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_1575985
_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, 3(C16 H36 N), C4 H10 O'
_chemical_formula_sum            'C60 H142 Ce Mo10 N5 O37'
_chemical_formula_weight         2625.30
_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                 108.1910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.92560(10)
_cell_length_b                   22.61610(10)
_cell_length_c                   18.27070(10)
_cell_measurement_reflns_used    110266
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      80.0360
_cell_measurement_theta_min      2.5180
_cell_volume                     9392.24(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 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 0.984
_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     44.00 111.00   0.50    0.77    --  113.25-125.00-120.00  134
  2  \w     44.00 111.00   0.50    0.77    --  113.25-125.00 -60.00  134
  3  \w     44.00 111.00   0.50    0.77    --  113.25-125.00 -30.00  134
  4  \w     42.00 106.00   0.50    0.77    --  113.25 -94.00   0.00  128
  5  \w     44.00 111.00   0.50    0.77    --  113.25-125.00 120.00  134
  6  \w     42.00 106.00   0.50    0.77    --  113.25 -94.00 120.00  128
  7  \w    -24.00  65.00   0.50    0.19    --   47.28 -64.00  88.00  178
  8  \w     42.00  79.00   0.50    0.77    --  113.25 -61.00 150.00   74
  9  \w     42.00  79.00   0.50    0.77    --  113.25 -61.00 120.00   74
 10  \w     42.00  84.00   0.50    0.77    --  113.25 -64.00  88.00   84
 11  \w     42.00  79.00   0.50    0.77    --  113.25 -61.00  60.00   74
 12  \w    -27.00  26.00   0.50    0.19    --   47.28 -19.00 -90.00  106
 13  \w     42.00  79.00   0.50    0.77    --  113.25 -61.00 -90.00   74
 14  \w     42.00  79.00   0.50    0.77    --  113.25 -61.00-120.00   74
 15  \w     41.00 111.00   0.50    0.77    --  113.25   0.00-150.00  140
 16  \w     91.00 178.00   0.50    0.77    --  113.25  77.00-180.00  174
 17  \w     96.00 178.00   0.50    0.77    --  113.25  64.00-135.00  164
 18  \w     97.00 178.00   0.50    0.77    --  113.25  61.00 -60.00  162
 19  \w     97.00 178.00   0.50    0.77    --  113.25  61.00 -60.00  162
 20  \w    101.00 167.00   0.50    0.77    --  113.25  45.00 -90.00  132
 21  \w    101.00 178.00   0.50    0.77    --  113.25  45.00 -30.00  154
 22  \w    101.00 178.00   0.50    0.77    --  113.25  30.00  30.00  154
 23  \w     97.00 178.00   0.50    0.77    --  113.25  61.00 150.00  162
 24  \w     32.00 120.00   0.50    0.19    --   47.28  57.00 150.00  176
 25  \w     32.00 120.00   0.50    0.19    --   47.28  57.00  60.00  176
 26  \w     25.00 120.00   0.50    0.19    --   47.28  77.00   0.00  190
 27  \w     32.00 120.00   0.50    0.19    --   47.28  57.00 -30.00  176
 28  \w     32.00 120.00   0.50    0.19    --   47.28  57.00 -90.00  176
 29  \w     30.00 120.00   0.50    0.19    --   47.28  64.00-135.00  180
 30  \w    -65.00  25.00   0.50    0.19    --  -47.28  64.00-135.00  180
 31  \w    -65.00  25.00   0.50    0.19    --  -47.28  64.00-135.00  180
 32  \w    -72.00 -19.00   0.50    0.77    --  -91.75  64.00-135.00  106
 33  \w    -14.00  28.00   0.50    0.19    --  -47.28  19.00  30.00   84
 34  \w    -67.00 -19.00   0.50    0.77    --  -91.75  61.00  60.00   96
 35  \w    -86.00 -13.00   0.50    0.19    --  -47.28 125.00 -30.00  146
 36  \w   -119.00 -30.00   0.50    0.19    --  -47.28 -64.00  88.00  178
 37  \w   -163.00 -74.00   0.50    0.77    --  -91.75 -64.00  88.00  178
;
_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      0.0494870000
_diffrn_orient_matrix_UB_12      0.0464971000
_diffrn_orient_matrix_UB_13      0.0228197000
_diffrn_orient_matrix_UB_21      0.0214158000
_diffrn_orient_matrix_UB_22      -0.0202599000
_diffrn_orient_matrix_UB_23      -0.0672240000
_diffrn_orient_matrix_UB_31      -0.0410463000
_diffrn_orient_matrix_UB_32      0.0454554000
_diffrn_orient_matrix_UB_33      -0.0533106000
_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  0.0475
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            162835
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.624
_diffrn_reflns_theta_min         2.756
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.876
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33105
_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    1.857
_exptl_crystal_description       block
_exptl_crystal_F_000             5244
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.795
_refine_diff_density_min         -0.880
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1112
_refine_ls_number_reflns         20285
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0274
_refine_ls_R_factor_gt           0.0263
_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^)+(0.0283P)^2^+21.5961P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0660
_refine_ls_wR_factor_ref         0.0667
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19589
_reflns_number_total             20285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06415e3.cif
_cod_data_source_block           matds37
_cod_depositor_comments
'Adding full bibliography for 1575982--1575985.cif.'
_cod_original_cell_volume        9392.23(9)
_cod_database_code               1575985
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.406
_shelx_estimated_absorpt_t_min   0.158
_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. 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
3. Same fragment restrains
{C57, C58, O37, C59, C60} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C57A, C58A, O37A, C59A, C60A}
{C60, C59, O37, C58, C57} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C57, C58, O37, C59, C60}
{C53, C54A, C55A, C56A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C53, C54, C55, C56}
4. Others
 Sof(H53C)=Sof(H53D)=Sof(C57A)=Sof(H57D)=Sof(H57E)=Sof(H57F)=Sof(C58A)=
 Sof(H58C)=Sof(H58D)=Sof(O37A)=Sof(C59A)=Sof(H59C)=Sof(H59D)=Sof(C60A)=
 Sof(H60D)=Sof(H60E)=Sof(H60F)=Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C55A)=
 Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(1)
 Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(O37)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=
 Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
5.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), 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),
  C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C45(H45A,H45B), C46(H46A,
 H46B), C47(H47A,H47B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B),
 C53(H53A,H53B), C53(H53C,H53D), C54(H54A,H54B), C55(H55A,H55B), C58(H58A,H58B),
  C59(H59A,H59B), C58A(H58C,H58D), C59A(H59C,H59D), C54A(H54C,H54D), C55A(H55C,
 H55D)
5.b Me refined with riding coordinates:
 C57(H57A,H57B,H57C), C60(H60A,H60B,H60C), C57A(H57D,H57E,H57F), C60A(H60D,
 H60E,H60F)
5.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), 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), C48(H48A,H48B,H48C), C52(H52A,H52B,H52C), C56(H56A,H56B,
 H56C), C56A(H56D,H56E,H56F)
;
_shelx_res_checksum              28474
_olex2_submission_original_sample_id matds37
_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 2.524
_oxdiff_exptl_absorpt_empirical_full_min 0.725