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_1571342
_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, 3.5(C7 H8)'
_chemical_formula_sum            'C90.5 H112 Ce O10 Si4'
_chemical_formula_weight         1612.27
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-08-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-08-30 deposited with the CCDC.	2024-03-22 downloaded from the CCDC.
;
_cell_angle_alpha                89.6876(9)
_cell_angle_beta                 88.7540(10)
_cell_angle_gamma                89.3655(8)
_cell_formula_units_Z            2
_cell_length_a                   14.49307(15)
_cell_length_b                   14.67810(14)
_cell_length_c                   20.2591(3)
_cell_measurement_reflns_used    31377
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      74.2270
_cell_measurement_theta_min      2.9700
_cell_volume                     4308.39(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.75a (Rigaku OD, 2022)'
_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 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.959
_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     33.00  72.00   0.50    1.00    --   66.10-125.00 150.00   78
  2  \w     35.00  66.00   0.50    1.00    --   66.10-125.00  90.00   62
  3  \w     36.00  72.00   0.50    1.00    --   66.10  15.00  60.00   72
  4  \w     83.00 111.00   0.50    1.00    --   66.10  15.00  60.00   56
  5  \w     28.00  73.00   0.50    1.00    --   66.10 -95.00 -30.00   90
  6  \w   -104.00 -79.00   0.50    1.00    --  -67.15   0.00-120.00   50
  7  \w    -72.00 -36.00   0.50    1.00    --  -67.15 125.00 -30.00   72
  8  \w   -100.00 -74.00   0.50    1.00    --  -67.15   0.00-180.00   52
  9  \w   -100.00 -74.00   0.50    1.00    --  -67.15   0.00 -30.00   52
 10  \w   -107.00 -82.00   0.50    1.00    --  -69.26   0.00   0.00   50
 11  \w    -96.00 -60.00   0.50    1.00    --  -69.26 125.00-180.00   72
 12  \w   -106.00 -73.00   0.50    1.00    --  -69.26   0.00  90.00   66
 13  \w   -101.00 -75.00   0.50    1.00    --  -69.26   0.00-120.00   52
 14  \w    -99.00 -62.00   0.50    1.00    --  -69.26 -15.00 120.00   74
 15  \w    -98.00 -44.00   0.50    1.00    --  -69.26 -15.00-150.00  108
 16  \w    -56.00 -27.00   0.50    1.00    --  -69.26 125.00-180.00   58
 17  \w     39.00  78.00   0.50    1.00    --   69.47 -95.00   0.00   78
 18  \w     32.00  58.00   0.50    1.00    --   69.47 -95.00-150.00   52
 19  \w     32.00  57.00   0.50    1.00    --   69.47 -95.00  90.00   50
 20  \w     50.00  75.00   0.50    1.00    --   69.47  15.00 -90.00   50
 21  \w     35.00  78.00   0.50    1.00    --   69.47 -95.00 150.00   86
 22  \w     32.00  75.00   0.50    1.00    --   69.47 -95.00  60.00   86
 23  \w     40.00  66.00   0.50    1.00    --   69.47 -95.00 120.00   52
 24  \w     43.00  99.00   0.50    1.00    --   69.47  15.00-180.00  112
 25  \w     35.00  68.00   0.50    1.00    --   69.47 -95.00-120.00   66
 26  \w     34.00  64.00   0.50    1.00    --   69.47 -95.00 -60.00   60
 27  \w    -70.00 -34.00   0.50    1.00    --  -74.76 141.00-147.18   72
 28  \w   -112.00 -84.00   0.50    1.00    --  -74.76 141.00-147.18   56
 29  \w    -90.00 -48.00   0.50    1.00    --  -74.76 105.00 144.58   84
 30  \w    -76.00 -36.00   0.50    1.00    --  -74.76 147.00 -96.34   80
 31  \w   -116.00 -85.00   0.50    1.00    --  -74.76 147.00 -96.34   62
 32  \w   -112.00 -34.00   0.50    1.00    --  -74.76 142.00  15.22  156
 33  \w     79.00 105.00   0.50    1.00    --   78.01-125.00 -60.00   52
 34  \w     47.00  75.00   0.50    1.00    --   78.01-125.00 -60.00   56
 35  \w     80.00 105.00   0.50    1.00    --   78.01-125.00-180.00   50
