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_1571354
_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         'C85 H68 K O4 Si4 Tb, 0.5[C7H8]'
_chemical_formula_sum            'C88.5 H72 K O4 Si4 Tb'
_chemical_formula_weight         1509.921
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     heavy
_audit_creation_date             2023-09-14
_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                77.38(1)
_cell_angle_beta                 74.179(9)
_cell_angle_gamma                63.234(11)
_cell_formula_units_Z            2
_cell_length_a                   14.0838(14)
_cell_length_b                   14.2282(17)
_cell_length_c                   21.775(3)
_cell_measurement_reflns_used    4925
_cell_measurement_temperature    200.00(11)
_cell_measurement_theta_max      64.7890
_cell_measurement_theta_min      3.4740
_cell_volume                     3725.0(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_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 0.9954
_diffrn_measured_fraction_theta_max 0.9581
_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    -78.00  14.00   1.00   10.00    --  -42.01  88.00 135.00   92
  2  \w     -7.00  48.00   1.00   10.00    --   42.01 -88.00  19.00   55
  3  \w    111.00 138.00   1.00   40.00    --  103.49  88.00 135.00   27
  4  \w     42.00  81.00   1.00   40.00    --  103.49 -88.00  19.00   39
  5  \w   -116.00 -19.00   1.00   10.00    --  -42.01 -37.00-150.00   97
  6  \w   -106.00 -19.00   1.00   10.00    --  -42.01 -37.00 -60.00   87
  7  \w    -13.00  12.00   1.00   10.00    --   42.01 -77.00  90.00   25
  8  \w     43.00  83.00   1.00   10.00    --   42.01-125.00 -30.00   40
  9  \w     30.00  58.00   1.00   40.00    --  103.49 -45.00 -90.00   28
 10  \w     33.00 130.00   1.00   40.00    --  103.49 -61.00  30.00   97
 11  \w     29.00 121.00   1.00   40.00    --  103.49 -30.00   0.00   92
 12  \w     30.00 105.00   1.00   40.00    --  103.49-111.00   0.00   75
 13  \w     89.00 178.00   1.00   40.00    --  103.49  30.00-180.00   89
 14  \w     75.00 108.00   1.00   40.00    --  103.49-111.00 150.00   33
 15  \w     65.00 176.00   1.00   40.00    --  103.49  15.00 -60.00  111
 16  \w     55.00 109.00   1.00   40.00    --  103.49-111.00-120.00   54
 17  \w    126.00 177.00   1.00   40.00    --  103.49 111.00 -60.00   51
 18  \w     83.00 145.00   1.00   40.00    --  103.49 178.00  30.00   62
 19  \w    152.00 177.00   1.00   40.00    --  103.49 111.00   0.00   25
 20  \w     30.00 109.00   1.00   40.00    --  103.49-111.00  30.00   79
 21  \w     28.00 129.00   1.00   40.00    --  103.49 -30.00 150.00  101
;
_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      0.1233581000
_diffrn_orient_matrix_UB_12      -0.0323337000
_diffrn_orient_matrix_UB_13      -0.0148646000
_diffrn_orient_matrix_UB_21      -0.0087695000
_diffrn_orient_matrix_UB_22      0.0693320000
_diffrn_orient_matrix_UB_23      -0.0651168000
_diffrn_orient_matrix_UB_31      -0.0184529000
_diffrn_orient_matrix_UB_32      0.0950722000
_diffrn_orient_matrix_UB_33      0.0318501000
_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  0.0757
_diffrn_reflns_av_unetI/netI     0.0949
_diffrn_reflns_Laue_measured_fraction_full 0.9954
_diffrn_reflns_Laue_measured_fraction_max 0.9581
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            29995
_diffrn_reflns_point_group_measured_fraction_full 0.9954
_diffrn_reflns_point_group_measured_fraction_max 0.9581
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         73.00
_diffrn_reflns_theta_min         3.50
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.186
_exptl_absorpt_correction_T_max  0.604
_exptl_absorpt_correction_T_min  0.405
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (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            'lustrous pale colourless'
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1539.958
