Siloxide tripodal ligands as a scaffold for stabilizing lanthanides in the +4 oxidation state.
Tricoire, Maxime; Hsueh, Fang-Che; Keener, Megan; Rajeshkumar, Thayalan; Scopelliti, Rosario; Zivkovic, Ivica; Maron, Laurent; Mazzanti, Marinella; Chemical science 15 (2024) 6874–6883; doi:10.1039/d4sc00051j

data_1571349
_publ_section_title
;
 Siloxide tripodal ligands as a scaffold for stabilizing lanthanides in
 the +4 oxidation state.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              6874
_journal_page_last               6883
_journal_paper_doi               10.1039/d4sc00051j
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C66 H84 Ce O10 Si4, 0.5(C20 H40 K O5), 0.5(C24 H48 K0.949 O6), 2.7[C4H8O]'
_chemical_formula_sum            'C88 H128 Ce K O15.5 Si4'
_chemical_formula_weight         1725.48
_space_group_crystal_system      hexagonal
_space_group_IT_number           182
_space_group_name_Hall           'P 6c 2c'
_space_group_name_H-M_alt        'P 63 2 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-09-22 deposited with the CCDC.	2024-03-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            4
_cell_length_a                   14.87393(16)
_cell_length_b                   14.87393(16)
_cell_length_c                   55.4259(7)
_cell_measurement_reflns_used    35991
_cell_measurement_temperature    200.00(11)
_cell_measurement_theta_max      72.3610
_cell_measurement_theta_min      3.1220
_cell_volume                     10619.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -68.00 -15.00   1.00    1.50    --  -43.01 113.00  27.00   53
  2  \w    -90.00  32.00   1.00    1.50    --  -43.01  17.00 -77.00  122
  3  \w    117.00 162.00   1.00    6.00    --  103.49  17.00 -77.00   45
  4  \w     62.00  87.00   1.00    6.00    --  103.49 -17.00 113.00   25
  5  \w    132.00 158.00   1.00    6.00    --  103.49 110.00  90.00   26
  6  \w     77.00 139.00   1.00    6.00    --  103.49 157.00 159.00   62
  7  \w    139.00 165.00   1.00    6.00    --  103.49 113.00  27.00   26
  8  \w     97.00 174.00   1.00    6.00    --  103.49 128.00 -21.00   77
  9  \w     69.00  94.00   1.00    6.00    --  103.49-113.00 -64.00   25
 10  \w    109.00 134.00   1.00    6.00    --  103.49 138.00 -46.00   25
 11  \w     71.00  97.00   1.00    6.00    --  103.49  17.00 -77.00   26
 12  \w    -42.00 -15.00   1.00    1.50    --  -43.01 -57.00   0.00   27
 13  \w    -44.00 -19.00   1.00    1.50    --  -43.01 -57.00 -60.00   25
 14  \w    -51.00 -26.00   1.00    1.50    --  -43.01 -57.00 -30.00   25
 15  \w     20.00  53.00   1.00    1.50    --   43.01  37.00   0.00   33
 16  \w     10.00  37.00   1.00    1.50    --   43.01  79.00  64.13   27
 17  \w     73.00  98.00   1.00    6.00    --  103.49  70.00  36.09   25
 18  \w     73.00  99.00   1.00    6.00    --  103.49  67.00  26.14   26
 19  \w     74.00 100.00   1.00    6.00    --  103.49  61.00  30.00   26
 20  \w     75.00 102.00   1.00    6.00    --  103.49  61.00  60.00   27
 21  \w     78.00 173.00   1.00    6.00    --  103.49  59.00  39.75   95
 22  \w     74.00 100.00   1.00    6.00    --  103.49  61.00   0.00   26
 23  \w     76.00 102.00   1.00    6.00    --  103.49  57.00  11.27   26
 24  \w     78.00 105.00   1.00    6.00    --  103.49  45.00   0.00   27
 25  \w     76.00 116.00   1.00    6.00    --  103.49  56.00  30.03   40
 26  \w     74.00 100.00   1.00    6.00    --  103.49  64.00  50.68   26
 27  \w     75.00 100.00   1.00    6.00    --  103.49  60.00 -10.06   25
 28  \w     77.00 121.00   1.00    6.00    --  103.49  60.00  12.54   44
 29  \w     80.00 107.00   1.00    6.00    --  103.49  47.00  10.13   27
 30  \w     73.00 100.00   1.00    6.00    --  103.49  69.00   5.70   27
 31  \w     77.00 159.00   1.00    6.00    --  103.49  61.00 -30.00   82
 32  \w     74.00  99.00   1.00    6.00    --  103.49  67.00  43.52   25
 33  \w     71.00 104.00   1.00    6.00    --  103.49-110.00  -4.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0257956000
_diffrn_orient_matrix_UB_12      -0.1115223000
_diffrn_orient_matrix_UB_13      0.0060002000
_diffrn_orient_matrix_UB_21      0.1167132000
_diffrn_orient_matrix_UB_22      0.0372398000
_diffrn_orient_matrix_UB_23      0.0021059000
_diffrn_orient_matrix_UB_31      -0.0032308000
_diffrn_orient_matrix_UB_32      0.0217965000
