A Cationic Thorium-Organic Framework with Triple Single-Crystal-to-Single-Crystal Transformation Peculiarities for Ultrasensitive Anion Recognition
Li, Zi-Jian; Lei, Min; Bao, Hong-liang; Yu, Ju; Lu, Huangjie; Li, Yongxin; Zhang, Zhi-Hui; Guo, Xiaofeng; Qian, Yuan; He, Mingyang; Wang, Jian-Qiang; Liu, Wei; Lin, Jian; Chemical Science  (2021) –; doi:10.1039/D1SC03709A

data_1565058
_publ_section_title
;
 A Cationic Thorium-Organic Framework with Triple
 Single-Crystal-to-Single-Crystal Transformation Peculiarities for
 Ultrasensitive Anion Recognition
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC03709A
_journal_year                    2021
_chemical_formula_moiety         'C161 H105 N5 O40 Th6'
_chemical_formula_sum            'C161 H105 N5 O40 Th6'
_chemical_formula_weight         4141.73
_chemical_name_systematic        Th-SINAP-200
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-07-10 deposited with the CCDC.	2021-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                117.118(2)
_cell_angle_beta                 114.422(2)
_cell_angle_gamma                91.982(2)
_cell_formula_units_Z            2
_cell_length_a                   24.6432(12)
_cell_length_b                   25.1083(12)
_cell_length_c                   25.5393(13)
_cell_measurement_reflns_used    9700
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      29.273
_cell_measurement_theta_min      2.294
_cell_volume                     12312.2(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0857
_diffrn_reflns_av_unetI/netI     0.0642
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            424684
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.432
_diffrn_reflns_theta_min         1.888
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.660
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6038
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1121 before and 0.0640 after correction. The Ratio of minimum to maximum transmission is 0.8095. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.117
_exptl_crystal_description       block
_exptl_crystal_F_000             3932
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         2.494
_refine_diff_density_min         -4.756
_refine_diff_density_rms         0.168
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2208
_refine_ls_number_reflns         67867
_refine_ls_number_restraints     2222
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1080
_refine_ls_R_factor_gt           0.0572
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+117.7502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1298
_refine_ls_wR_factor_ref         0.1563
_reflns_Friedel_coverage         0.000
_reflns_number_gt                40744
_reflns_number_total             67867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03709a2.cif
_cod_data_source_block           Th-SINAP-200_sq
_cod_database_code               1565058
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.668
_shelx_estimated_absorpt_t_min   0.592
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C27
 1.48 with sigma of 0.02
 N1-C27A
 1.48 with sigma of 0.02
 C33-C30
 1.51 with sigma of 0.02
 C33-C30A
 1.51 with sigma of 0.02
 N4-C131 = N4A-C13A = N4A-C12D = N4-C128 = N4-C144 = N4A-C15A
 1.48 with sigma of 0.02
 C150-C147 = C150-C15D = C134-C137 = C13D-C14A = C125-C122 = C12A-C122 = C143-
 C140 = C143-C14D
 1.51 with sigma of 0.02
 C12D-N4A
 1.48 with sigma of 0.02
 C104-C101 = C11A-C1AA
 1.51 with sigma of 0.02
 C98A-C95 = C98-C95 = C1AA-C101 = C11A-C1AA
 1.51 with sigma of 0.02
 O16A-O15A
 2.2 with sigma of 0.02
 O16-C1AA = O16A-C1AA = O15A-C1AA = O15-C1AA
 1.25 with sigma of 0.02
 O15-C104 = O16-C104 = O16A-C1AA = O15A-C1AA
 1.25 with sigma of 0.02
 C72-C69 = C72A-C69 = C78-C75 = C78-C75A
 1.51 with sigma of 0.02
 C10A-C1AA \\sim C1AA-C0AA
 with sigma of 0.02
 C102-C104 \\sim C104-C100
 with sigma of 0.02
3. Restrained planarity
 C101, C102, C103, C98, C99, C100, C104
