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_1565794
_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 Ce K O6 Si4, 2(C7 H8)'
_chemical_formula_sum            'C94 H92 Ce K O6 Si4'
_chemical_formula_weight         1609.25
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-07-07
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-08 deposited with the CCDC.	2021-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.5527(9)
_cell_length_b                   26.7995(12)
_cell_length_c                   38.849(2)
_cell_measurement_reflns_used    2474
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      71.7300
_cell_measurement_theta_min      3.2380
_cell_volume                     16192.4(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (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 0.999
_diffrn_measured_fraction_theta_max 0.978
_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    -21.00   9.00   1.00   15.00    --   43.13 -79.00-171.00   30
  2  \w     38.00 130.00   1.00   60.00    --  103.80 -46.00  24.00   92
  3  \w    126.00 170.00   1.00   60.00    --  103.80  79.00 -47.00   44
  4  \w     51.00 114.00   1.00   60.00    --  103.80 -79.00-171.00   63
  5  \w     50.00  76.00   1.00   60.00    --  103.80-108.00 -59.00   26
  6  \w   -106.00 -20.00   1.00   15.00    --  -43.13 -57.00 -60.00   86
  7  \w      8.00  62.00   1.00   15.00    --   43.13 -99.00  30.00   54
  8  \w    153.00 178.00   1.00   60.00    --  103.80 111.00-180.00   25
  9  \w    142.00 167.00   1.00   60.00    --  103.80 111.00   0.00   25
 10  \w    105.00 133.00   1.00   60.00    --  103.80 111.00-180.00   28
 11  \w     27.00 102.00   1.00   60.00    --  103.80-111.00  30.00   75
;
_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      0.0284168000
_diffrn_orient_matrix_UB_12      -0.0049868000
_diffrn_orient_matrix_UB_13      -0.0378386000
_diffrn_orient_matrix_UB_21      0.0796865000
_diffrn_orient_matrix_UB_22      0.0323841000
_diffrn_orient_matrix_UB_23      0.0075313000
_diffrn_orient_matrix_UB_31      0.0515096000
_diffrn_orient_matrix_UB_32      -0.0472248000
_diffrn_orient_matrix_UB_33      0.0092080000
_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  0.1776
_diffrn_reflns_av_unetI/netI     0.1639
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            54117
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.602
_diffrn_reflns_theta_min         3.298
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.796
_exptl_absorpt_correction_T_max  0.667
_exptl_absorpt_correction_T_min  0.456
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (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    1.320
_exptl_crystal_description       prism
_exptl_crystal_F_000             6696
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.823
_refine_diff_density_min         -0.797
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.980
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     998
_refine_ls_number_reflns         15729
_refine_ls_number_restraints     224
_refine_ls_restrained_S_all      0.974
_refine_ls_R_factor_all          0.1530
_refine_ls_R_factor_gt           0.0679
_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^)+(0.0613P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1426
_refine_ls_wR_factor_ref         0.1858
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8219
_reflns_number_total             15729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05517h2.cif
_cod_data_source_block           aw826-2
_cod_depositor_comments
'Adding full bibliography for 1565790--1565796.cif.'
_cod_original_cell_volume        16192.4(15)
_cod_database_code               1565794
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C94 H92 O6 Si4 K1 Ce1'
_shelx_estimated_absorpt_t_max   0.629
_shelx_estimated_absorpt_t_min   0.376
_reflns_odcompleteness_completeness 99.87
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C95-C101 = C94-C88
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C88 \\sim C93 \\sim C92 \\sim C91 \\sim C90 \\sim C89 \\sim C94 \\sim C95 \\sim
C100 \\sim C99 \\sim C98 \\sim C97 \\sim C96 \\sim C101: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C95)=Sof(C100)=Sof(H100)=Sof(C99)=Sof(H99)=Sof(C98)=Sof(H98)=Sof(C97)=
 Sof(H97)=Sof(C96)=Sof(H96)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=1-FVAR(1)
 Sof(C88)=Sof(C93)=Sof(H93)=Sof(C92)=Sof(H92)=Sof(C91)=Sof(H91)=Sof(C90)=
 Sof(H90)=Sof(C89)=Sof(H89)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=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)
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), C82(H82), C83(H83),
  C84(H84), C85(H85), C86(H86), C93(H93), C92(H92), C91(H91), C90(H90),
 C89(H89), C100(H100), C99(H99), C98(H98), C97(H97), C96(H96)
5.c Fitted hexagon refined as free rotating group:
 C88(C93,C92,C91,C90,C89), C95(C100,C99,C98,C97,C96)
5.d Idealised Me refined as rotating group:
 C87(H87A,H87B,H87C), C94(H94A,H94B,H94C), C101(H10A,H10B,H10C)
;
_shelx_res_checksum              23068
_shelx_hkl_checksum              7600
_olex2_date_sample_data_collection 2021-07-01
_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 1.230
_oxdiff_exptl_absorpt_empirical_full_min 0.845