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_1571345
_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 H54 N3 O3 Si3 Tb'
_chemical_formula_sum            'C66 H54 N3 O3 Si3 Tb'
_chemical_formula_weight         1180.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-28
_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                 91.7441(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.79296(19)
_cell_length_b                   22.3194(2)
_cell_length_c                   18.4603(2)
_cell_measurement_reflns_used    23197
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.2310
_cell_measurement_theta_min      1.9660
_cell_volume                     5680.38(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (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                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_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   -114.00 -38.00   0.50    1.00    --  -69.26 -15.00  30.00  152
  2  \w   -107.00 -32.00   0.50    1.00    --  -69.26   0.00  60.00  150
  3  \w    -72.00 -29.00   0.50    1.00    --  -66.85   0.00 120.00   86
  4  \w     32.00  78.00   0.50    1.00    --   69.46 -95.00 120.00   92
  5  \w     37.00  69.00   0.50    1.00    --   78.01-125.00  90.00   64
  6  \w     32.00  78.00   0.50    1.00    --   69.46 -95.00  90.00   92
  7  \w     68.00 105.00   0.50    1.00    --   78.01-125.00  60.00   74
  8  \w     75.00 104.00   0.50    1.00    --   78.01-125.00-150.00   58
  9  \w     36.00  69.00   0.50    1.00    --   78.01-125.00-150.00   66
 10  \w     32.00  78.00   0.50    1.00    --   69.46 -95.00-180.00   92
 11  \w     28.00  75.00   0.50    1.00    --   66.10 -95.00 -30.00   94
 12  \w     41.00  69.00   0.50    1.00    --   78.01 -95.00 -90.00   56
 13  \w     32.00  78.00   0.50    1.00    --   69.46 -95.00 -60.00   92
 14  \w     28.00  75.00   0.50    1.00    --   66.10 -95.00  60.00   94
 15  \w     46.00  81.00   0.50    1.00    --   78.01 -95.00 120.00   70
 16  \w     28.00  75.00   0.50    1.00    --   66.10 -95.00 150.00   94
 17  \w     42.00 104.00   0.50    1.00    --   78.01   0.00  60.00  124
 18  \w     58.00  93.00   0.50    1.00    --   78.01  15.00  90.00   70
 19  \w     41.00 108.00   0.50    1.00    --   78.01   0.00 150.00  134
 20  \w     35.00 111.00   0.50    1.00    --   66.10  15.00 -30.00  152
 21  \w     47.00 123.00   0.50    1.00    --   78.01  15.00 -30.00  152
 22  \w     35.00 111.00   0.50    1.00    --   66.10  15.00-120.00  152
 23  \w     29.00 104.00   0.50    1.00    --   66.10   0.00-180.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0771562000
_diffrn_orient_matrix_UB_12      0.0172150000
_diffrn_orient_matrix_UB_13      -0.0549278000
_diffrn_orient_matrix_UB_21      -0.0273832000
_diffrn_orient_matrix_UB_22      -0.0554283000
_diffrn_orient_matrix_UB_23      -0.0460426000
_diffrn_orient_matrix_UB_31      -0.0759572000
_diffrn_orient_matrix_UB_32      0.0373857000
_diffrn_orient_matrix_UB_33      -0.0428794000
_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  0.0370
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            57303
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.747
_diffrn_reflns_theta_min         3.107
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.113
_exptl_absorpt_correction_T_max  0.942
_exptl_absorpt_correction_T_min  0.342
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       prism
_exptl_crystal_F_000             2408
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.147
_exptl_crystal_size_min          0.115
_refine_diff_density_max         1.732
_refine_diff_density_min         -1.125
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     784
_refine_ls_number_reflns         11268
_refine_ls_number_restraints     421
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0650
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0691P)^2^+17.2126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1472
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9232
_reflns_number_total             11268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mk-1063
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_cell_volume        5680.36(12)
_cod_database_code               1571345
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C66 H54 N3 O3 Si3 Tb1'
_shelx_estimated_absorpt_t_max   0.495
_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. Restrained distances
 Si3-C67 \\sim Si3-C55 \\sim Si3-C49 \\sim Si3-C61
 with sigma of 0.02
 C79-C77 \\sim C78-C77
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si3 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim
C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim
C72 \\sim C77 \\sim C78 \\sim C79: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
4. Others
 Sof(C61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(C65)=
 Sof(H65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=1-FVAR(1)
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=FVAR(1)
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=1-FVAR(2)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=FVAR(2)
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), C68(H68), C69(H69), C70(H70),
 C71(H71), C72(H72)
5.b Fitted hexagon refined as free rotating group:
 C49(C50,C51,C52,C53,C54), C67(C68,C69,C70,C71,C72)
5.c Idealised Me refined as rotating group:
 C74(H74A,H74B,H74C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,
 H79C)
;
_shelx_res_checksum              53561
_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 1.705
_oxdiff_exptl_absorpt_empirical_full_min 0.602