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_1575983
_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, 3(C16 H36 N), 3(C H4 O)'
_chemical_formula_sum            'C59 H144 Ce Mo2 N5 O39 W8'
_chemical_formula_weight         3350.58
_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   mixed
_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                77.0060(6)
_cell_angle_beta                 89.2214(5)
_cell_angle_gamma                75.4995(5)
_cell_formula_units_Z            2
_cell_length_a                   13.11989(7)
_cell_length_b                   14.37437(10)
_cell_length_c                   25.9380(2)
_cell_measurement_reflns_used    100625
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.9810
_cell_measurement_theta_min      3.2630
_cell_volume                     4609.83(6)
_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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.981
_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    -35.00  26.00   0.50    0.14    --  -47.28  38.00 -37.00  122
  2  \w   -120.00 -35.00   0.50    0.14    --  -47.28 -38.00 166.00  170
  3  \w     35.00 120.00   0.50    0.14    --   47.28  38.00 -37.00  170
  4  \w     35.00 120.00   0.50    0.14    --   47.28  38.00 -37.00  170
  5  \w    101.00 178.00   0.50    0.55    --  113.25  38.00 -37.00  154
  6  \w    101.00 178.00   0.50    0.55    --  113.25  38.00 -37.00  154
  7  \w    -14.00  28.00   0.50    0.14    --  -47.28  19.00 -30.00   84
  8  \w   -119.00 -25.00   0.50    0.14    --  -47.28 -77.00   0.00  188
  9  \w    -14.00  28.00   0.50    0.14    --  -47.28  19.00-120.00   84
 10  \w    -86.00 -13.00   0.50    0.14    --  -47.28 125.00-180.00  146
 11  \w     34.00  93.00   0.50    0.14    --   47.28-125.00  30.00  118
 12  \w    -26.00  47.00   0.50    0.14    --   47.28 -38.00 166.00  146
 13  \w    -27.00  26.00   0.50    0.14    --   47.28 -19.00-150.00  106
 14  \w     34.00  93.00   0.50    0.14    --   47.28-125.00-150.00  118
 15  \w    -85.00 -22.00   0.50    0.55    --  -91.75 125.00  30.00  126
 16  \w    -67.00 -19.00   0.50    0.55    --  -91.75  61.00 150.00   96
 17  \w    -69.00 -20.00   0.50    0.55    --  -91.75   0.00-180.00   98
 18  \w   -165.00 -78.00   0.50    0.55    --  -91.75 -38.00 166.00  174
 19  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00-120.00  128
 20  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00  60.00   74
 21  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00-180.00   74
 22  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00-120.00   74
 23  \w    101.00 178.00   0.50    0.55    --  113.25  45.00-150.00  154
 24  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00  60.00  128
 25  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00  90.00   74
 26  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00 120.00  128
 27  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00  30.00   74
 28  \w     41.00 111.00   0.50    0.55    --  113.25   0.00-120.00  140
 29  \w     41.00 111.00   0.50    0.55    --  113.25   0.00-120.00  140
 30  \w     44.00 111.00   0.50    0.55    --  113.25-125.00 -30.00  134
 31  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00  30.00  128
 32  \w    101.00 178.00   0.50    0.55    --  113.25  30.00 -90.00  154
 33  \w    101.00 178.00   0.50    0.55    --  113.25  30.00-150.00  154
 34  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00   0.00  128
 35  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00 -60.00   74
 36  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00 -30.00   74
 37  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00-150.00  128
 38  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00 -60.00  128
 39  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00 120.00   74
 40  \w     44.00 111.00   0.50    0.55    --  113.25-125.00-150.00  134
 41  \w     97.00 178.00   0.50    0.55    --  113.25  61.00 120.00  162
