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_1571351
_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         'C82 H66 N2 O4 Si4 Tb, C2 H3 N, 1.5[CH3CN]'
_chemical_formula_sum            'C87 H73.5 N4.5 O4 Si4 Tb'
_chemical_formula_weight         1517.28
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 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                 91.3763(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.6194(3)
_cell_length_b                   13.8469(3)
_cell_length_c                   31.8914(5)
_cell_measurement_reflns_used    16717
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      72.0540
_cell_measurement_theta_min      2.6990
_cell_volume                     7778.4(2)
_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      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_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    -28.00  30.00   1.00    5.00    --  -43.01  89.00-175.00   58
  2  \w     11.00  36.00   1.00    5.00    --   43.01 -89.00  69.00   25
  3  \w     46.00  75.00   1.00   20.00    --  103.18 -89.00  69.00   29
  4  \w    116.00 141.00   1.00   20.00    --  103.18  89.00-175.00   25
  5  \w   -116.00 -20.00   1.00    5.00    --  -43.01 -37.00-120.00   96
  6  \w      9.00  77.00   1.00    5.00    --   43.01 -99.00  30.00   68
  7  \w     38.00  97.00   1.00    5.00    --   43.01-125.00 -90.00   59
  8  \w     73.00  98.00   1.00   20.00    --  103.18-111.00-150.00   25
  9  \w    104.00 176.00   1.00   20.00    --  103.18 111.00 -30.00   72
 10  \w    104.00 173.00   1.00   20.00    --  103.18  77.00-180.00   69
 11  \w    108.00 175.00   1.00   20.00    --  103.18  77.00 -90.00   67
 12  \w    150.00 176.00   1.00   20.00    --  103.18  77.00  60.00   26
 13  \w    103.00 129.00   1.00   20.00    --  103.18  77.00  60.00   26
 14  \w     21.00  98.00   1.00   20.00    --  103.18 -94.00 120.00   77
 15  \w     61.00 143.00   1.00   20.00    --  103.18 178.00 -30.00   82
 16  \w    112.00 140.00   1.00   20.00    --  103.18  77.00-120.00   28
 17  \w    112.00 169.00   1.00   20.00    --  103.18  77.00 120.00   57
;
_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      0.0603878000
_diffrn_orient_matrix_UB_12      0.0607635000
_diffrn_orient_matrix_UB_13      -0.0221414000
_diffrn_orient_matrix_UB_21      0.0092247000
_diffrn_orient_matrix_UB_22      -0.0807408000
_diffrn_orient_matrix_UB_23      -0.0326680000
_diffrn_orient_matrix_UB_31      -0.0626336000
_diffrn_orient_matrix_UB_32      0.0467204000
_diffrn_orient_matrix_UB_33      -0.0278007000
_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  0.0369
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            42724
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.539
_diffrn_reflns_theta_min         2.772
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.474
_exptl_absorpt_correction_T_max  0.507
_exptl_absorpt_correction_T_min  0.352
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (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 dark orange'
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       prism
_exptl_crystal_F_000             3120
_exptl_crystal_size_max          0.314
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.188
_refine_diff_density_max         0.730
_refine_diff_density_min         -0.467
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     868
_refine_ls_number_reflns         15006
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0412
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0434P)^2^+5.1014P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0997
_refine_ls_wR_factor_ref         0.1069
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11807
_reflns_number_total             15006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mk1061
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_original_formula_sum        'C87 H73.50 N4.50 O4 Si4 Tb'
_cod_database_code               1571351
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C87 H75.5 N4.5 O4 Si4 Tb1'
_shelx_estimated_absorpt_t_max   0.426
_shelx_estimated_absorpt_t_min   0.278
_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. Rigid body (RIGU) restrains
 C31, C32, C33, C34, C35, C36
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.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), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78)
3.b Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 128 electrons were 
found in a volume of 996\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.5[CH3CN] per Asymmetric Unit 
which account for 132 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80092
_shelx_fab_checksum              87024
_olex2_date_sample_data_collection 2023-08-22
_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 1.492
_oxdiff_exptl_absorpt_empirical_full_min 0.701