_diffrn_orient_matrix_UB_33      0.0270734000
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       68
_diffrn_reflns_limit_l_min       -62
_diffrn_reflns_number            86994
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.678
_diffrn_reflns_theta_min         3.189
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.508
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.218
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.079
_exptl_crystal_description       prism
_exptl_crystal_F_000             3652
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.277
_exptl_crystal_size_min          0.229
_refine_diff_density_max         0.909
_refine_diff_density_min         -0.600
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.071(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     400
_refine_ls_number_reflns         7038
_refine_ls_number_restraints     551
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0581
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0731P)^2^+17.4658P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1554
_refine_ls_wR_factor_ref         0.1561
_reflns_Friedel_coverage         0.669
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                6906
_reflns_number_total             7038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           ah543
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_cell_volume        10619.3(3)
_cod_original_formula_sum        'C88 H128 Ce K O15.50 Si4'
_cod_database_code               1571349
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C88 H128 O15.5 Si4 K1 Ce1'
_shelx_estimated_absorpt_t_max   0.425
_shelx_estimated_absorpt_t_min   0.259
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.929(10)
 0.071(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O6-C33 = O6-C30
 1.44 with sigma of 0.02
 C32-C31
 1.54 with sigma of 0.02
 C33-C32 = C31-C30
 1.53 with sigma of 0.02
 C26-C27 = C28-C29
 1.53 with sigma of 0.02
 O5-C26 = O5-C29
 1.44 with sigma of 0.02
 C27-C28
 1.54 with sigma of 0.02
 O6-C32 = O6-C31 = C33-C31 = C32-C30
 2.38 with sigma of 0.04
 O5-C27 = O5-C28 = C26-C28 = C27-C29
 2.38 with sigma of 0.04
 C15-C9 \\sim C12-C9 \\sim C11-C9 \\sim C14-C9 \\sim C10-C9 \\sim C13-C9
 with sigma of 0.02
 C14-C15 \\sim C15-C13
 with sigma of 0.02
 C10-C11 \\sim C11-C12
 with sigma of 0.02
 C32-C30 \\sim C33-C31
 with sigma of 0.04
 O6-C32 \\sim O6-C31
 with sigma of 0.04
 O6-C33 \\sim O6-C30
 with sigma of 0.02
 C33-C32 \\sim C32-C31 \\sim C31-C30
 with sigma of 0.02
 C26-C27 \\sim C27-C28 \\sim C28-C29
 with sigma of 0.02
 O5-C26 \\sim O5-C29
 with sigma of 0.02
 O5-C27 \\sim O5-C28
 with sigma of 0.04
 C27-C29 \\sim C26-C28
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O6 \\sim C30 \\sim C31 \\sim C32 \\sim C33: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O5 \\sim C26 \\sim C27 \\sim C28 \\sim C29: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 O6, C30, C31, C32, C33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C26, C27, C28, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=1-FVAR(1)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Fixed Sof: O5(0.5) O6(0.333333) C26(0.5) H26A(0.5) H26B(0.5) C27(0.5)
 H27A(0.5) H27B(0.5) C28(0.5) H28A(0.5) H28B(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 C30(0.333333) H30A(0.333333) H30B(0.333333) C31(0.333333) H31A(0.333333)
 H31B(0.333333) C32(0.333333) H32A(0.333333) H32B(0.333333) C33(0.333333)
 H33A(0.333333) H33B(0.333333)
7.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,
 H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B),
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6), C7(H7), C21(H21), C22(H22), C23(H23),
 C24(H24), C25(H25)
7.c Fitted pentagon refined as free rotating group:
 O7(C34,C35,C36,C37)
7.d Fitted hexagon refined as free rotating group:
 C20(C21,C22,C23,C24,C25)
7.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 410 electrons were 
found in a volume of 1878\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2.7[C4H8O] per Asymmetric Unit 
which account for 432 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              35582
_shelx_fab_checksum              67154
_olex2_date_sample_data_collection 2023-01-25
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.464
_oxdiff_exptl_absorpt_empirical_full_min 0.767