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_1571353
_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         'C164 H132 K2 N4 O8 Si8 Tb2, 1[C4H10O]'
_chemical_formula_sum            'C168 H142 K2 N4 O9 Si8 Tb2'
_chemical_formula_weight         2981.61
_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
_audit_creation_date             2024-02-02
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-02 deposited with the CCDC.	2024-03-22 downloaded from the CCDC.
;
_cell_angle_alpha                87.191(3)
_cell_angle_beta                 67.976(3)
_cell_angle_gamma                65.256(4)
_cell_formula_units_Z            1
_cell_length_a                   14.6865(6)
_cell_length_b                   15.3137(6)
_cell_length_c                   18.9586(6)
_cell_measurement_reflns_used    15912
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.4530
_cell_measurement_theta_min      3.4390
_cell_volume                     3560.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.972
_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    -45.00 -12.00   1.00    2.00    --  -43.01  35.00 -68.00   33
  2  \w   -118.00 -18.00   1.00    2.00    --  -43.01 -35.00 134.00  100
  3  \w     -6.00  19.00   1.00    2.00    --   43.01 -35.00 134.00   25
  4  \w     42.00 113.00   1.00    2.00    --   43.01  35.00 -68.00   71
  5  \w     29.00 107.00   1.00    8.00    --  103.49 -35.00 134.00   78
  6  \w     85.00 178.00   1.00    8.00    --  103.49  35.00 -68.00   93
  7  \w     10.00  75.00   1.00    2.00    --   43.01 -77.00-180.00   65
  8  \w      7.00  55.00   1.00    2.00    --   43.01 -99.00   0.00   48
  9  \w    -20.00  56.00   1.00    2.00    --   43.01 -77.00  60.00   76
 10  \w    108.00 177.00   1.00    8.00    --  103.49  77.00-150.00   69
 11  \w     61.00 137.00   1.00    8.00    --  103.49 178.00   0.00   76
 12  \w    117.00 172.00   1.00    8.00    --  103.49 111.00-120.00   55
 13  \w    107.00 158.00   1.00    8.00    --  103.49  77.00 150.00   51
 14  \w     81.00 108.00   1.00    8.00    --  103.49-111.00  90.00   27
 15  \w    150.00 177.00   1.00    8.00    --  103.49 111.00 -30.00   27
 16  \w     78.00 104.00   1.00    8.00    --  103.49  61.00-180.00   26
 17  \w    124.00 175.00   1.00    8.00    --  103.49  61.00-180.00   51
 18  \w     41.00 108.00   1.00    8.00    --  103.49-111.00 -30.00   67
 19  \w     39.00  95.00   1.00    8.00    --  103.49-111.00-180.00   56
 20  \w     36.00 126.00   1.00    8.00    --  103.49 -61.00 -30.00   90
 21  \w     62.00 108.00   1.00    8.00    --  103.49 178.00  60.00   46
 22  \w     84.00 109.00   1.00    8.00    --  103.49-111.00-150.00   25
 23  \w     81.00 109.00   1.00    8.00    --  103.49-111.00  60.00   28
;
_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      -0.0734480000
_diffrn_orient_matrix_UB_12      0.0783740000
_diffrn_orient_matrix_UB_13      -0.0337843000
_diffrn_orient_matrix_UB_21      0.0782494000
_diffrn_orient_matrix_UB_22      0.0485465000
_diffrn_orient_matrix_UB_23      -0.0216662000
_diffrn_orient_matrix_UB_31      0.0650175000
_diffrn_orient_matrix_UB_32      -0.0630541000
_diffrn_orient_matrix_UB_33      -0.0787473000
_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  0.0322
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            28996
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.469
_diffrn_reflns_theta_min         2.535
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.477
_exptl_absorpt_correction_T_max  0.661
_exptl_absorpt_correction_T_min  0.379
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
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    1.391
_exptl_crystal_description       prism
_exptl_crystal_F_000             1530
_exptl_crystal_size_max          0.224
_exptl_crystal_size_mid          0.127
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.634
_refine_diff_density_min         -0.699
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     849
_refine_ls_number_reflns         13709
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0378
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0430P)^2^+1.9705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0841
_refine_ls_wR_factor_ref         0.0871
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12635
_reflns_number_total             13709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-363-mecn
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_database_code               1571353
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C168 H142 N4 O9 Si8 K2 Tb2'
_shelx_estimated_absorpt_t_max   0.593
_shelx_estimated_absorpt_t_min   0.325
_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.a 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)
2.b Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C82(H82A,H82B,H82C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 40 electrons were 
found in a volume of 213\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C4H10O] per Asymmetric Unit 
which account for 42 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              74330
_shelx_fab_checksum              41823
_olex2_date_sample_data_collection 2024-02-01
_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 1.537
_oxdiff_exptl_absorpt_empirical_full_min 0.847