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_1571343
_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         'C52 H77 O10 Si3 Tb'
_chemical_formula_sum            'C52 H77 O10 Si3 Tb'
_chemical_formula_weight         1105.32
_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             2023-09-13
_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                89.0799(15)
_cell_angle_beta                 88.765(2)
_cell_angle_gamma                87.017(2)
_cell_formula_units_Z            4
_cell_length_a                   13.9674(4)
_cell_length_b                   18.1707(4)
_cell_length_c                   21.7736(4)
_cell_measurement_reflns_used    17069
_cell_measurement_temperature    140.01(10)
_cell_measurement_theta_max      72.3410
_cell_measurement_theta_min      3.8760
_cell_volume                     5516.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (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      140.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.970
_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    -30.00  -3.00   1.00    8.50    --  -40.66  56.00  69.00   27
  2  \w   -112.00 -15.00   1.00    8.50    --  -40.66 -56.00 -73.00   97
  3  \w     19.00  44.00   1.00    8.50    --   40.66 -56.00 -73.00   25
  4  \w     69.00  98.00   1.00    8.50    --   40.66  56.00  69.00   29
  5  \w     32.00  69.00   1.00   34.00    --  105.15 -56.00 -73.00   37
  6  \w    136.00 177.00   1.00   34.00    --  105.15  56.00  69.00   41
  7  \w   -111.00 -14.00   1.00    8.50    --  -40.66 -57.00-150.00   97
  8  \w    -19.00  73.00   1.00    8.50    --   40.66 -77.00   0.00   92
  9  \w    -19.00  58.00   1.00    8.50    --   40.66 -77.00 150.00   77
 10  \w     28.00  92.00   1.00    8.50    --   40.66-125.00 120.00   64
 11  \w     62.00 109.00   1.00   34.00    --  105.15-111.00 120.00   47
 12  \w     63.00 105.00   1.00   34.00    --  105.15 178.00 -60.00   42
 13  \w     77.00 136.00   1.00   34.00    --  105.15  30.00-180.00   59
 14  \w     63.00  93.00   1.00   34.00    --  105.15 178.00  60.00   30
 15  \w     33.00  60.00   1.00   34.00    --  105.15-111.00 120.00   27
 16  \w    117.00 146.00   1.00   34.00    --  105.15 178.00  60.00   29
 17  \w     32.00 108.00   1.00   34.00    --  105.15-111.00  30.00   76
 18  \w    135.00 174.00   1.00   34.00    --  105.15 111.00  30.00   39
 19  \w    115.00 143.00   1.00   34.00    --  105.15  77.00 150.00   28
 20  \w    107.00 177.00   1.00   34.00    --  105.15 111.00-180.00   70
 21  \w     77.00 175.00   1.00   34.00    --  105.15  30.00 -90.00   98
 22  \w    139.00 174.00   1.00   34.00    --  105.15  30.00-180.00   35
 23  \w    150.00 175.00   1.00   34.00    --  105.15  77.00 150.00   25
 24  \w     77.00 109.00   1.00   34.00    --  105.15-111.00-180.00   32
 25  \w     40.00 109.00   1.00   34.00    --  105.15-111.00 -90.00   69
 26  \w    111.00 138.00   1.00   34.00    --  105.15 111.00-150.00   27
 27  \w     35.00 132.00   1.00   34.00    --  105.15 -61.00  90.00   97
;
_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      0.0100978000
_diffrn_orient_matrix_UB_12      0.0611564000
_diffrn_orient_matrix_UB_13      0.0472683000
_diffrn_orient_matrix_UB_21      0.1096849000
_diffrn_orient_matrix_UB_22      -0.0144396000
_diffrn_orient_matrix_UB_23      -0.0017860000
_diffrn_orient_matrix_UB_31      0.0084266000
_diffrn_orient_matrix_UB_32      0.0571022000
_diffrn_orient_matrix_UB_33      -0.0526502000
_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  0.0435
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            45368
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.726
_diffrn_reflns_theta_min         3.148
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.350
_exptl_absorpt_correction_T_max  0.749
_exptl_absorpt_correction_T_min  0.504
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (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    1.331
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2304
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.063
_refine_diff_density_max         1.043
_refine_diff_density_min         -1.382
_refine_diff_density_rms         0.077
_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     1293
_refine_ls_number_reflns         21318
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0488P)^2^+1.7509P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0986
_refine_ls_wR_factor_ref         0.1072
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16912
_reflns_number_total             21318
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-201
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_database_code               1571343
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C52 H77 O10 Si3 Tb1'
_shelx_estimated_absorpt_t_max   0.655
_shelx_estimated_absorpt_t_min   0.379
_olex2_refinement_description
;
1. 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
2. Restrained distances
 O10-C53 \\sim O10-C49 \\sim O10-C56 \\sim O10-C52
 with sigma of 0.02
 C53-C54 \\sim C49-C50 \\sim C55-C54 \\sim C50-C51 \\sim C52-C51 \\sim C56-C55
 with sigma of 0.02
 C74-C69 \\sim C71-C69 \\sim C73-C69 \\sim C70-C69 \\sim C75-C69 \\sim C72-C69
 with sigma of 0.02
 C74-C73 \\sim C73-C75
 with sigma of 0.02
 C72-C71 \\sim C71-C70
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O10 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=1-FVAR(1)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=FVAR(1)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=1-FVAR(2)
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,
 H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C108(H10S,H10T),
 C109(H10U,H10V), C110(H11A,H11B), C111(H11C,H11D)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C22(H22),
 C23(H23), C24(H24), C25(H25), C36(H36), C37(H37), C38(H38), C39(H39), C58(H58),
  C60(H60), C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), C81(H81),
 C82(H82), C83(H83), C84(H84), C95(H95), C96(H96), C97(H97), C98(H98)
5.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,
 H78C), C79(H79A,H79B,H79C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C),
 C101(H10A,H10B,H10C), C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C105(H10J,
 H10K,H10L), C106(H10M,H10N,H10O), C107(H10P,H10Q,H10R)
;
_shelx_res_checksum              9993
_olex2_date_sample_data_collection 2023-01-19
_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 1.997
_oxdiff_exptl_absorpt_empirical_full_min 0.466