflns_theta_min         3.467
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.645
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12773
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.011
_exptl_crystal_description       needle
_exptl_crystal_F_000             4692
_exptl_crystal_size_max          0.212
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.579
_refine_diff_density_min         -2.231
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.112
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1131
_refine_ls_number_reflns         16997
_refine_ls_number_restraints     740
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0503
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0290P)^2^+62.0663P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1102
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16179
_reflns_number_total             16997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06415e3.cif
_cod_data_source_block           matng01
_cod_depositor_comments
'Adding full bibliography for 1575982--1575985.cif.'
_cod_original_formula_sum        'C44 H104 Ce Mo10 N5 O36.50'
_cod_database_code               1575982
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.371
_shelx_estimated_absorpt_t_min   0.118
_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
 = 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 \\sim O25-C7 \\sim O25-C7A
 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(C34) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C43) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 N4, C25, C26, C27, C28, C29, C30, C31, C32, N4A, C37A, C38A, C39A, C40A, C33,
 C34, C35, C36, C37, C38, C39, C40, C25A, C26A, C27A, C28A, C29A, C30A, C31A,
 C32A, C33A, C34A, C35A, C36A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C43, C44, O37, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C13, C14A, C15A, C16A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C13, C14, C15, C16}
{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
{N4A, C37A, C38A, C39A, C40A} 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, 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, C25A, C26A, C27A, C28A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N4, C25, C26, C27, C28}
{C22, C23A, C24A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C22, C23, C24}
{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(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=
 Sof(H15D)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=1-FVAR(2)
 Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 Sof(H24C)=FVAR(2)
 Sof(N4A)=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)=
 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(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(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)=1-FVAR(3)
 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(3)
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=1-FVAR(4)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(4)
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-FVAR(5)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(5)
 Fixed Sof: C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5) C44(0.5) H44A(0.5)
 H44B(0.5) O37(0.5) C45(0.5) H45A(0.5) H45B(0.5) C46(0.5) H46A(0.5) H46B(0.5)
 H46C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C13(H13C,H13D),
 C14(H14A,H14B), C15(H15A,H15B), C14A(H14C,H14D), C15A(H15C,H15D), C17(H17A,
 H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B), C22(H22A,H22B),
 C22(H22C,H22D), C23(H23A,H23B), C23A(H23C,H23D), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
 C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,H39D), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B),
 C25A(H25C,H25D), C26A(H26C,H26D), C27A(H27C,H27D), C29A(H29C,H29D), C30A(H30C,
 H30D), C31A(H31C,H31D), C33A(H33C,H33D), C34A(H34C,H34D), C35A(H35C,H35D),
 C44(H44A,H44B), C45(H45A,H45B)
7.b Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C32(H32A,H32B,H32C), C40A(H40D,H40E,H40F), C36(H36A,H36B,
 H36C), C40(H40A,H40B,H40C), C28A(H28D,H28E,H28F), C32A(H32D,H32E,H32F),
 C36A(H36D,H36E,H36F), C43(H43A,H43B,H43C)
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), C12(H12A,H12B,
 H12C), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C20(H20A,H20B,H20C),
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C42(H42A,H42B,H42C), C46(H46A,H46B,
 H46C), C3A(H3AA,H3AB,H3AC), C7A(H7AA,H7AB,H7AC)
;
_shelx_res_checksum              69812
_olex2_submission_original_sample_id matng01
_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 4.840
_oxdiff_exptl_absorpt_empirical_full_min 0.627