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_1574134
_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 H140 N4 O8 Si8 Tb2, 2(C7 H8), 2[C7H8], 2[C7H8]'
_chemical_formula_sum            'C210 H188 N4 O8 Si8 Tb2'
_chemical_formula_weight         3438.19
_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             2025-02-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-25 deposited with the CCDC.	2025-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                109.037(4)
_cell_angle_beta                 101.480(3)
_cell_angle_gamma                90.122(3)
_cell_formula_units_Z            2
_cell_length_a                   17.8325(16)
_cell_length_b                   21.184(2)
_cell_length_c                   25.671(2)
_cell_measurement_reflns_used    5616
_cell_measurement_temperature    200.0(2)
_cell_measurement_theta_max      53.895
_cell_measurement_theta_min      3.000
_cell_volume                     8960.2(14)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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'
_diffrn_ambient_temperature      200.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0747
_diffrn_reflns_av_unetI/netI     0.0590
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            32561
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.162
_diffrn_reflns_theta_min         1.924
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           2.51
_diffrn_source_power             0.17532349999999997
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.85
_exptl_absorpt_coefficient_mu    4.694
_exptl_absorpt_correction_T_max  0.750
_exptl_absorpt_correction_T_min  0.452
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 2:
 wR2(int) was 0.1261 before and 0.1010 after correction.

Final HKLF 4 output contains 285901 reflections, Rint = 0.0747
 (157284 with I > 3sig(I), Rint = 0.0674)
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.274
_exptl_crystal_description       plate
_exptl_crystal_F_000             3564
_exptl_crystal_preparation       'Magnetic properties,Luminescent'
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.787
_refine_diff_density_min         -1.599
_refine_diff_density_rms         0.092
_refine_ls_extinction_coef       0.00065(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.159
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2082
_refine_ls_number_reflns         32561
_refine_ls_number_restraints     1011
_refine_ls_restrained_S_all      1.144
_refine_ls_R_factor_all          0.0732
_refine_ls_R_factor_gt           0.0600
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1232P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1757
_refine_ls_wR_factor_ref         0.1856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25770
_reflns_number_total             32561
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08731c2.cif
_cod_data_source_block           2351767
_cod_depositor_comments
'Adding full bibliography for 1574130--1574134.cif.'
_cod_database_code               1574134
_shelx_shelxl_version_number     2019/2
_olex2_refinement_description
;
1. Restrained distances
 Tb1-N3 \\sim Tb1-N3A
 with sigma of 0.02
 N4-C167 \\sim N4A-C1I
 with sigma of 0.02
 N4-C166 \\sim N4A-C1J
 with sigma of 0.02
 N3-C157 \\sim N3A-C1D
 with sigma of 0.02
 N3-C161 \\sim N3A-C169
 with sigma of 0.02
 C167-C168 \\sim C1I-C1H