 36  \w     62.00  87.00   0.50    1.00    --   78.01 -95.00-120.00   50
 37  \w     41.00  66.00   0.50    1.00    --   78.01-125.00-180.00   50
 38  \w     69.00 105.00   0.50    1.00    --   78.01-125.00-120.00   72
 39  \w     45.00 105.00   0.50    1.00    --   78.01-125.00  60.00  120
 40  \w     36.00  62.00   0.50    1.00    --   78.01-125.00-120.00   52
 41  \w     75.00 105.00   0.50    1.00    --   78.01-125.00 150.00   60
 42  \w     80.00 105.00   0.50    1.00    --   78.01-125.00 -30.00   50
 43  \w     51.00 114.00   0.50    1.00    --   78.01  15.00 150.00  126
 44  \w     40.00  65.00   0.50    1.00    --   78.01-125.00 -30.00   50
 45  \w     78.00 105.00   0.50    1.00    --   78.01-125.00-150.00   54
 46  \w     49.00 103.00   0.50    1.00    --   78.01  15.00 -60.00  108
 47  \w     45.00  71.00   0.50    1.00    --   78.01-125.00-150.00   52
 48  \w     80.00 105.00   0.50    1.00    --   78.01-125.00  30.00   50
 49  \w     52.00 123.00   0.50    1.00    --   78.01  15.00-150.00  142
 50  \w     80.00 105.00   0.50    1.00    --   78.01-125.00 120.00   50
 51  \w     80.00 105.00   0.50    1.00    --   78.01-125.00   0.00   50
 52  \w     70.00 121.00   0.50    1.00    --   78.01  15.00  60.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0400917000
_diffrn_orient_matrix_UB_12      -0.0976301000
_diffrn_orient_matrix_UB_13      -0.0014640000
_diffrn_orient_matrix_UB_21      -0.0003755000
_diffrn_orient_matrix_UB_22      0.0016802000
_diffrn_orient_matrix_UB_23      -0.0760334000
_diffrn_orient_matrix_UB_31      0.0984792000
_diffrn_orient_matrix_UB_32      0.0385105000
_diffrn_orient_matrix_UB_33      -0.0014749000
_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  0.0278
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            69611
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.959
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.677
_diffrn_reflns_theta_min         3.011
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.052
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.491
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.75a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.243
_exptl_crystal_description       plate
_exptl_crystal_F_000             1698
_exptl_crystal_size_max          0.175
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.753
_refine_diff_density_min         -0.590
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1146
_refine_ls_number_reflns         16949
_refine_ls_number_restraints     1139
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0483P)^2^+3.1838P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0887
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15368
_reflns_number_total             16949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           ah557
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1571342--1571354.cif.
;
_cod_original_cell_volume        4308.40(8)
_cod_original_formula_sum        'C90.50 H112 Ce O10 Si4'
_cod_database_code               1571342
_shelx_shelxl_version_number     2019/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C89.50 H112 Ce O11 Si4'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C94A-C88A
 1.5 with sigma of 0.02
 C74B-C80B
 1.5 with sigma of 0.02
 C81B-C87B
 1.5 with sigma of 0.02
 C74A-C80A
 1.5 with sigma of 0.02
 C88B-C94B
 1.5 with sigma of 0.02
 C81A-C87A
 1.5 with sigma of 0.02
 C73-C67
 1.5 with sigma of 0.02
 C86A-C87A \\sim C87A-C82A
 with sigma of 0.02
 C38A-C37 \\sim C39B-C37 \\sim C40A-C37 \\sim C38B-C37 \\sim C39A-C37 \\sim
C40B-C37
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38A \\sim C38B \\sim C39A \\sim
