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_7714287
_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         'C72 H69 O6 Pr Si3, 3[C4H8O]'
_chemical_formula_sum            'C72 H69 O6 Pr Si3'
_chemical_formula_weight         1255.45
_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
_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                90
_cell_angle_beta                 102.716(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.894(3)
_cell_length_b                   30.171(6)
_cell_length_c                   18.312(3)
_cell_measurement_reflns_used    9953
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      22.43
_cell_measurement_theta_min      2.28
_cell_volume                     8027(3)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_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  0.1592
_diffrn_reflns_av_unetI/netI     0.1477
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            68983
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.474
_diffrn_reflns_theta_min         1.325
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.692
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.3514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1114 before and 0.0700 after correction.
The Ratio of minimum to maximum transmission is 0.4713.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.039
_exptl_crystal_description       block
_exptl_crystal_F_000             2600
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.21
_refine_diff_density_max         1.497
_refine_diff_density_min         -1.115
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     972
_refine_ls_number_reflns         18199
_refine_ls_number_restraints     1686
_refine_ls_restrained_S_all      0.956
_refine_ls_R_factor_all          0.1555
_refine_ls_R_factor_gt           0.0792
_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^)+(0.0966P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1795
_refine_ls_wR_factor_ref         0.2132
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9006
_reflns_number_total             18199
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02519e2.cif
_cod_data_source_block           1
_cod_database_code               7714287
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.840
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Si1-C19A \\sim Si1-C19
 with sigma of 0.02
 Si1-C13A \\sim Si1-C13
 with sigma of 0.02
 Si2-C31A \\sim Si2-C31
 with sigma of 0.02
 Si2-C37 \\sim Si2-C37A
 with sigma of 0.02
 C37-C31 \\sim C37A-C31A
 with sigma of 0.02
 C13-C19 \\sim C13A-C19A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim
C39 \\sim C40 \\sim C41 \\sim C42 \\sim C31A \\sim C32A \\sim C33A \\sim C34A
\\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A
\\sim C42A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
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 C20A \\sim C21A \\sim C22A \\sim C23A
\\sim C24A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
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
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C69A \\sim C70A \\sim C71A \\sim C72A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
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
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C66A)
\\sim Ueq, Uanis(C67A) \\sim Ueq, Uanis(C68A) \\sim Ueq, Uanis(C65) \\sim Ueq,
Uanis(C65A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C69A) \\sim Ueq, Uanis(C70A) \\sim Ueq, Uanis(C71A) \\sim Ueq,
Uanis(C72A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 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
 O4, C61, C62, C63, C64, C61A, C62A, C63A, C64A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 O6, C69, C70, C71, C72, C69A, C70A, C71A, C72A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C13, C14, C15, C16, C17, C18, C13A, C14A, C15A, C16A, C17A, C18A, Si1, C19,
 C20, C21, C22, C23, C24, C19A, C20A, C21A, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Si2, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C31A, C32A,
 C33A, C34A, C35A, C36A, C37A, C38A, C39A, C40A, C41A, C42A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Same fragment restrains
{O4, C61A, C62A, C63A, C64A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O4, C61, C62, C63, C64}
{O5, C65A, C66A, C67A, C68A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5, C65, C66, C67, C68}
{O6, C69A, C70A, C71A, C72A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O6, C69, C70, C71, C72}
6. Others
 Sof(C13A)=Sof(C18A)=Sof(H18A)=Sof(C17A)=Sof(H17A)=Sof(C16A)=Sof(H16A)=
 Sof(C15A)=Sof(H15A)=Sof(C14A)=Sof(H14A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=1-FVAR(1)
 Sof(C13)=Sof(C18)=Sof(H18)=Sof(C17)=Sof(H17)=Sof(C16)=Sof(H16)=Sof(C15)=
 Sof(H15)=Sof(C14)=Sof(H14)=Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=FVAR(1)
 Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=
 Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(C42A)=Sof(H42A)=
 Sof(C41A)=Sof(H41A)=Sof(C40A)=Sof(H40A)=Sof(C39A)=Sof(H39A)=Sof(C38A)=
 Sof(H38A)=1-FVAR(2)
 Sof(C31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=
 Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(C42)=Sof(H42)=Sof(C41)=Sof(H41)=
 Sof(C40)=Sof(H40)=Sof(C39)=Sof(H39)=Sof(C38)=Sof(H38)=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)
 Sof(C69A)=Sof(H69C)=Sof(H69D)=Sof(C70A)=Sof(H70C)=Sof(H70D)=Sof(C71A)=
 Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(H72C)=Sof(H72D)=1-FVAR(5)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(H71A)=
 Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=FVAR(5)
7.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C61A(H61C,H61D), C62A(H62C,
 H62D), C63A(H63C,H63D), C64A(H64C,H64D), C65A(H65C,H65D), C66A(H66C,H66D),
 C67A(H67C,H67D), C68A(H68C,H68D), C69A(H69C,H69D), C70A(H70C,H70D), C71A(H71C,
 H71D), C72A(H72C,H72D)
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), C44(H44), C45(H45), C46(H46), C47(H47), C50(H50),
  C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
 C59(H59), C60(H60), C18(H18), C17(H17), C16(H16), C15(H15), C14(H14), C20(H20),
  C21(H21), C22(H22), C23(H23), C24(H24), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36), C42(H42), C41(H41), C40(H40), C39(H39), C38(H38),
 C18A(H18A), C17A(H17A), C16A(H16A), C15A(H15A), C14A(H14A), C20A(H20A),
 C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C32A(H32A), C33A(H33A),
 C34A(H34A), C35A(H35A), C36A(H36A), C42A(H42A), C41A(H41A), C40A(H40A),
 C39A(H39A), C38A(H38A)
7.c Fitted hexagon refined as free rotating group:
 C13(C18,C17,C16,C15,C14), C19(C20,C21,C22,C23,C24), C31(C32,C33,C34,C35,C36),
 C37(C42,C41,C40,C39,C38), C13A(C18A,C17A,C16A,C15A,C14A), C19A(C20A,C21A,C22A,
 C23A,C24A), C31A(C32A,C33A,C34A,C35A,C36A), C37A(C42A,C41A,C40A,C39A,C38A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 490 electrons were 
found in a volume of 2212\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[C4H8O] per Asymmetric Unit 
which account for 480 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56381
_shelx_fab_checksum              87960
_olex2_submission_special_instructions 'No special instructions were received'