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_1571344
_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         'C72 H69 O6 Si3 Tb, 2(C7 H8)'
_chemical_formula_sum            'C86 H85 O6 Si3 Tb'
_chemical_formula_weight         1457.72
_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             2023-09-15
_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                106.0855(17)
_cell_angle_beta                 99.4980(18)
_cell_angle_gamma                93.6846(16)
_cell_formula_units_Z            2
_cell_length_a                   11.1371(2)
_cell_length_b                   14.2669(3)
_cell_length_c                   24.2013(5)
_cell_measurement_reflns_used    15210
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4570
_cell_measurement_theta_min      3.8640
_cell_volume                     3619.56(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (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      140.00(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 0.973
_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    -80.00   1.00   1.00   10.00    --  -40.91 111.00  27.00   81
  2  \w     30.00  79.00   1.00   10.00    --   40.91-111.00 -66.00   49
  3  \w    107.00 153.00   1.00   40.00    --  105.15 111.00  27.00   46
  4  \w     67.00 108.00   1.00   40.00    --  105.15-111.00 -66.00   41
  5  \w   -114.00 -16.00   1.00   10.00    --  -40.91 -38.00 -30.00   98
  6  \w    -44.00 -18.00   1.00   10.00    --  -40.91  38.00-180.00   26
  7  \w   -113.00 -24.00   1.00   10.00    --  -40.91 -38.00-120.00   89
  8  \w     13.00 107.00   1.00   10.00    --   40.91  57.00-180.00   94
  9  \w     79.00 143.00   1.00   40.00    --  105.15 178.00 -60.00   64
 10  \w    145.00 173.00   1.00   40.00    --  105.15 111.00 150.00   28
 11  \w     29.00 133.00   1.00   40.00    --  105.15 -30.00 -90.00  104
 12  \w    104.00 170.00   1.00   40.00    --  105.15 111.00   0.00   66
 13  \w     34.00 105.00   1.00   40.00    --  105.15-111.00  90.00   71
 14  \w     33.00  60.00   1.00   40.00    --  105.15-111.00 150.00   27
 15  \w     62.00  87.00   1.00   40.00    --  105.15-111.00 150.00   25
 16  \w     79.00 163.00   1.00   40.00    --  105.15  30.00-180.00   84
 17  \w     71.00 109.00   1.00   40.00    --  105.15-111.00-180.00   38
 18  \w    128.00 168.00   1.00   40.00    --  105.15 111.00  60.00   40
 19  \w     80.00 165.00   1.00   40.00    --  105.15  45.00  90.00   85
 20  \w     83.00 124.00   1.00   40.00    --  105.15 -45.00  60.00   41
 21  \w     55.00 109.00   1.00   40.00    --  105.15-111.00   0.00   54
 22  \w     32.00  79.00   1.00   40.00    --  105.15 -45.00  60.00   47
;
_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      -0.0220612000
_diffrn_orient_matrix_UB_12      0.0114361000
_diffrn_orient_matrix_UB_13      -0.0622158000
_diffrn_orient_matrix_UB_21      -0.0585159000
_diffrn_orient_matrix_UB_22      0.0949191000
_diffrn_orient_matrix_UB_23      0.0222230000
_diffrn_orient_matrix_UB_31      0.1266000000
_diffrn_orient_matrix_UB_32      0.0605117000
_diffrn_orient_matrix_UB_33      0.0137816000
_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  0.0333
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            28022
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.633
_diffrn_reflns_theta_min         3.246
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.704
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.515
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (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    1.338
_exptl_crystal_description       prism
_exptl_crystal_F_000             1512
_exptl_crystal_size_max          0.206
_exptl_crystal_size_mid          0.064
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.678
_refine_diff_density_min         -0.946
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     964
_refine_ls_number_reflns         13994
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0316
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0448P)^2^+0.4138P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13011
_reflns_number_total             13994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-241
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_cell_volume        3619.57(13)
_cod_database_code               1571344
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C86 H85 O6 Si3 Tb1'
_shelx_estimated_absorpt_t_max   0.779
_shelx_estimated_absorpt_t_min   0.386
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C71-C72 \\sim C76-C75 \\sim C73-C72 \\sim C76-C77 \\sim C77-C78 \\sim C73-C74
\\sim C67-C66 \\sim C69-C66
 \\sim C70-C69 \\sim C68-C67
 with sigma of 0.02
 O5-C70 \\sim O5-C68 \\sim O6-C74 \\sim O6-C78 \\sim O6-C71 \\sim O6-C75
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O6 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim
C78: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim
C94 \\sim C95 \\sim C96 \\sim C97 \\sim C98 \\sim C99: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(C77)=Sof(H77A)=
 Sof(H77B)=Sof(C78)=Sof(H78A)=Sof(H78B)=1-FVAR(1)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=FVAR(1)
 Sof(H66C)=Sof(H66D)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 1-FVAR(2)
 Sof(H66A)=Sof(H66B)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=
 FVAR(2)
 Sof(C93)=Sof(C94)=Sof(H94)=Sof(C95)=Sof(H95)=Sof(C96)=Sof(H96)=Sof(C97)=
 Sof(H97)=Sof(C98)=Sof(H98)=Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(H99C)=1-FVAR(3)
 Sof(C86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=Sof(C89)=Sof(H89)=Sof(C90)=
 Sof(H90)=Sof(C91)=Sof(H91)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C66(H66C,H66D), C67(H67A,H67B), C68(H68A,H68B),
 C69(H69A,H69B), C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B),
  C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B)
5.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), C80(H80),
  C81(H81), C82(H82), C83(H83), C84(H84), C87(H87), C88(H88), C89(H89),
 C90(H90), C91(H91), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98)
5.c Fitted hexagon refined as free rotating group:
 C86(C87,C88,C89,C90,C91), C93(C94,C95,C96,C97,C98)
5.d Idealised Me refined as rotating group:
 C85(H85A,H85B,H85C), C92(H92A,H92B,H92C), C99(H99A,H99B,H99C)
;
_shelx_res_checksum              27055
_olex2_date_sample_data_collection 2023-03-07
_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 2.569
_oxdiff_exptl_absorpt_empirical_full_min 0.449