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.138
_exptl_crystal_size_min          0.116
_refine_diff_density_max         1.2250
_refine_diff_density_min         -1.2251
_refine_diff_density_rms         0.1630
_refine_ls_d_res_high            0.8062
_refine_ls_d_res_low             12.6245
_refine_ls_goodness_of_fit_ref   1.0844
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    177
_refine_ls_number_parameters     985
_refine_ls_number_reflns         14275
_refine_ls_number_restraints     630
_refine_ls_restrained_S_all      1.0596
_refine_ls_R_factor_all          0.1308
_refine_ls_R_factor_gt           0.0850
_refine_ls_shift/su_max          0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0982P)^2^+8.2457P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2142
_refine_ls_wR_factor_ref         0.2509
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              17
_reflns_limit_h_min              -16
_reflns_limit_k_max              17
_reflns_limit_k_min              -16
_reflns_limit_l_max              26
_reflns_limit_l_min              0
_reflns_number_gt                9012
_reflns_number_total             14275
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-374
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_cell_volume        3724.9(8)
_cod_original_formula_sum        'C88.5 H72 K1 O4 Si4 Tb1'
_cod_database_code               1571354
_chemical_oxdiff_formula         'C88.5 H72 O4 Si4 K1 Tb1'
_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
 Si4-C67 \\sim Si4-C73 \\sim Si4-C85 \\sim Si4-C79
 with sigma of 0.02
 C98-C104 \\sim C97-C91
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C67 \\sim C72 \\sim C71 \\sim C70 \\sim C69 \\sim C68 \\sim C78 \\sim C77 \\sim
C76 \\sim C75 \\sim C74 \\sim C73 \\sim C79 \\sim C84 \\sim C83 \\sim C82 \\sim
C81 \\sim C80 \\sim C85 \\sim C90 \\sim C89 \\sim C88 \\sim C87 \\sim C86 \\sim
C91 \\sim C96 \\sim C95 \\sim C94 \\sim C93 \\sim C92 \\sim C97 \\sim C98 \\sim
C103 \\sim C102 \\sim C101 \\sim C100 \\sim C99 \\sim C104: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C85)=Sof(C90)=Sof(H90)=Sof(C89)=Sof(H89)=Sof(C88)=Sof(H88)=Sof(C87)=
 Sof(H87)=Sof(C86)=Sof(H86)=1-FVAR(1)
 Sof(C79)=Sof(C84)=Sof(H84)=Sof(C83)=Sof(H83)=Sof(C82)=Sof(H82)=Sof(C81)=
 Sof(H81)=Sof(C80)=Sof(H80)=FVAR(1)
 Sof(C78)=Sof(H78)=Sof(C77)=Sof(H77)=Sof(C76)=Sof(H76)=Sof(C75)=Sof(H75)=
 Sof(C74)=Sof(H74)=Sof(C73)=1-FVAR(2)
 Sof(C67)=Sof(C72)=Sof(H72)=Sof(C71)=Sof(H71)=Sof(C70)=Sof(H70)=Sof(C69)=
 Sof(H69)=Sof(C68)=Sof(H68)=FVAR(2)
 Sof(C98)=Sof(C103)=Sof(H103)=Sof(C102)=Sof(H102)=Sof(C101)=Sof(H101)=
 Sof(C100)=Sof(H100)=Sof(C99)=Sof(H99)=Sof(C104)=Sof(H10a)=Sof(H10b)=Sof(H10c)=
 1-FVAR(3)
 Sof(C91)=Sof(C96)=Sof(H96)=Sof(C95)=Sof(H95)=Sof(C94)=Sof(H94)=Sof(C93)=
 Sof(H93)=Sof(C92)=Sof(H92)=Sof(C97)=Sof(H97a)=Sof(H97b)=Sof(H97c)=FVAR(3)
5.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), C72(H72), C71(H71), C70(H70),
 C69(H69), C68(H68), C78(H78), C77(H77), C76(H76), C75(H75), C74(H74), C84(H84),
  C83(H83), C82(H82), C81(H81), C80(H80), C90(H90), C89(H89), C88(H88),
 C87(H87), C86(H86), C96(H96), C95(H95), C94(H94), C93(H93), C92(H92),
 C103(H103), C102(H102), C101(H101), C100(H100), C99(H99)
5.b Fitted hexagon refined as free rotating group:
 C67(C72,C71,C70,C69,C68), C78(C77,C76,C75,C74,C73), C79(C84,C83,C82,C81,C80),
 C85(C90,C89,C88,C87,C86), C91(C96,C95,C94,C93,C92), C98(C103,C102,C101,C100,
 C99)
5.c Idealised Me refined as rotating group:
 C97(H97a,H97b,H97c), C104(H10a,H10b,H10c)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 46 electrons were 
found in a volume of 342\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.5[C7H8] per Asymmetric Unit 
which account for 50 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_date_sample_data_collection 2023-09-12
_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 1.751
_oxdiff_exptl_absorpt_empirical_full_min 0.662