C39B \\sim C40A \\sim C40B \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45
\\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53
\\sim C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61
\\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69
\\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74A \\sim C75A \\sim C76A \\sim
C77A \\sim C78A \\sim C79A \\sim C80A \\sim C74B \\sim C79B \\sim C78B \\sim
C77B \\sim C76B \\sim C75B \\sim C80B \\sim C81A \\sim C82A \\sim C83A \\sim
C84A \\sim C85A \\sim C86A \\sim C87A \\sim C81B \\sim C86B \\sim C85B \\sim
C84B \\sim C83B \\sim C82B \\sim C87B \\sim C88A \\sim C93A \\sim C92A \\sim
C91A \\sim C90A \\sim C89A \\sim C94A \\sim C89B \\sim C88B \\sim C93B \\sim
C92B \\sim C91B \\sim C90B \\sim C94B: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
4. Others
 Sof(C74B)=Sof(C79B)=Sof(H79B)=Sof(C78B)=Sof(H78B)=Sof(C77B)=Sof(H77B)=
 Sof(C76B)=Sof(H76B)=Sof(C75B)=Sof(H75B)=Sof(C80B)=Sof(H80D)=Sof(H80E)=
 Sof(H80F)=1-FVAR(1)
 Sof(C74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=
 Sof(C78A)=Sof(H78A)=Sof(C79A)=Sof(H79A)=Sof(C80A)=Sof(H80A)=Sof(H80B)=
 Sof(H80C)=FVAR(1)
 Sof(C81B)=Sof(C86B)=Sof(H86B)=Sof(C85B)=Sof(H85B)=Sof(C84B)=Sof(H84B)=
 Sof(C83B)=Sof(H83B)=Sof(C82B)=Sof(H82B)=Sof(C87B)=Sof(H87D)=Sof(H87E)=
 Sof(H87F)=1-FVAR(2)
 Sof(C81A)=Sof(C82A)=Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=
 Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=Sof(H87B)=
 Sof(H87C)=FVAR(2)
 Sof(C89B)=Sof(H89B)=Sof(C88B)=Sof(C93B)=Sof(H93B)=Sof(C92B)=Sof(H92B)=
 Sof(C91B)=Sof(H91B)=Sof(C90B)=Sof(H90B)=Sof(C94B)=Sof(H94D)=Sof(H94E)=
 Sof(H94F)=1-FVAR(3)
 Sof(C88A)=Sof(C93A)=Sof(H93A)=Sof(C92A)=Sof(H92A)=Sof(C91A)=Sof(H91A)=
 Sof(C90A)=Sof(H90A)=Sof(C89A)=Sof(H89A)=Sof(C94A)=Sof(H94A)=Sof(H94B)=
 Sof(H94C)=FVAR(3)
 Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39B)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=Sof(C40B)=Sof(H40D)=Sof(H40E)=Sof(H40F)=1-FVAR(4)
 Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39A)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(4)
 Fixed Sof: C67(0.5) C68(0.5) H68(0.5) C69(0.5) H69(0.5) C70(0.5) H70(0.5)
 C71(0.5) H71(0.5) C72(0.5) H72(0.5) C73(0.5) H73A(0.5) H73B(0.5) H73C(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C10(H10), C12(H12), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), 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), C75A(H75A), C76A(H76A), C77A(H77A),
 C78A(H78A), C79A(H79A), C79B(H79B), C78B(H78B), C77B(H77B), C76B(H76B),
 C75B(H75B), C82A(H82A), C83A(H83A), C84A(H84A), C85A(H85A), C86A(H86A),
 C86B(H86B), C85B(H85B), C84B(H84B), C83B(H83B), C82B(H82B), C93A(H93A),
 C92A(H92A), C91A(H91A), C90A(H90A), C89A(H89A), C89B(H89B), C93B(H93B),
 C92B(H92B), C91B(H91B), C90B(H90B)
5.b Fitted hexagon refined as free rotating group:
 C67(C68,C69,C70,C71,C72), C74A(C75A,C76A,C77A,C78A,C79A), C74B(C79B,C78B,C77B,
 C76B,C75B), C81A(C82A,C83A,C84A,C85A,C86A), C81B(C86B,C85B,C84B,C83B,C82B),
 C88A(C93A,C92A,C91A,C90A,C89A), C89B(C88B,C93B,C92B,C91B,C90B)
5.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C38A(H38A,H38B,H38C), C38B(H38D,H38E,H38F),
 C39A(H39A,H39B,H39C), C39B(H39D,H39E,H39F), C40A(H40A,H40B,H40C), C40B(H40D,
 H40E,H40F), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C),
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C73(H73A,H73B,
 H73C), C80A(H80A,H80B,H80C), C80B(H80D,H80E,H80F), C87A(H87A,H87B,H87C),
 C87B(H87D,H87E,H87F), C94A(H94A,H94B,H94C), C94B(H94D,H94E,H94F)
;
_shelx_res_checksum              34800
_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 1.350
_oxdiff_exptl_absorpt_empirical_full_min 0.770