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_1571350
_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_absolute_configuration rmad
_chemical_formula_moiety         'C86 H76 Ce O6 Si4, 2(C4 H8 O), 2[C4H8O]'
_chemical_formula_sum            'C102 H108 Ce O10 Si4'
_chemical_formula_weight         1746.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-31
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 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                90
_cell_formula_units_Z            4
_cell_length_a                   15.94855(11)
_cell_length_b                   22.45159(16)
_cell_length_c                   25.03370(19)
_cell_measurement_reflns_used    23610
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.4160
_cell_measurement_theta_min      4.3020
_cell_volume                     8963.82(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_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      8.00  64.00   1.00    5.00    --   40.66-101.00 169.00   56
  2  \w    122.00 177.00   1.00   20.00    --  105.15  30.00  79.00   55
  3  \w    104.00 170.00   1.00   20.00    --  105.15 101.00 -86.00   66
  4  \w     43.00 108.00   1.00   20.00    --  105.15-106.00  77.00   65
  5  \w     77.00 110.00   1.00   20.00    --  105.15  30.00  79.00   33
  6  \w   -112.00 -13.00   1.00    5.00    --  -40.66 -57.00   0.00   99
  7  \w    -68.00 -36.00   1.00    5.00    --  -40.66 125.00  30.00   32
  8  \w    -34.00   3.00   1.00    5.00    --   40.66 -30.00 -81.00   37
  9  \w     61.00 142.00   1.00   20.00    --  105.15 178.00 -90.00   81
 10  \w    144.00 178.00   1.00   20.00    --  105.15 111.00  90.00   34
 11  \w    107.00 132.00   1.00   20.00    --  105.15 111.00  90.00   25
 12  \w     75.00 140.00   1.00   20.00    --  105.15 178.00-150.00   65
 13  \w    103.00 177.00   1.00   20.00    --  105.15  77.00-150.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0376245000
_diffrn_orient_matrix_UB_12      -0.0488259000
_diffrn_orient_matrix_UB_13      0.0359978000
_diffrn_orient_matrix_UB_21      0.0004580000
_diffrn_orient_matrix_UB_22      -0.0436495000
_diffrn_orient_matrix_UB_23      -0.0474804000
_diffrn_orient_matrix_UB_31      0.0889264000
_diffrn_orient_matrix_UB_32      -0.0204880000
_diffrn_orient_matrix_UB_33      0.0154655000
_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  0.0272
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            39009
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.628
_diffrn_reflns_theta_min         3.286
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.902
_exptl_absorpt_correction_T_max  0.729
_exptl_absorpt_correction_T_min  0.368
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3656
_exptl_crystal_size_max          0.306
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.592
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Flack x determined using 7128 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0133(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1035
_refine_ls_number_reflns         17348
_refine_ls_number_restraints     534
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0431
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0651P)^2^+7.4734P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1073
_refine_ls_wR_factor_ref         0.1097
_reflns_Friedel_coverage         0.821
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                16665
_reflns_number_total             17348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           ah588
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_database_code               1571350
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C94 H92 O8 Si4 Ce1'
_shelx_estimated_absorpt_t_max   0.722
_shelx_estimated_absorpt_t_min   0.315
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 O8-C107 = O8-C104 = O7-C100 = O7-C103
 1.43 with sigma of 0.02
 C101-C100 = C102-C101 = C103-C102 = C105-C104 = C106-C105 = C107-C106
 1.54 with sigma of 0.02
 Si4-C92 \\sim Si4-C67
 with sigma of 0.02
 Si1-C93 \\sim Si1-C13
 with sigma of 0.02
 C99-C86 \\sim C86-C85 \\sim C99-C84 \\sim C85-C84
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C93 \\sim C94 \\sim
C95 \\sim C96 \\sim C97 \\sim C98: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C87 \\sim C88 \\sim
C89 \\sim C90 \\sim C91 \\sim C92: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C84 \\sim C85 \\sim C86 \\sim C99: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
Uanis(O7) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C101)
\\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq,
Uanis(C106) \\sim Ueq, Uanis(C107) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O8) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 O8, C104, C105, C106, C107
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C49, C54, C53, C52, C51, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(H17)=Sof(C18)=Sof(H18)=Sof(C92)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=
 Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91)=1-FVAR(1)
 Sof(C67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C71)=
 Sof(H71)=Sof(C72)=Sof(H72)=Sof(C93)=Sof(C94)=Sof(H94)=Sof(C95)=Sof(H95)=
 Sof(C96)=Sof(H96)=Sof(C97)=Sof(H97)=Sof(C98)=Sof(H98)=FVAR(1)
 Sof(H84C)=Sof(H84D)=Sof(H86C)=Sof(H86D)=Sof(C99)=Sof(H99A)=Sof(H99B)=1-FVAR(2)
 Sof(H84A)=Sof(H84B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H86A)=Sof(H86B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,
 H83B), C84(H84A,H84B), C84(H84C,H84D), C85(H85A,H85B), C86(H86A,H86B),
 C86(H86C,H86D), C99(H99A,H99B), C100(H10A,H10B), C101(H10C,H10D), C102(H10E,
 H10F), C103(H10G,H10H), C104(H10I,H10J), C105(H10K,H10L), C106(H10M,H10N),
 C107(H10O,H10P)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23),
  C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42),
  C44(H44), C45(H45), C46(H46), C47(H47), C50(H50), C51(H51), C52(H52),
 C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C62(H62),
  C63(H63), C64(H64), C65(H65), C66(H66), C68(H68), C69(H69), C70(H70),
 C71(H71), C72(H72), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C87(H87),
  C88(H88), C89(H89), C90(H90), C91(H91), C94(H94), C95(H95), C96(H96),
 C97(H97), C98(H98)
6.c Fitted hexagon refined as free rotating group:
 C13(C14,C15,C16,C17,C18), C67(C68,C69,C70,C71,C72), C92(C87,C88,C89,C90,C91),
 C93(C94,C95,C96,C97,C98)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 304 electrons were 
found in a volume of 1444\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2[C4H8O] per Asymmetric Unit 
which account for 320 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              97605
_shelx_fab_checksum              97717
_olex2_date_sample_data_collection 2023-05-02
_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 1.507
_oxdiff_exptl_absorpt_empirical_full_min 0.547