Structure, reactivity and luminescence studies of triphenylsiloxide complexes of tetravalent lanthanides
Willauer, Aurélien R.; Douair, Iskander; Chauvin, Anne-Sophie; Fadaei-Tirani, Farzaneh; Bünzli, Jean-Claude G.; Maron, Laurent; Mazzanti, Marinella; Chemical Science 13 (2022) 681–691; doi:10.1039/D1SC05517H

data_1565791
_publ_section_title
;
 Structure, reactivity and luminescence studies of triphenylsiloxide
 complexes of tetravalent lanthanides
;
_journal_issue                   3
_journal_name_full               'Chemical Science'
_journal_page_first              681
_journal_page_last               691
_journal_paper_doi               10.1039/D1SC05517H
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C80 H76 O6 Si4 Tb, C4 H8 O'
_chemical_formula_sum            'C84 H84 O7 Si4 Tb'
_chemical_formula_weight         1476.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-21
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-22 deposited with the CCDC.	2021-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.923(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4450(4)
_cell_length_b                   23.0841(7)
_cell_length_c                   21.7459(6)
_cell_measurement_reflns_used    5910
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      71.6550
_cell_measurement_theta_min      3.2470
_cell_volume                     8211.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.981
_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    -32.00  -6.00   1.00   10.00    --  -43.13 125.00 -60.00   26
  2  \w    -84.00 -53.00   1.00   10.00    --  -43.13 125.00 -60.00   31
  3  \w    -70.00  27.00   1.00   10.00    --  -43.13  57.00-120.00   97
  4  \w   -115.00 -21.00   1.00   10.00    --  -43.13 -57.00  90.00   94
  5  \w    -31.00  60.00   1.00   10.00    --   43.13 -37.00 -60.00   91
  6  \w    114.00 177.00   1.00   40.00    --  103.80  77.00-180.00   63
  7  \w     84.00 130.00   1.00   40.00    --  103.80 178.00 -90.00   46
  8  \w    109.00 171.00   1.00   40.00    --  103.80  77.00  30.00   62
  9  \w     81.00 106.00   1.00   40.00    --  103.80-111.00-180.00   25
 10  \w     35.00  61.00   1.00   40.00    --  103.80 -94.00   0.00   26
 11  \w     52.00 127.00   1.00   40.00    --  103.80 -61.00  30.00   75
 12  \w     43.00 107.00   1.00   40.00    --  103.80 -94.00 -60.00   64
 13  \w     25.00 156.00   1.00   40.00    --  103.80 -15.00  30.00  131
 14  \w     83.00 108.00   1.00   40.00    --  103.80-111.00  90.00   25
 15  \w    111.00 138.00   1.00   40.00    --  103.80  77.00-120.00   27
 16  \w     86.00 133.00   1.00   40.00    --  103.80 178.00 120.00   47
 17  \w    114.00 140.00   1.00   40.00    --  103.80 111.00   0.00   26
 18  \w    143.00 174.00   1.00   40.00    --  103.80 111.00   0.00   31
 19  \w     28.00 120.00   1.00   40.00    --  103.80 -30.00-120.00   92
 20  \w     81.00 107.00   1.00   40.00    --  103.80 -94.00   0.00   26
 21  \w     77.00 108.00   1.00   40.00    --  103.80-106.00-117.35   31
 22  \w     28.00  76.00   1.00   40.00    --  103.80-106.00-117.35   48
;
_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      0.0139686000
_diffrn_orient_matrix_UB_12      -0.0368207000
_diffrn_orient_matrix_UB_13      0.0592411000
_diffrn_orient_matrix_UB_21      -0.0026613000
_diffrn_orient_matrix_UB_22      0.0551846000
_diffrn_orient_matrix_UB_23      0.0395526000
_diffrn_orient_matrix_UB_31      -0.0931119000
_diffrn_orient_matrix_UB_32      -0.0071253000
_diffrn_orient_matrix_UB_33      0.0003247000
_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  0.0841
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            30838
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.561
_diffrn_reflns_theta_min         3.742
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.179
_exptl_absorpt_correction_T_max  0.831
_exptl_absorpt_correction_T_min  0.626
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
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 intense orange'
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       prism
_exptl_crystal_F_000             3060
_exptl_crystal_size_max          0.137
_exptl_crystal_size_mid          0.064
_exptl_crystal_size_min          0.045
_refine_diff_density_max         0.935
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         8008
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      0.927
_refine_ls_R_factor_all          0.0699
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0471P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0904
_refine_ls_wR_factor_ref         0.0988
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5726
_reflns_number_total             8008
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05517h2.cif
_cod_data_source_block           aw778
_cod_depositor_comments
'Adding full bibliography for 1565790--1565796.cif.'
_cod_database_code               1565791
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C92 H100 O9 Si4 Tb1'
_shelx_estimated_absorpt_t_max   0.800
_shelx_estimated_absorpt_t_min   0.537
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C38-C37 \\sim C41-C37 \\sim C39-C38 \\sim C42-C41 \\sim C40-C39 \\sim C42-C40
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O3 \\sim C37 \\sim C38 \\sim C41 \\sim C42 \\sim C39 \\sim C40: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(O4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H37C)=Sof(H37D)=Sof(H40C)=Sof(H40D)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=1-FVAR(1)
 Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H40A)=Sof(H40B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C37(H37C,H37D), C38(H38A,H38B), C39(H39A,H39B), C40(H40A,
 H40B), C40(H40C,H40D), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), 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),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 312 electrons were 
found in a volume of 1350\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C4H8O] per Asymmetric Unit 
which account for 320 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              13289
_shelx_hkl_checksum              99492
_shelx_fab_checksum              12986
_olex2_date_sample_data_collection 2021-01-22
_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 1.187
_oxdiff_exptl_absorpt_empirical_full_min 0.765