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_1571352
_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         'C84 H69 K N3 O4 Pr Si4, C2 H3 N, 3[CH3CN]'
_chemical_formula_sum            'C92 H81 K N7 O4 Pr Si4'
_chemical_formula_weight         1641.00
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-09-12
_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                 100.1850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.65640(10)
_cell_length_b                   43.2742(5)
_cell_length_c                   14.24030(10)
_cell_measurement_reflns_used    39035
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      75.5260
_cell_measurement_theta_min      2.0220
_cell_volume                     8282.97(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.99(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 0.974
_diffrn_measured_fraction_theta_max 0.963
_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    -60.00 -35.00   0.50    0.50    --  -71.07   0.00-120.00   50
  2  \w    -77.00 -45.00   0.50    0.50    --  -71.07  97.00 -34.00   64
  3  \w    -60.00 -27.00   0.50    0.50    --  -64.90  97.00 -34.00   66
  4  \w    -68.00 -42.00   0.50    0.50    --  -76.25  90.00 104.66   52
  5  \w    -66.00 -41.00   0.50    0.50    --  -76.25  61.00 125.54   50
  6  \w    -54.00 -28.00   0.50    0.50    --  -64.90   0.00-150.00   52
  7  \w    -80.00 -55.00   0.50    0.50    --  -48.00 -72.00 -78.04   50
  8  \w   -114.00 -87.00   0.50    0.50    --  -76.25 -65.00 -35.70   54
  9  \w   -110.00 -85.00   0.50    0.50    --  -68.00 -58.00 -68.62   50
 10  \w   -113.00 -87.00   0.50    0.50    --  -72.00 -62.00  72.82   52
 11  \w   -118.00 -92.00   0.50    0.50    --  -76.25 -51.00   3.11   52
 12  \w   -118.00 -92.00   0.50    0.50    --  -72.00 -40.00  23.91   52
 13  \w    -92.00 -67.00   0.50    0.50    --  -52.00 -64.00 155.34   50
 14  \w     49.00  77.00   0.50    0.50    --   79.75  14.00  -1.45   56
 15  \w     89.00 118.00   0.50    0.50    --   79.75  67.00-124.34   58
 16  \w     46.00  77.00   0.50    0.50    --   40.00  72.00 -88.22   62
 17  \w     85.00 111.00   0.50    0.50    --   79.75  76.00 -22.01   52
 18  \w     89.00 114.00   0.50    0.50    --   79.75  61.00  42.00   50
 19  \w     90.00 116.00   0.50    0.50    --   79.75  69.00 100.04   52
 20  \w     45.00  73.00   0.50    0.50    --   36.00  67.00 158.12   56
 21  \w     89.00 114.00   0.50    0.50    --   79.75  60.00 143.48   50
 22  \w     84.00 110.00   0.50    0.50    --   79.75  27.00 127.20   52
 23  \w     94.00 119.00   0.50    0.50    --   79.75  27.00  92.97   50
 24  \w     74.00 126.00   0.50    0.50    --   79.75  25.00  42.42  104
 25  \w     91.00 118.00   0.50    0.50    --   79.75  47.00 -48.35   54
 26  \w     96.00 124.00   0.50    0.50    --   79.75  36.00-170.50   56
 27  \w    100.00 126.00   0.50    0.50    --   79.75  25.00-179.26   52
 28  \w     47.00  80.00   0.50    0.50    --   79.75  17.00 -80.40   66
 29  \w     92.00 118.00   0.50    0.50    --   79.75  26.00-104.75   52
 30  \w    100.00 126.00   0.50    0.50    --   79.75  17.00 -80.40   52
 31  \w     83.00 111.00   0.50    0.50    --   79.75  14.00  -1.45   56
 32  \w     39.00  64.00   0.50    0.50    --   79.75 -57.00  35.48   50
 33  \w     45.00  70.00   0.50    0.50    --   79.75 -78.00  71.76   50
 34  \w     62.00  88.00   0.50    0.50    --   79.75-128.00  -9.71   52
 35  \w     45.00  89.00   0.50    0.50    --   79.75-112.00 -10.81   88
 36  \w     68.00  94.00   0.50    0.50    --   76.57-125.00 -30.00   52
 37  \w     52.00  96.00   0.50    0.50    --   79.75-109.00 -79.90   88
 38  \w     79.00 105.00   0.50    0.50    --   79.75-123.00 -96.30   52
 39  \w     53.00 104.00   0.50    0.50    --   79.75-121.00-123.78  102
 40  \w     28.00  71.00   0.50    0.50    --   63.98 -97.00-141.00   86
 41  \w     38.00  63.00   0.50    0.50    --   75.80 -97.00-141.00   50
 42  \w     39.00  64.00   0.50    0.50    --   76.57 -97.00-141.00   50
 43  \w     44.00  73.00   0.50    0.50    --   79.75 -72.00-104.84   58
 44  \w     59.00  84.00   0.50    0.50    --   75.80 -95.00 150.00   50
;
_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      -0.1133058000
_diffrn_orient_matrix_UB_12      0.0012975000
_diffrn_orient_matrix_UB_13      -0.0032244000
_diffrn_orient_matrix_UB_21      -0.0096488000
_diffrn_orient_matrix_UB_22      -0.0334386000
_diffrn_orient_matrix_UB_23      -0.0375708000
_diffrn_orient_matrix_UB_31      0.0144689000
_diffrn_orient_matrix_UB_32      -0.0121204000
_diffrn_orient_matrix_UB_33      0.1032401000
_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  0.0684
_diffrn_reflns_av_unetI/netI     0.0420
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       54
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            84003
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.748
_diffrn_reflns_theta_min         3.314
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.951
_exptl_absorpt_correction_T_max  0.806
_exptl_absorpt_correction_T_min  0.386
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (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 pale colourless'
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       prism
_exptl_crystal_F_000             3392
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.082
_refine_diff_density_max         1.523
_refine_diff_density_min         -1.476
_refine_diff_density_rms         0.104
_refine_ls_extinction_coef       0.00014(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     906
_refine_ls_number_reflns         16596
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0597
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0834P)^2^+23.5686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1539
_refine_ls_wR_factor_ref         0.1610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14190
_reflns_number_total             16596
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 5.1219\% 
around [-0.60 -0.51 0.62] (reciprocal) or [-0.72 -0.07 0.69] (direct)
Component 3 rotated by 2.5243\% 
around [-0.01 -0.44 0.90] (reciprocal) or [0.17 -0.05 0.98] (direct)
;
_cod_data_source_file            d4sc00051j2.cif
_cod_data_source_block           mt-364
_cod_depositor_comments
'Adding full bibliography for 1571342--1571354.cif.'
_cod_database_code               1571352
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C92 H86 N5 O5 Si4 K1 Pr1'
_shelx_estimated_absorpt_t_max   0.641
_shelx_estimated_absorpt_t_min   0.284
_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.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)
2.b Idealised Me refined as rotating group:
 C80(H80A,H80B,H80C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C86(H86A,H86B,
 H86C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 248 electrons were 
found in a volume of 1252\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
3[CH3CN] per Asymmetric Unit 
which account for 264 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              51539
_shelx_fab_checksum              29270
_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 2.791
_oxdiff_exptl_absorpt_empirical_full_min 0.496
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               3