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_1571347
_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 O10 Si4 Tb, 0.917(C24 H48 K O6), 2.7[C4H8O]'
_chemical_formula_sum            'C98.8 H149.6 K O18.2 Si4 Tb'
_chemical_formula_weight         1938.96
_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             2023-09-22
_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                120
_cell_formula_units_Z            4
_cell_length_a                   14.7864(3)
_cell_length_b                   14.7864(3)
_cell_length_c                   55.7285(10)
_cell_measurement_reflns_used    14238
_cell_measurement_temperature    199.99(12)
_cell_measurement_theta_max      71.4470
_cell_measurement_theta_min      3.3960
_cell_volume                     10552.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (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      199.99(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_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   -117.00 -19.00   1.00   10.00    --  -43.13 -70.00 -89.00   98
  2  \w    -31.00  39.00   1.00   10.00    --   43.13 -41.00 116.00   70
  3  \w     43.00  69.00   1.00   40.00    --  103.49-139.00 -41.00   26
  4  \w    101.00 148.00   1.00   40.00    --  103.49 130.00-155.00   47
  5  \w     90.00 166.00   1.00   40.00    --  103.49  41.00 -90.00   76
  6  \w    113.00 176.00   1.00   40.00    --  103.49 106.00 127.00   63
  7  \w   -117.00 -21.00   1.00   10.00    --  -43.13 -37.00  90.00   96
  8  \w     50.00  76.00   1.00   10.00    --   43.13-125.00-180.00   26
  9  \w     84.00 155.00   1.00   40.00    --  103.49  45.00  30.00   71
 10  \w     61.00 144.00   1.00   40.00    --  103.49 178.00 -30.00   83
 11  \w     38.00 108.00   1.00   40.00    --  103.49-111.00 150.00   70
 12  \w     23.00  93.00   1.00   40.00    --  103.49 -94.00  60.00   70
 13  \w    106.00 173.00   1.00   40.00    --  103.49 111.00 -30.00   67
;
_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      -0.0565539000
_diffrn_orient_matrix_UB_12      0.0611144000
_diffrn_orient_matrix_UB_13      0.0056226000
_diffrn_orient_matrix_UB_21      0.0374917000
_diffrn_orient_matrix_UB_22      0.0131423000
_diffrn_orient_matrix_UB_23      0.0262344000
_diffrn_orient_matrix_UB_31      0.0993749000
_diffrn_orient_matrix_UB_32      0.1027866000
_diffrn_orient_matrix_UB_33      -0.0067054000
_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  0.0585
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       68
_diffrn_reflns_limit_l_min       -68
_diffrn_reflns_number            58647
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.734
_diffrn_reflns_theta_min         3.172
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.568
_exptl_absorpt_correction_T_max  0.684
_exptl_absorpt_correction_T_min  0.283
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (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    1.221
_exptl_crystal_description       irregular
_exptl_crystal_F_000             4112
_exptl_crystal_size_max          0.293
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.569
_refine_diff_density_min         -0.689
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.429(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     394
_refine_ls_number_reflns         6978
_refine_ls_number_restraints     484
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0751
_refine_ls_R_factor_gt           0.0695
_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^)+(0.0745P)^2^+22.2319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1709
_refine_ls_wR_factor_ref         0.1747
_reflns_Friedel_coverage         0.663
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                6285
_reflns_number_total             6978
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-210
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_cell_volume        10551.9(4)
_cod_original_formula_sum        'C98.80 H149.60 K O18.20 Si4 Tb'
_cod_database_code               1571347
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C66 H84 O10 Si4 Tb1'
_shelx_estimated_absorpt_t_max   0.717
_shelx_estimated_absorpt_t_min   0.348
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.571(12)
 0.429(12)
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. Uiso/Uaniso restraints and constraints
O5 \\sim C26 \\sim C27 \\sim C28 \\sim C29: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O6 \\sim K2 \\sim O7 \\sim C30 \\sim C33 \\sim C37 \\sim C34 \\sim C31 \\sim
C32 \\sim C36 \\sim C35: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(O5) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(1)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
 Fixed Sof: O6(0.333333) 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) O7(0.5) C37(0.5)
 H37A(0.5) H37B(0.5) C36(0.5) H36A(0.5) H36B(0.5) C35(0.5) H35A(0.5) H35B(0.5)
 C34(0.5) H34A(0.5) H34B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C28(H28A,H28B), C27(H27A,H27B), C26(H26A,H26B), C30(H30A,
 H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C37(H37A,H37B),
 C36(H36A,H36B), C35(H35A,H35B), C34(H34A,H34B)
6.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)
6.c Fitted pentagon refined as free rotating group:
 O5(C29,C28,C27,C26), O6(C30,C31,C32,C33), O7(C37,C36,C35,C34)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 404 electrons were 
found in a volume of 1872\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[C4H8O] per Asymmetric Unit 
which account for 480 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              83671
_shelx_fab_checksum              20377
_olex2_date_sample_data_collection 2023-02-01
_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 1.277
_oxdiff_exptl_absorpt_empirical_full_min 0.673