Tripodal tris(siloxide) Ligand Supported Trivalent Rare-earth Metal Complexes and Redox Reactivity
Guo, Hui; Hong, Dongjing; Cui, Peng; Dalton Transactions  (2023) –; doi:10.1039/D3DT02519E

data_7714289
_publ_section_title
;
 Tripodal tris(siloxide) Ligand Supported Trivalent Rare-earth Metal
 Complexes and Redox Reactivity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02519E
_journal_year                    2023
_chemical_formula_moiety         'C68 H61 Ce Cl O5 Si3, 0.75[C4H8O]'
_chemical_formula_sum            'C68 H61 Ce Cl O5 Si3'
_chemical_formula_weight         1218.00
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-07-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-07-14 deposited with the CCDC.	2023-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                97.802(2)
_cell_angle_beta                 101.973(2)
_cell_angle_gamma                116.853(2)
_cell_formula_units_Z            2
_cell_length_a                   13.824(2)
_cell_length_b                   14.321(2)
_cell_length_c                   19.077(3)
_cell_measurement_reflns_used    3711
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      20.108
_cell_measurement_theta_min      2.234
_cell_volume                     3180.2(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART APEX II diffractrometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX II 300K'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1014
_diffrn_reflns_av_unetI/netI     0.1945
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            28414
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.713
_diffrn_reflns_theta_min         1.652
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.861
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4135
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1128 before and 0.0608 after correction.
The Ratio of minimum to maximum transmission is 0.5546.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_description       block
_exptl_crystal_F_000             1252
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.492
_refine_diff_density_min         -1.350
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.958
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     899
_refine_ls_number_reflns         14516
_refine_ls_number_restraints     1518
_refine_ls_restrained_S_all      0.917
_refine_ls_R_factor_all          0.1805
_refine_ls_R_factor_gt           0.0750
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0751P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1485
_refine_ls_wR_factor_ref         0.1903
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6840
_reflns_number_total             14516
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02519e2.cif
_cod_data_source_block           6
_cod_original_cell_volume        3180.1(9)
_cod_database_code               7714289
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.882
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Si3-C49A \\sim Si3-C49
 with sigma of 0.02
 Si3-C55A \\sim Si3-C55
 with sigma of 0.02
 C49A-C55A \\sim C49-C55
 with sigma of 0.02
 Si1-C19 \\sim Si1-C19A
 with sigma of 0.02
 Si1-C13 \\sim Si1-C13A
 with sigma of 0.02
 C19-C13 \\sim C19A-C13A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C61A \\sim C62A \\sim C63A
\\sim C64A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Si3 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C49A \\sim C50A \\sim C51A
\\sim C52A \\sim C53A \\sim C54A \\sim C55A \\sim C60A \\sim C59A \\sim C58A
\\sim C57A \\sim C56A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Si1 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C13A \\sim C14A \\sim C15A
\\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C24A \\sim C23A \\sim C22A
\\sim C21A \\sim C20A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O5 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C65A \\sim C66A \\sim C67A
\\sim C68A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Rigid body (RIGU) restrains
 O4, C61, C63, C64, C61A, C62A, C63A, C64A, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Si3, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C49A, C50A,
 C51A, C52A, C53A, C54A, C55A, C60A, C59A, C58A, C57A, C56A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Si1, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C13A, C14A,
 C15A, C16A, C17A, C18A, C19A, C24A, C23A, C22A, C21A, C20A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O5, C65, C66, C67, C68, C65A, C66A, C67A, C68A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Same fragment restrains
{C65A, C66A, C67A, C68A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C65, C66, C67, C68}
{C61A, C62A, C63A, C64A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C61, C62, C63, C64}
6. Others
 Sof(C49A)=Sof(C50A)=Sof(H50A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=
 Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(C60A)=Sof(H60A)=
 Sof(C59A)=Sof(H59A)=Sof(C58A)=Sof(H58A)=Sof(C57A)=Sof(H57A)=Sof(C56A)=
 Sof(H56A)=1-FVAR(1)
 Sof(C49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C53)=
 Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57)=
 Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=FVAR(1)
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(C24A)=Sof(H24A)=
 Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(H21A)=Sof(C20A)=
 Sof(H20A)=1-FVAR(2)
 Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(H17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=FVAR(2)
 Sof(C61A)=Sof(H61C)=Sof(H61D)=Sof(C62A)=Sof(H62C)=Sof(H62D)=Sof(C63A)=
 Sof(H63C)=Sof(H63D)=Sof(C64A)=Sof(H64C)=Sof(H64D)=1-FVAR(3)
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=FVAR(3)
 Sof(C65A)=Sof(H65C)=Sof(H65D)=Sof(C66A)=Sof(H66C)=Sof(H66D)=Sof(C67A)=
 Sof(H67C)=Sof(H67D)=Sof(C68A)=Sof(H68C)=Sof(H68D)=1-FVAR(4)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C67)=Sof(H67A)=
 Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C61(H61A,
 H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C61A(H61C,H61D),
 C62A(H62C,H62D), C63A(H63C,H63D), C64A(H64C,H64D), C65A(H65C,H65D), C66A(H66C,
 H66D), C67A(H67C,H67D), C68A(H68C,H68D)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), 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), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20),
  C21(H21), C22(H22), C23(H23), C24(H24), C50(H50), C51(H51), C52(H52),
 C53(H53), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60),
 C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C24A(H24A),
 C23A(H23A), C22A(H22A), C21A(H21A), C20A(H20A), C50A(H50A), C51A(H51A),
 C52A(H52A), C53A(H53A), C54A(H54A), C60A(H60A), C59A(H59A), C58A(H58A),
 C57A(H57A), C56A(H56A)
7.c Fitted hexagon refined as free rotating group:
 C13(C14,C15,C16,C17,C18), C19(C20,C21,C22,C23,C24), C49(C50,C51,C52,C53,C54),
 C55(C56,C57,C58,C59,C60), C13A(C14A,C15A,C16A,C17A,C18A), C19A(C24A,C23A,C22A,
 C21A,C20A), C49A(C50A,C51A,C52A,C53A,C54A), C55A(C60A,C59A,C58A,C57A,C56A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 61 electrons were 
found in a volume of 291\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.75[C4H8O] per Asymmetric Unit 
which account for 60 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24919
_shelx_fab_checksum              41716
_olex2_submission_special_instructions 'No special instructions were received'