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_1565790
_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 K Nd O6 Si4, 3[C7H8]'
_chemical_formula_sum            'C80 H76 K Nd O6 Si4'
_chemical_formula_weight         1429.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-31
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-08-22 deposited with the CCDC.	2021-12-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.8279(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.07667(12)
_cell_length_b                   18.20509(11)
_cell_length_c                   36.5229(3)
_cell_measurement_reflns_used    40561
_cell_measurement_temperature    139.99(11)
_cell_measurement_theta_max      72.4850
_cell_measurement_theta_min      3.6360
_cell_volume                     9988.95(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.984
_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    -67.00   7.00   1.00    4.00    --  -40.91 109.00  -0.00   74
  2  \w     31.00  79.00   1.00    4.00    --   40.91-109.00 -95.00   48
  3  \w     64.00 102.00   1.00   16.00    --  105.15-109.00 -95.00   38
  4  \w    116.00 145.00   1.00   16.00    --  105.15 109.00  -0.00   29
  5  \w   -113.00 -18.00   1.00    4.00    --  -40.91 -38.00-150.00   95
  6  \w   -105.00 -32.00   1.00    4.00    --  -40.91 -38.00 -60.00   73
  7  \w     13.00 111.00   1.00    4.00    --   40.91  57.00 150.00   98
  8  \w     83.00 132.00   1.00   16.00    --  105.15 -30.00-120.00   49
  9  \w     56.00 106.00   1.00   16.00    --  105.15 -94.00   0.00   50
 10  \w     30.00  55.00   1.00   16.00    --  105.15 -77.00 -60.00   25
 11  \w     72.00 137.00   1.00   16.00    --  105.15 178.00 -90.00   65
 12  \w     72.00  99.00   1.00   16.00    --  105.15 178.00-150.00   27
 13  \w    117.00 143.00   1.00   16.00    --  105.15 178.00-150.00   26
 14  \w     34.00  86.00   1.00   16.00    --  105.15 -61.00-180.00   52
 15  \w     85.00 173.00   1.00   16.00    --  105.15  30.00-180.00   88
 16  \w    103.00 177.00   1.00   16.00    --  105.15  77.00  90.00   74
 17  \w     79.00 177.00   1.00   16.00    --  105.15  45.00  60.00   98
 18  \w     58.00 116.00   1.00   16.00    --  105.15 -77.00 -60.00   58
 19  \w     42.00  68.00   1.00   16.00    --  105.15 -30.00-120.00   26
 20  \w     81.00 106.00   1.00   16.00    --  105.15-111.00-180.00   25
 21  \w     35.00 109.00   1.00   16.00    --  105.15-111.00 -60.00   74
 22  \w     51.00  76.00   1.00   16.00    --  105.15-111.00  60.00   25
 23  \w     85.00 110.00   1.00   16.00    --  105.15  30.00   0.00   25
 24  \w    151.00 176.00   1.00   16.00    --  105.15  30.00   0.00   25
 25  \w     49.00 109.00   1.00   16.00    --  105.15-111.00  90.00   60
 26  \w     32.00 112.00   1.00   16.00    --  105.15 -45.00  30.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0672739000
_diffrn_orient_matrix_UB_12      -0.0213250000
_diffrn_orient_matrix_UB_13      -0.0276858000
_diffrn_orient_matrix_UB_21      0.0763074000
_diffrn_orient_matrix_UB_22      0.0050646000
_diffrn_orient_matrix_UB_23      0.0306968000
_diffrn_orient_matrix_UB_31      -0.0128347000
_diffrn_orient_matrix_UB_32      -0.0817511000
_diffrn_orient_matrix_UB_33      0.0090932000
_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  0.0302
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            84946
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.870
_diffrn_reflns_theta_min         3.434
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.091
_exptl_absorpt_correction_T_max  0.911
_exptl_absorpt_correction_T_min  0.270
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
 Numerical absorption correction based on Gaussian integration over
 a multifaceted crystal model.
 Empirical absorption correction using spherical harmonics
 as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    0.950
_exptl_crystal_description       prism
_exptl_crystal_F_000             2956
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.238
_exptl_crystal_size_min          0.132
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.729
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         19622
_refine_ls_number_restraints     823
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0435
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0837P)^2^+6.5657P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1228
_refine_ls_wR_factor_ref         0.1248
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18427
_reflns_number_total             19622
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05517h2.cif
_cod_data_source_block           aw609
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1565790--1565796.cif.