 42  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00  90.00  128
 43  \w    101.00 178.00   0.50    0.55    --  113.25  45.00   0.00  154
 44  \w     42.00  79.00   0.50    0.55    --  113.25 -61.00   0.00   74
 45  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00-180.00  128
 46  \w     97.00 178.00   0.50    0.55    --  113.25  61.00-120.00  162
 47  \w    101.00 178.00   0.50    0.55    --  113.25  30.00  90.00  154
 48  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00 150.00  128
 49  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00-120.00  128
 50  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00 -30.00  128
 51  \w    101.00 178.00   0.50    0.55    --  113.25  45.00  30.00  154
 52  \w    101.00 178.00   0.50    0.55    --  113.25  45.00-150.00  154
 53  \w    100.00 178.00   0.50    0.55    --  113.25  15.00  60.00  156
 54  \w     42.00 106.00   0.50    0.55    --  113.25 -94.00 -90.00  128
 55  \w   -119.00 -25.00   0.50    0.14    --  -47.28 -77.00 120.00  188
 56  \w   -119.00 -25.00   0.50    0.14    --  -47.28 -77.00 -90.00  188
 57  \w   -119.00 -25.00   0.50    0.14    --  -47.28 -77.00-150.00  188
 58  \w   -119.00 -25.00   0.50    0.14    --  -47.28 -77.00 -30.00  188
 59  \w   -119.00 -32.00   0.50    0.14    --  -47.28 -57.00 150.00  174
 60  \w   -119.00 -32.00   0.50    0.14    --  -47.28 -57.00  30.00  174
 61  \w     25.00 120.00   0.50    0.14    --   47.28  77.00  90.00  190
 62  \w     25.00 120.00   0.50    0.14    --   47.28  77.00-150.00  190
 63  \w     25.00 120.00   0.50    0.14    --   47.28  77.00  30.00  190
 64  \w     34.00  93.00   0.50    0.14    --   47.28-125.00 120.00  118
 65  \w     35.00 120.00   0.50    0.14    --   47.28  38.00-180.00  170
 66  \w   -163.00 -69.00   0.50    0.55    --  -91.75 -77.00 -90.00  188
 67  \w   -163.00 -70.00   0.50    0.55    --  -91.75 -75.00 -37.30  186
 68  \w   -163.00 -69.00   0.50    0.55    --  -91.75 -77.00  60.00  188
 69  \w   -163.00 -70.00   0.50    0.55    --  -91.75 -74.00 137.84  186
 70  \w   -163.00 -69.00   0.50    0.55    --  -91.75 -77.00  11.99  188
;
_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      -0.1139046000
_diffrn_orient_matrix_UB_12      -0.0047403000
_diffrn_orient_matrix_UB_13      0.0126592000
_diffrn_orient_matrix_UB_21      0.0397705000
_diffrn_orient_matrix_UB_22      -0.1105930000
_diffrn_orient_matrix_UB_23      0.0264124000
_diffrn_orient_matrix_UB_31      0.0135800000
_diffrn_orient_matrix_UB_32      0.0260386000
_diffrn_orient_matrix_UB_33      0.0535280000
_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  0.0439
_diffrn_reflns_av_unetI/netI     0.0214
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            153233
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.330
_diffrn_reflns_theta_min         3.262
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    24.444
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29542
_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            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.414
_exptl_crystal_description       block
_exptl_crystal_F_000             3158
_exptl_crystal_size_max          0.137
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.027
_refine_diff_density_max         1.665
_refine_diff_density_min         -1.759
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1211
_refine_ls_number_reflns         19810
_refine_ls_number_restraints     360
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0298
_refine_ls_R_factor_gt           0.0287
_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^)+(0.0166P)^2^+29.5327P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0627
_refine_ls_wR_factor_ref         0.0632
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19202
_reflns_number_total             19810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06415e3.cif
_cod_data_source_block           matds33
_cod_depositor_comments
'Adding full bibliography for 1575982--1575985.cif.'