 with sigma of 0.02
 C158-C157 \\sim C1C-C1D
 with sigma of 0.02
 C158-C159 \\sim C1C-C1B
 with sigma of 0.02
 C166-C165 \\sim C1J-C1K
 with sigma of 0.02
 C164-C165 \\sim C1G-C1K
 with sigma of 0.02
 C164-C168 \\sim C1G-C1H
 with sigma of 0.02
 C164-C163 \\sim C1G-C1F
 with sigma of 0.02
 C159-C160 \\sim C1B-C1A
 with sigma of 0.02
 C159-C162 \\sim C1B-C1E
 with sigma of 0.02
 C161-C160 \\sim C169-C1A
 with sigma of 0.02
 C162-C163 \\sim C1E-C1F
 with sigma of 0.02
 Tb1-C157 \\sim Tb1-C1D
 with sigma of 0.04
 Tb1-C161 \\sim Tb1-C169
 with sigma of 0.04
 N4-C165 \\sim N4A-C1K
 with sigma of 0.04
 N4-C168 \\sim N4A-C1H
 with sigma of 0.04
 N3-C158 \\sim N3A-C1C
 with sigma of 0.04
 N3-C160 \\sim N3A-C1A
 with sigma of 0.04
 C167-C166 \\sim C1I-C1J
 with sigma of 0.04
 C167-C164 \\sim C1I-C1G
 with sigma of 0.04
 C158-C160 \\sim C1C-C1A
 with sigma of 0.04
 C158-C162 \\sim C1C-C1E
 with sigma of 0.04
 C157-C159 \\sim C1D-C1B
 with sigma of 0.04
 C157-C161 \\sim C1D-C169
 with sigma of 0.04
 C166-C164 \\sim C1J-C1G
 with sigma of 0.04
 C164-C162 \\sim C1G-C1E
 with sigma of 0.04
 C159-C161 \\sim C1B-C169
 with sigma of 0.04
 C159-C163 \\sim C1B-C1F
 with sigma of 0.04
 C165-C168 \\sim C1K-C1H
 with sigma of 0.04
 C165-C163 \\sim C1K-C1F
 with sigma of 0.04
 C168-C163 \\sim C1H-C1F
 with sigma of 0.04
 C160-C162 \\sim C1A-C1E
 with sigma of 0.04
 Tb1-N1 \\sim Tb1-N1A
 with sigma of 0.02
 Tb2-N2 \\sim Tb2-N2A
 with sigma of 0.02
 N2-C82 \\sim N2A-C82A
 with sigma of 0.02
 N2-C155 \\sim N2A-C170
 with sigma of 0.02
 N1-C73 \\sim N1A-C73A
 with sigma of 0.02
 N1-C77 \\sim N1A-C77A
 with sigma of 0.02
 C73-C74 \\sim C73A-C74A
 with sigma of 0.02
 C81-C80 \\sim C81A-C80A
 with sigma of 0.02
 C81-C82 \\sim C81A-C82A
 with sigma of 0.02
 C80-C156 \\sim C80A-C1L
 with sigma of 0.02
 C80-C79 \\sim C80A-C79A
 with sigma of 0.02
 C155-C156 \\sim C170-C1L
 with sigma of 0.02
 C77-C76 \\sim C77A-C76A
 with sigma of 0.02
 C74-C75 \\sim C74A-C75A
 with sigma of 0.02
 C75-C76 \\sim C75A-C76A
 with sigma of 0.02
 C75-C78 \\sim C75A-C78A
 with sigma of 0.02
 C79-C78 \\sim C79A-C78A
 with sigma of 0.02
 Tb1-C73 \\sim Tb1-C73A
 with sigma of 0.04
 Tb1-C77 \\sim Tb1-C77A
 with sigma of 0.04
 Tb2-C82 \\sim Tb2-C82A
 with sigma of 0.04
 Tb2-C155 \\sim Tb2-C170
 with sigma of 0.04
 N2-C81 \\sim N2A-C81A
 with sigma of 0.04
 N2-C156 \\sim N2A-C1L
 with sigma of 0.04
 N1-C74 \\sim N1A-C74A
 with sigma of 0.04
 N1-C76 \\sim N1A-C76A
 with sigma of 0.04
 C73-C77 \\sim C73A-C77A
 with sigma of 0.04
 C73-C75 \\sim C73A-C75A
 with sigma of 0.04
 C81-C156 \\sim C81A-C1L
 with sigma of 0.04
 C81-C79 \\sim C81A-C79A
 with sigma of 0.04
 C80-C82 \\sim C80A-C82A
 with sigma of 0.04
 C80-C155 \\sim C80A-C170
 with sigma of 0.04
 C80-C78 \\sim C80A-C78A
 with sigma of 0.04
 C82-C155 \\sim C82A-C170
 with sigma of 0.04
 C77-C75 \\sim C77A-C75A
 with sigma of 0.04
 C74-C76 \\sim C74A-C76A
 with sigma of 0.04
 C74-C78 \\sim C74A-C78A
 with sigma of 0.04
 C75-C79 \\sim C75A-C79A
 with sigma of 0.04
 C156-C79 \\sim C1L-C79A
 with sigma of 0.04
 C76-C78 \\sim C76A-C78A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
N3 \\sim N3A \\sim N4 \\sim N4A \\sim C1A \\sim C1B \\sim C1C \\sim C1D \\sim
C1E \\sim C1F \\sim C1G \\sim C1H \\sim C1I \\sim C1J \\sim C1K \\sim C157
\\sim C158 \\sim C159 \\sim C160 \\sim C161 \\sim C162 \\sim C163 \\sim C164
