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_1565795
_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         'C84 H84 Gd K O7 Si4'
_chemical_formula_sum            'C84 H84 Gd K O7 Si4'
_chemical_formula_weight         1514.22
_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             2021-06-04
_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                 100.959(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4724(4)
_cell_length_b                   28.4527(9)
_cell_length_c                   22.4563(8)
_cell_measurement_reflns_used    10797
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      70.0690
_cell_measurement_theta_min      3.5060
_cell_volume                     8451.1(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (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 0.985
_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    -78.00  32.00   1.00   10.00    --  -42.88  85.00 174.00  110
  2  \w      9.00  34.00   1.00   10.00    --   42.88 -85.00  56.00   25
  3  \w     54.00 120.00   1.00   40.00    --  103.80 -85.00  56.00   66
  4  \w    103.00 142.00   1.00   40.00    --  103.80  85.00 174.00   39
  5  \w   -117.00 -23.00   1.00   10.00    --  -42.88 -37.00  30.00   94
  6  \w    -74.00  -9.00   1.00   10.00    --  -42.88 125.00 -60.00   65
  7  \w     37.00  64.00   1.00   10.00    --   42.88 -99.00 -90.00   27
  8  \w     16.00 116.00   1.00   10.00    --   42.88  57.00 -60.00  100
  9  \w    109.00 174.00   1.00   40.00    --  103.80  77.00 -30.00   65
 10  \w     26.00 106.00   1.00   40.00    --  103.80 -94.00 -30.00   80
 11  \w     24.00  72.00   1.00   40.00    --  103.80 -94.00-120.00   48
 12  \w     26.00 107.00   1.00   40.00    --  103.80 -94.00-180.00   81
 13  \w    110.00 165.00   1.00   40.00    --  103.80  77.00  30.00   55
 14  \w     31.00 108.00   1.00   40.00    --  103.80-111.00  60.00   77
 15  \w    107.00 134.00   1.00   40.00    --  103.80  77.00 -90.00   27
 16  \w    150.00 176.00   1.00   40.00    --  103.80  77.00 -90.00   26
 17  \w     58.00 108.00   1.00   40.00    --  103.80-111.00 150.00   50
 18  \w     46.00 108.00   1.00   40.00    --  103.80-111.00 -60.00   62
 19  \w     30.00 131.00   1.00   40.00    --  103.80 -30.00   0.00  101
 20  \w    105.00 176.00   1.00   40.00    --  103.80  77.00 120.00   71
 21  \w    136.00 161.00   1.00   40.00    --  103.80 111.00 120.00   25
 22  \w     83.00 108.00   1.00   40.00    --  103.80-111.00 -30.00   25
 23  \w    115.00 172.00   1.00   40.00    --  103.80  77.00  60.00   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      0.0035898000
_diffrn_orient_matrix_UB_12      0.0208622000
_diffrn_orient_matrix_UB_13      -0.0628339000
_diffrn_orient_matrix_UB_21      -0.0567734000
_diffrn_orient_matrix_UB_22      -0.0433127000
_diffrn_orient_matrix_UB_23      -0.0304401000
_diffrn_orient_matrix_UB_31      -0.1017078000
_diffrn_orient_matrix_UB_32      0.0249443000
_diffrn_orient_matrix_UB_33      -0.0004031000
_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  0.1171
_diffrn_reflns_av_unetI/netI     0.0962
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            72125
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.769
_diffrn_reflns_theta_min         3.106
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.438
_exptl_absorpt_correction_T_max  0.842
_exptl_absorpt_correction_T_min  0.364
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (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 pale colourless'
_exptl_crystal_density_diffrn    1.190
_exptl_crystal_description       needle
_exptl_crystal_F_000             3132
_exptl_crystal_size_max          0.363
_exptl_crystal_size_mid          0.038
_exptl_crystal_size_min          0.031
_refine_diff_density_max         1.159
_refine_diff_density_min         -0.945
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.948
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         16567
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      0.948
_refine_ls_R_factor_all          0.0970
_refine_ls_R_factor_gt           0.0531
_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^)+(0.0675P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1207
_refine_ls_wR_factor_ref         0.1413
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10539
_reflns_number_total             16567
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05517h2.cif
_cod_data_source_block           aw828-1
_cod_depositor_comments
'Adding full bibliography for 1565790--1565796.cif.'
_cod_database_code               1565795
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C92 H100 O9 Si4 K1 Gd1'
_shelx_estimated_absorpt_t_max   0.825
_shelx_estimated_absorpt_t_min   0.203
_reflns_odcompleteness_completeness 99.97
_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
 C83-C84 \\sim C86-C84 \\sim C82-C83 \\sim C86-C85 \\sim C85-C81 \\sim C82-C81
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(H81C)=Sof(H81D)=Sof(H84C)=Sof(H84D)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C86)=
 Sof(H86A)=Sof(H86B)=1-FVAR(1)
 Sof(H81A)=Sof(H81B)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(C83)=Sof(H83A)=Sof(H83B)=
 Sof(H84A)=Sof(H84B)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,
 H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B),
 C81(H81C,H81D), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B), C84(H84C,H84D),
  C85(H85A,H85B), C86(H86A,H86B)
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), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), 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)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 304 electrons were 
found in a volume of 1492\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[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              64286
_shelx_hkl_checksum              12904
_shelx_fab_checksum              3944
_olex2_date_sample_data_collection 2021-05-21
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.639
_oxdiff_exptl_absorpt_empirical_full_min 0.541