_cod_original_cell_volume        4609.84(6)
_cod_database_code               1575983
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.558
_shelx_estimated_absorpt_t_min   0.135
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O11-C1 \\sim O11-C1A \\sim O24-C6 \\sim O24-C6A
 with sigma of 0.02
 O39-C59 \\sim O39A-C59A \\sim O38-C58
 with sigma of 0.02
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(C1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C59A) \\sim Ueq:
with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 N5, C49, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N5A, C49A, C50A, C51A, C52A, C53A, C54A, C55A, C56A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Same fragment restrains
{N5, C53, C54, C55, C56} sigma for 1-2: 0.02, 1-3: 0.04
{N5, C49A, C50A, C51A, C52A} sigma for 1-2: 0.02, 1-3: 0.04
{N5, C53A, C54A, C55A, C56A} sigma for 1-2: 0.02, 1-3: 0.04
{N5, C45A, C46A, C47A, C48A} sigma for 1-2: 0.02, 1-3: 0.04
{N5, C41, C42, C43, C44} sigma for 1-2: 0.02, 1-3: 0.04
{N5, C49, C50, C51, C52} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N5, C45, C46, C47, C48}
6. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(2)
 Sof(H38C)=Sof(O39A)=Sof(H39C)=Sof(C59A)=Sof(H59D)=Sof(H59E)=Sof(H59F)=1-FVAR(3)
 Sof(H38)=Sof(O39)=Sof(H39)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(3)
 Fixed Sof: N5(0.5) C45(0.5) H45A(0.5) H45B(0.5) C46(0.5) H46A(0.5) H46B(0.5)
 C47(0.5) H47A(0.5) H47B(0.5) C48(0.5) H48A(0.5) H48B(0.5) H48C(0.5) H41C(0.5)
 H41D(0.5) H41A(0.5) H41B(0.5) C49(0.5) H49A(0.5) H49B(0.5) C50(0.5) H50A(0.5)
 H50B(0.5) C51(0.5) H51A(0.5) H51B(0.5) C52(0.5) H52A(0.5) H52B(0.5) H52C(0.5)
 C53(0.5) H53A(0.5) H53B(0.5) C54(0.5) H54A(0.5) H54B(0.5) C55(0.5) H55A(0.5)
 H55B(0.5) C56(0.5) H56A(0.5) H56B(0.5) H56C(0.5) N5A(0.5) C45A(0.5) H45C(0.5)
 H45D(0.5) C46A(0.5) H46C(0.5) H46D(0.5) C47A(0.5) H47C(0.5) H47D(0.5)
 C48A(0.5) H48D(0.5) H48E(0.5) H48F(0.5) C49A(0.5) H49C(0.5) H49D(0.5)
 C50A(0.5) H50C(0.5) H50D(0.5) C51A(0.5) H51C(0.5) H51D(0.5) C52A(0.5)
 H52D(0.5) H52E(0.5) H52F(0.5) C53A(0.5) H53C(0.5) H53D(0.5) C54A(0.5)
 H54C(0.5) H54D(0.5) C55A(0.5) H55C(0.5) H55D(0.5) C56A(0.5) H56D(0.5)
 H56E(0.5) H56F(0.5)
7.a Riding coordinates:
 O38(H38,H38C), O39(H39)
7.b 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), C23(H23A,H23B), 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),
  C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C41(H41C,H41D), C41(H41A,
 H41B), C42(H42A,H42B), C43(H43A,H43B), C49(H49A,H49B), C50(H50A,H50B),
 C51(H51A,H51B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C45A(H45C,
 H45D), C46A(H46C,H46D), C47A(H47C,H47D), C49A(H49C,H49D), C50A(H50C,H50D),
 C51A(H51C,H51D), C53A(H53C,H53D), C54A(H54C,H54D), C55A(H55C,H55D)
7.c Me refined with riding coordinates:
 C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C56(H56A,H56B,H56C), C48A(H48D,H48E,
 H48F), C52A(H52D,H52E,H52F), C56A(H56D,H56E,H56F)
7.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C1A(H1AA,H1AB,
 H1AC), C6A(H6AA,H6AB,H6AC), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C20(H20A,
 H20B,H20C), C24(H24A,H24B,H24C), C28(H28A,H28B,H28C), C32(H32A,H32B,H32C),
 C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C44(H44A,H44B,H44C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C59A(H59D,H59E,H59F)
7.e Idealised tetrahedral OH refined as rotating group:
 O39A(H39C)
;
_shelx_res_checksum              2586
_olex2_submission_original_sample_id matds33
_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 2.469
_oxdiff_exptl_absorpt_empirical_full_min 0.663