Supramolecular assemblies of tetravalent terbium complex units: syntheses, structure, and materials properties
Xue, Tianjiao; Yang, Qing-Song; Li, Lei; Chang, Xiao-Yong; Ding, You-Song; Zheng, Zhiping; Chemical Science 16 (2025) 6805–6811; doi:10.1039/D4SC08731C

data_1574133
_publ_section_title
;
 Supramolecular assemblies of tetravalent terbium complex units:
 syntheses, structure, and materials properties
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              6805
_journal_page_last               6811
_journal_paper_doi               10.1039/D4SC08731C
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C168 H144 N4 O8 Si8 Tb2, 8(C4 H8 O), 4[C4H8O]'
_chemical_formula_sum            'C208 H224 N4 O18 Si8 Tb2'
_chemical_formula_weight         3610.46
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-14 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   32.2780(17)
_cell_length_b                   34.1126(16)
_cell_length_c                   39.4068(17)
_cell_measurement_reflns_used    9664
_cell_measurement_temperature    99.9
_cell_measurement_theta_max      27.49
_cell_measurement_theta_min      2.66
_cell_volume                     43390(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.9
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\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  0.0544
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            173686
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.573
_diffrn_reflns_theta_min         2.388
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.746
_exptl_absorpt_correction_T_max  0.0949
_exptl_absorpt_correction_T_min  0.0629
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0908 before and 0.0744 after correction.
The Ratio of minimum to maximum transmission is 0.6670.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_description       octahedral
_exptl_crystal_F_000             15088
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.305
_refine_diff_density_min         -0.833
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     654
_refine_ls_number_reflns         12500
_refine_ls_number_restraints     525
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0777P)^2^+373.6990P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1505
_refine_ls_wR_factor_ref         0.1600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10716
_reflns_number_total             12500
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08731c2.cif
_cod_data_source_block           20231003_0930_tbbpa_thf_0m
_cod_depositor_comments
'Adding full bibliography for 1574130--1574134.cif.'
_cod_original_sg_symbol_H-M      'F d d d'
_cod_database_code               1574133
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.964
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 O5-C21 = O5-C45
 1.44 with sigma of 0.02
 O3-C23 = O3-C49
 1.44 with sigma of 0.02
 C23-C47 = C3-C49
 1.53 with sigma of 0.02
 C21-C43 = C11-C45
 1.53 with sigma of 0.02
 C47-C3
 1.54 with sigma of 0.02
 C43-C11
 1.54 with sigma of 0.02
 O6-C25 = O6-C53
 1.44 with sigma of 0.02
 O4-C27 = O4-C57
 1.44 with sigma of 0.02
 C25-C51 = C13-C53
 1.53 with sigma of 0.02
 C55-C7
 1.54 with sigma of 0.02
 C27-C55 = C7-C57
 1.53 with sigma of 0.02
 C51-C13
 1.54 with sigma of 0.02
 O7-C1A = O7-C1D
 1.44 with sigma of 0.02
 C1A-C1B = C1C-C1D
 1.53 with sigma of 0.02
 C1B-C1C
 1.54 with sigma of 0.02
 O3-C47 = O3-C3 = C23-C3 = C47-C49
 2.38 with sigma of 0.04
 O5-C43 = O5-C11 = C21-C11 = C43-C45
 2.38 with sigma of 0.04
 O4-C55 = O4-C7 = C27-C7 = C55-C57
 2.38 with sigma of 0.04
 O6-C51 = O6-C13 = C25-C13 = C51-C53
 2.38 with sigma of 0.04
 O7-C1B = O7-C1C = C1A-C1C = C1B-C1D
 2.38 with sigma of 0.04