\\sim C165 \\sim C166 \\sim C167 \\sim C168 \\sim C169: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
N1 \\sim N1A \\sim N2 \\sim N2A \\sim C1L \\sim C73 \\sim C73A \\sim C74 \\sim
C74A \\sim C75 \\sim C75A \\sim C76 \\sim C76A \\sim C77 \\sim C77A \\sim C78
\\sim C78A \\sim C79 \\sim C79A \\sim C80 \\sim C80A \\sim C81 \\sim C81A \\sim
C82 \\sim C82A \\sim C155 \\sim C156 \\sim C170: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(N3A)=Sof(N4A)=Sof(C1A)=Sof(H1A)=Sof(C1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=
 Sof(H1D)=Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(H1F)=Sof(C1G)=Sof(C1H)=Sof(H1H)=
 Sof(C1I)=Sof(H1I)=Sof(C1J)=Sof(H1J)=Sof(C1K)=Sof(H1K)=Sof(C169)=Sof(H169)=1-
 FVAR(1)
 Sof(N3)=Sof(N4)=Sof(C157)=Sof(H157)=Sof(C158)=Sof(H158)=Sof(C159)=Sof(C160)=
 Sof(H160)=Sof(C161)=Sof(H161)=Sof(C162)=Sof(H162)=Sof(C163)=Sof(H163)=
 Sof(C164)=Sof(C165)=Sof(H165)=Sof(C166)=Sof(H166)=Sof(C167)=Sof(H167)=
 Sof(C168)=Sof(H168)=FVAR(1)
 Sof(N1A)=Sof(N2A)=Sof(C1L)=Sof(H1L)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74A)=
 Sof(C75A)=Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=
 Sof(C79A)=Sof(H79A)=Sof(C80A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=
 Sof(C170)=Sof(H170)=1-FVAR(2)
 Sof(N1)=Sof(N2)=Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(C76)=
 Sof(H76)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=Sof(C80)=
 Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=Sof(C155)=Sof(H155)=Sof(C156)=Sof(H156)=
 FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1H(H1H), C1I(H1I),
 C1J(H1J), C1K(H1K), C1L(H1L), 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), C73(H73), C73A(H73A), C74(H74), C74A(H74A), C76(H76), C76A(H76A),
 C77(H77), C77A(H77A), C78(H78), C78A(H78A), C79(H79), C79A(H79A), C81(H81),
 C81A(H81A), C82(H82), C82A(H82A), C84(H84), C85(H85), C86(H86), C87(H87),
 C88(H88), C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C96(H96), C97(H97),
  C98(H98), C99(H99), C100(H100), C102(H102), C103(H103), C104(H104),
 C105(H105), C106(H106), C108(H108), C109(H109), C110(H110), C111(H111),
 C112(H112), C114(H114), C115(H115), C116(H116), C117(H117), C118(H118),
 C120(H120), C121(H121), C122(H122), C123(H123), C124(H124), C126(H126),
 C127(H127), C128(H128), C129(H129), C130(H130), C132(H132), C133(H133),
 C134(H134), C135(H135), C136(H136), C138(H138), C139(H139), C140(H140),
 C141(H141), C142(H142), C144(H144), C145(H145), C146(H146), C147(H147),
 C148(H148), C150(H150), C151(H151), C152(H152), C153(H153), C154(H154),
 C155(H155), C156(H156), C157(H157), C158(H158), C160(H160), C161(H161),
 C162(H162), C163(H163), C165(H165), C166(H166), C167(H167), C168(H168),
 C169(H169), C170(H170), C181(H181), C177(H177), C178(H178), C179(H179),
 C180(H180), C184(H184), C185(H185), C186(H186), C187(H187), C188(H188)
4.b Fitted hexagon refined as free rotating group:
 C181(C176,C177,C178,C179,C180)
4.c Idealised Me refined as rotating group:
 C182(H18A,H18B,H18C), C189(H18D,H18E,H18F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 436 electrons were 
found in a volume of 1992\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2[C7H8], 2[C7H8] per formula unit 
which account for 400 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              96359
_shelx_fab_checksum              13385
_olex2_submission_special_instructions 'No special instructions were received'