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_1571348
_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 Pr Si3, 2(C7 H8)'
_chemical_formula_sum            'C86 H85 O6 Pr Si3'
_chemical_formula_weight         1439.71
_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             2023-09-19
_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                106.237(3)
_cell_angle_beta                 99.362(3)
_cell_angle_gamma                93.699(3)
_cell_formula_units_Z            2
_cell_length_a                   11.1967(4)
_cell_length_b                   14.3423(5)
_cell_length_c                   24.4587(6)
_cell_measurement_reflns_used    20542
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      72.3070
_cell_measurement_theta_min      3.1710
_cell_volume                     3695.7(2)
_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      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.974
_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   -115.00 -66.00   1.00    5.00    --  -43.01-140.00 -38.00   49
  2  \w    -98.00 -54.00   1.00    5.00    --  -43.01 140.00  21.00   44
  3  \w    -73.00 -48.00   1.00    5.00    --  -43.01 129.00-152.00   25
  4  \w     41.00  66.00   1.00    5.00    --   43.01-129.00 135.00   25
  5  \w     71.00  96.00   1.00    5.00    --   43.01-140.00 -38.00   25
  6  \w     94.00 131.00   1.00   20.00    --  103.18 140.00  21.00   37
  7  \w     70.00 112.00   1.00   20.00    --  103.18-129.00 135.00   42
  8  \w    111.00 136.00   1.00   20.00    --  103.18 129.00-152.00   25
  9  \w     68.00 116.00   1.00   20.00    --  103.18-140.00 -38.00   48
 10  \w    -66.00  31.00   1.00    5.00    --  -43.01  37.00 -30.00   97
 11  \w   -115.00 -20.00   1.00    5.00    --  -43.01 -37.00 -30.00   95
 12  \w     20.00 113.00   1.00    5.00    --   43.01  37.00-150.00   93
 13  \w    126.00 175.00   1.00   20.00    --  103.18 111.00 -30.00   49
 14  \w     42.00 109.00   1.00   20.00    --  103.18-111.00-180.00   67
 15  \w     37.00  79.00   1.00   20.00    --  103.18 -61.00-180.00   42
 16  \w     80.00 177.00   1.00   20.00    --  103.18  30.00-150.00   97
 17  \w     36.00  80.00   1.00   20.00    --  103.18-111.00  30.00   44
 18  \w     34.00 115.00   1.00   20.00    --  103.18 -30.00-180.00   81
 19  \w     33.00 121.00   1.00   20.00    --  103.18 -30.00 -30.00   88
 20  \w     86.00 135.00   1.00   20.00    --  103.18 -77.00 -60.00   49
 21  \w    104.00 167.00   1.00   20.00    --  103.18 111.00-120.00   63
 22  \w    107.00 163.00   1.00   20.00    --  103.18 111.00  90.00   56
 23  \w     57.00 109.00   1.00   20.00    --  103.18-111.00 -30.00   52
 24  \w     86.00 164.00   1.00   20.00    --  103.18  45.00 150.00   78
;
_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      0.0243071000
_diffrn_orient_matrix_UB_12      0.0493166000
_diffrn_orient_matrix_UB_13      0.0659908000
_diffrn_orient_matrix_UB_21      -0.0484336000
_diffrn_orient_matrix_UB_22      0.0931398000
_diffrn_orient_matrix_UB_23      -0.0100740000
_diffrn_orient_matrix_UB_31      -0.1295174000
_diffrn_orient_matrix_UB_32      -0.0397525000
_diffrn_orient_matrix_UB_33      0.0024941000
_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  0.0257
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            32715
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.480
_diffrn_reflns_theta_min         3.231
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.938
_exptl_absorpt_correction_T_max  0.751
_exptl_absorpt_correction_T_min  0.608
_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    1.294
_exptl_crystal_description       prism
_exptl_crystal_F_000             1500
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.107
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.630
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     942
_refine_ls_number_reflns         14258
_refine_ls_number_restraints     418
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0312
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0411P)^2^+0.4214P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0668
_refine_ls_wR_factor_ref         0.0692
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13154
_reflns_number_total             14258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-245
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_database_code               1571348
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C86 H85 O6 Si3 Pr1'
_shelx_estimated_absorpt_t_max   0.725
_shelx_estimated_absorpt_t_min   0.536
_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
 C84-C90 = C97-C91
 1.5 with sigma of 0.02
 C96-C97
 2.5 with sigma of 0.02
 C92-C97
 2.5 with sigma of 0.02
 C69-C70 \\sim C74-C73 \\sim C75-C74 \\sim C70-C71 \\sim C76-C75 \\sim C72-C71
 with sigma of 0.02
 O6-C69 \\sim O6-C73 \\sim O6-C72 \\sim O6-C76
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim
C96 \\sim C95 \\sim C94 \\sim C93 \\sim C92 \\sim C97: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O6 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim
C76: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C78, C77, C82, C83, C79, C81, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 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)=1-FVAR(1)
 Sof(C84)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=
 Sof(H88)=Sof(C89)=Sof(H89)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=FVAR(1)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=
 Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=1-FVAR(2)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(H71A)=
 Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=FVAR(2)
 Fixed X: Pr1(0.59167)
 Fixed Y: Pr1(0.53889)
 Fixed Z: Pr1(0.75857)
6.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), 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)
6.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), C78(H78),
  C79(H79), C80(H80), C81(H81), C82(H82), C85(H85), C86(H86), C87(H87),
 C88(H88), C89(H89), C96(H96), C95(H95), C94(H94), C93(H93), C92(H92)
6.c Fitted hexagon refined as free rotating group:
 C84(C85,C86,C87,C88,C89), C91(C96,C95,C94,C93,C92)
6.d Idealised Me refined as rotating group:
 C83(H83A,H83B,H83C), C90(H90A,H90B,H90C), C97(H97A,H97B,H97C)
;
_shelx_res_checksum              26754
_olex2_date_sample_data_collection 2023-03-09
_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 1.166
_oxdiff_exptl_absorpt_empirical_full_min 0.860