;
_cod_original_cell_volume        9988.94(12)
_cod_database_code               1565790
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C115 H116 K Nd O6 Si4'
_shelx_estimated_absorpt_t_max   0.553
_shelx_estimated_absorpt_t_min   0.252
_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
2. Restrained distances
 O5-C73A = O5-C76A = O5-C73B = O5-C76B
 1.44 with sigma of 0.02
 O6-C80A = O6-C77A = O6-C80B = O6-C77B
 1.44 with sigma of 0.02
 C79A-C78A = C79B-C78B
 1.54 with sigma of 0.02
 C80A-C79A = C78A-C77A = C80B-C79B = C78B-C77B
 1.53 with sigma of 0.02
 C73B-C74B = C75B-C76B = C73A-C74A = C75A-C76A
 1.53 with sigma of 0.02
 C74B-C75B = C74A-C75A
 1.54 with sigma of 0.02
 O6-C79A = O6-C78A = C80A-C78A = C79A-C77A = O6-C79B = O6-C78B = C80B-C78B =
 C79B-C77B
 2.38 with sigma of 0.04
 C73B-C75B = C74B-C76B = O5-C74A = O5-C75A = C73A-C75A = C74A-C76A
 2.38 with sigma of 0.04
 Si1-C13A \\sim Si1-C13B
 with sigma of 0.02
 Si2-C31A \\sim Si2-C31B
 with sigma of 0.02
 Si3-C49A \\sim Si3-C49B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim C13B \\sim
C14B \\sim C15B \\sim C16B \\sim C17B \\sim C18B \\sim C31A \\sim C32A \\sim
C33A \\sim C34A \\sim C35A \\sim C36A \\sim C31B \\sim C32B \\sim C33B \\sim
C34B \\sim C35B \\sim C36B \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim
C53A \\sim C54A \\sim C49B \\sim C50B \\sim C51B \\sim C52B \\sim C53B \\sim
C54B \\sim O5 \\sim C76A \\sim C75A \\sim C74A \\sim C73A \\sim C76B \\sim C75B
\\sim C74B \\sim C73B \\sim O6 \\sim C80A \\sim C79A \\sim C78A \\sim C77A
\\sim C80B \\sim C79B \\sim C78B \\sim C77B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C13B)=Sof(C18B)=Sof(H18B)=Sof(C17B)=Sof(H17B)=Sof(C16B)=Sof(H16B)=
 Sof(C15B)=Sof(H15B)=Sof(C14B)=Sof(H14B)=Sof(C31B)=Sof(C36B)=Sof(H36B)=
 Sof(C35B)=Sof(H35B)=Sof(C34B)=Sof(H34B)=Sof(C33B)=Sof(H33B)=Sof(C32B)=
 Sof(H32B)=Sof(C49B)=Sof(C54B)=Sof(H54B)=Sof(C53B)=Sof(H53B)=Sof(C52B)=
 Sof(H52B)=Sof(C51B)=Sof(H51B)=Sof(C50B)=Sof(H50B)=1-FVAR(1)
 Sof(C13A)=Sof(C18A)=Sof(H18A)=Sof(C17A)=Sof(H17A)=Sof(C16A)=Sof(H16A)=
 Sof(C15A)=Sof(H15A)=Sof(C14A)=Sof(H14A)=Sof(C31A)=Sof(C36A)=Sof(H36A)=
 Sof(C35A)=Sof(H35A)=Sof(C34A)=Sof(H34A)=Sof(C33A)=Sof(H33A)=Sof(C32A)=
 Sof(H32A)=Sof(C49A)=Sof(C54A)=Sof(H54A)=Sof(C53A)=Sof(H53A)=Sof(C52A)=
 Sof(H52A)=Sof(C51A)=Sof(H51A)=Sof(C50A)=Sof(H50A)=FVAR(1)
 Sof(C73B)=Sof(H73C)=Sof(H73D)=Sof(C74B)=Sof(H74C)=Sof(H74D)=Sof(C75B)=
 Sof(H75C)=Sof(H75D)=Sof(C76B)=Sof(H76C)=Sof(H76D)=Sof(C77B)=Sof(H77C)=
 Sof(H77D)=Sof(C78B)=Sof(H78C)=Sof(H78D)=Sof(C79B)=Sof(H79C)=Sof(H79D)=
 Sof(C80B)=Sof(H80C)=Sof(H80D)=1-FVAR(2)
 Sof(C73A)=Sof(H73A)=Sof(H73B)=Sof(C74A)=Sof(H74A)=Sof(H74B)=Sof(C75A)=
 Sof(H75A)=Sof(H75B)=Sof(C76A)=Sof(H76A)=Sof(H76B)=Sof(C77A)=Sof(H77A)=
 Sof(H77B)=Sof(C78A)=Sof(H78A)=Sof(H78B)=Sof(C79A)=Sof(H79A)=Sof(H79B)=
 Sof(C80A)=Sof(H80A)=Sof(H80B)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C73A(H73A,H73B), C73B(H73C,H73D), C74A(H74A,H74B), C74B(H74C,H74D), C75A(H75A,
 H75B), C75B(H75C,H75D), C76A(H76A,H76B), C76B(H76C,H76D), C77A(H77A,H77B),
 C77B(H77C,H77D), C78A(H78A,H78B), C78B(H78C,H78D), C79A(H79A,H79B), C79B(H79C,
 H79D), C80A(H80A,H80B), C80B(H80C,H80D)
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), C18A(H18A), C17A(H17A), C16A(H16A), C15A(H15A), C14A(H14A),
 C18B(H18B), C17B(H17B), C16B(H16B), C15B(H15B), C14B(H14B), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C36A(H36A), C35A(H35A), C34A(H34A), C33A(H33A), C32A(H32A),
 C36B(H36B), C35B(H35B), C34B(H34B), C33B(H33B), C32B(H32B), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C54A(H54A), C53A(H53A), C52A(H52A), C51A(H51A), C50A(H50A),
 C54B(H54B), C53B(H53B), C52B(H52B), C51B(H51B), C50B(H50B), 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)
5.c Fitted hexagon refined as free rotating group:
 C13A(C18A,C17A,C16A,C15A,C14A), C13B(C18B,C17B,C16B,C15B,C14B), C31A(C36A,
 C35A,C34A,C33A,C32A), C31B(C36B,C35B,C34B,C33B,C32B), C49A(C54A,C53A,C52A,C51A,
 C50A), C49B(C54B,C53B,C52B,C51B,C50B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              45887
_shelx_hkl_checksum              22878
_shelx_fab_checksum              23680
_olex2_date_sample_data_collection 2020-03-03
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.775