 C23-C47 \\sim C47-C3 \\sim C3-C49
 with sigma of 0.02
 O3-C23 \\sim O3-C49
 with sigma of 0.02
 O3-C47 \\sim O3-C3
 with sigma of 0.04
 C47-C49 \\sim C23-C3
 with sigma of 0.04
 C21-C43 \\sim C43-C11 \\sim C11-C45
 with sigma of 0.02
 O5-C21 \\sim O5-C45
 with sigma of 0.02
 O5-C43 \\sim O5-C11
 with sigma of 0.04
 C43-C45 \\sim C21-C11
 with sigma of 0.04
 O6-C25 \\sim O6-C53
 with sigma of 0.02
 O4-C55 \\sim O4-C7
 with sigma of 0.04
 O6-C51 \\sim O6-C13
 with sigma of 0.04
 C55-C57 \\sim C27-C7
 with sigma of 0.04
 C25-C51 \\sim C51-C13 \\sim C13-C53
 with sigma of 0.02
 C27-C55 \\sim C55-C7 \\sim C7-C57
 with sigma of 0.02
 C51-C53 \\sim C25-C13
 with sigma of 0.04
 O4-C27 \\sim O4-C57
 with sigma of 0.02
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D
 with sigma of 0.02
 O7-C1A \\sim O7-C1D
 with sigma of 0.02
 O7-C1B \\sim O7-C1C
 with sigma of 0.04
 C1B-C1D \\sim C1A-C1C
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O3 \\sim C23 \\sim C47 \\sim C3 \\sim C49: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O4 \\sim C27 \\sim C55 \\sim C7 \\sim C57: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O5 \\sim C21 \\sim C43 \\sim C11 \\sim C45: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O6 \\sim C25 \\sim C51 \\sim C13 \\sim C53: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O7 \\sim C1A \\sim C1B \\sim C1C \\sim C1D: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C57) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C55)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(O6) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.01
Uanis(C23) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.01
Uanis(C43) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.01
Uanis(C1B) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1D)
\\sim Ueq, Uanis(C1C) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Rigid body (RIGU) restrains
 O4, C27, C55, C7, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C25, C51, C13, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C23, C47, C3, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C21, C43, C11, C45
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, C1A, C1B, C1C, C1D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O5(0.5) C21(0.5) H21A(0.5) H21B(0.5) C43(0.5) H43A(0.5) H43B(0.5)
 C11(0.5) H11A(0.5) H11B(0.5) C45(0.5) H45A(0.5) H45B(0.5) O3(0.5) C23(0.5)
 H23A(0.5) H23B(0.5) C47(0.5) H47A(0.5) H47B(0.5) C3(0.5) H3A(0.5) H3B(0.5)
 C49(0.5) H49A(0.5) H49B(0.5) O6(0.5) C25(0.5) H25A(0.5) H25B(0.5) C51(0.5)
 H51A(0.5) H51B(0.5) C13(0.5) H13A(0.5) H13B(0.5) C53(0.5) H53A(0.5) H53B(0.5)
 O4(0.5) C27(0.5) H27A(0.5) H27B(0.5) C55(0.5) H55A(0.5) H55B(0.5) C7(0.5)
 H7A(0.5) H7B(0.5) C57(0.5) H57A(0.5) H57B(0.5) O7(0.5) C1A(0.5) H1AA(0.5)
 H1AB(0.5) C1B(0.5) H1BA(0.5) H1BB(0.5) C1C(0.5) H1CA(0.5) H1CB(0.5) C1D(0.5)
 H1DA(0.5) H1DB(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C21(H21A,H21B), C43(H43A,H43B), C11(H11A,H11B), C45(H45A,
 H45B), C23(H23A,H23B), C47(H47A,H47B), C3(H3A,H3B), C49(H49A,H49B), C25(H25A,
 H25B), C51(H51A,H51B), C13(H13A,H13B), C53(H53A,H53B), C27(H27A,H27B),
 C55(H55A,H55B), C7(H7A,H7B), C57(H57A,H57B), C1A(H1AA,H1AB), C1B(H1BA,H1BB),
 C1C(H1CA,H1CB), C1D(H1DA,H1DB)
6.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C60(H60), C10(H10), C12(H12), C16(H16), C20(H20), C26(H26), C28(H28),
 C30(H30), C32(H32), C34(H34), C36(H36), C40(H40), C42(H42), C44(H44), C46(H46),
  C48(H48), C50(H50), C52(H52), C54(H54), C58(H58), C29(H29), C15(H15),
 C31(H31), C2(H2), C33(H33), C17(H17), C35(H35), C9(H9), C37(H37), C19(H19),
 C39(H39), C5(H5), C41(H41)
;
_shelx_res_checksum              9868
_olex2_submission_special_instructions 'No special instructions were received'