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C156 \\sim C153 \\sim C154 \\sim C155 \\sim C150 \\sim C151 \\sim C152 \\sim
O23 \\sim O24: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C27A \\sim C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C14B \\sim C14C \\sim C14D \\sim C14E \\sim C14F \\sim C14A \\sim C153 \\sim
C154 \\sim C155 \\sim C150 \\sim C151 \\sim C152 \\sim N4A \\sim C12A \\sim
C12B \\sim C12C \\sim C12D \\sim C12E \\sim C12F \\sim C15F \\sim C15E \\sim
C15D \\sim C15C \\sim C15B \\sim C15A \\sim C13E \\sim C13F \\sim C13A \\sim
C13B \\sim C13C \\sim C13D \\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim
C130 \\sim C125 \\sim C131 \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim
C136 \\sim N4 \\sim C142 \\sim C137 \\sim C138 \\sim C139 \\sim C140 \\sim C141
\\sim C149 \\sim C148 \\sim C147 \\sim C146 \\sim C145 \\sim C144: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
O15 \\sim O16 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97 \\sim
C101 \\sim C102 \\sim C103 \\sim C98 \\sim C99 \\sim C100 \\sim C0AA \\sim C3AA
\\sim C98A \\sim C99A \\sim C10A \\sim C11A \\sim C1AA \\sim O15A \\sim O16A
\\sim C104: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C72 \\sim C77 \\sim C76 \\sim C75 \\sim C74 \\sim C73: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C75A \\sim C76A \\sim C77A \\sim C72A \\sim C73A \\sim C74A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C156, C153, C154, C155, C150, C151, C152, O23, O24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27A, C28A, C29A, C30A, C31A, C32A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14B, C14C, C14D, C14E, C14F, C14A, C153, C154, C155, C150, C151, C152, N4A,
 C12A, C12B, C12C, C12D, C12E, C12F, C15F, C15E, C15D, C15C, C15B, C15A, C13E,
 C13F, C13A, C13B, C13C, C13D, C126, C127, C128, C129, C130, C125, C131, C132,
 C133, C134, C135, C136, N4, C142, C137, C138, C139, C140, C141, C149, C148,
 C147, C146, C145, C144
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O40, N5, C159, C160, C161
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15, O16, C92, C93, C94, C95, C96, C97, C101, C102, C103, C98, C99, C100,
 C0AA, C3AA, C98A, C99A, C10A, C11A, C1AA, O15A, O16A, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C72, C77, C76, C75, C74, C73
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C75A, C76A, C77A, C72A, C73A, C74A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C0AA)=Sof(H0AA)=Sof(C3AA)=Sof(H3AA)=Sof(C98A)=Sof(C99A)=Sof(H99A)=
 Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(C1AA)=Sof(O15A)=Sof(O16A)=1-FVAR(1)
 Sof(O15)=Sof(O16)=Sof(C101)=Sof(C102)=Sof(H102)=Sof(C103)=Sof(H103)=Sof(C98)=
 Sof(C99)=Sof(H99)=Sof(C100)=Sof(H100)=Sof(C104)=FVAR(1)
 Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32A)=1-FVAR(2)
 Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(C31)=Sof(H31)=
 Sof(C32)=Sof(H32)=FVAR(2)
 Sof(C14B)=Sof(H14B)=Sof(C14C)=Sof(H14C)=Sof(C14D)=Sof(C14E)=Sof(H14E)=
 Sof(C14F)=Sof(H14F)=Sof(C14A)=Sof(C12A)=Sof(C12B)=Sof(H12B)=Sof(C12C)=
 Sof(H12C)=Sof(C12D)=Sof(C12E)=Sof(H12E)=Sof(C12F)=Sof(H12F)=Sof(C15F)=
 Sof(H15F)=Sof(C15E)=Sof(H15E)=Sof(C15D)=Sof(C15C)=Sof(H15C)=Sof(C15B)=
 Sof(H15B)=Sof(C15A)=Sof(C13E)=Sof(H13E)=Sof(C13F)=Sof(H13F)=Sof(C13A)=
 Sof(C13B)=Sof(H13B)=Sof(C13C)=Sof(H13C)=Sof(C13D)=1-FVAR(3)
 Sof(C126)=Sof(H126)=Sof(C127)=Sof(H127)=Sof(C128)=Sof(C129)=Sof(H129)=
 Sof(C130)=Sof(H130)=Sof(C125)=Sof(C131)=Sof(C132)=Sof(H132)=Sof(C133)=
 Sof(H133)=Sof(C134)=Sof(C135)=Sof(H135)=Sof(C136)=Sof(H136)=Sof(C142)=
 Sof(H142)=Sof(C137)=Sof(C138)=Sof(H138)=Sof(C139)=Sof(H139)=Sof(C140)=
 Sof(C141)=Sof(H141)=Sof(C149)=Sof(H149)=Sof(C148)=Sof(H148)=Sof(C147)=
 Sof(C146)=Sof(H146)=Sof(C145)=Sof(H145)=Sof(C144)=FVAR(3)
 Sof(C75A)=Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(C72A)=Sof(C73A)=
 Sof(H73A)=Sof(C74A)=Sof(H74A)=1-FVAR(4)
 Sof(C72)=Sof(C77)=Sof(H77)=Sof(C76)=Sof(H76)=Sof(C75)=Sof(C74)=Sof(H74)=
 Sof(C73)=Sof(H73)=FVAR(4)
 Sof(N4A)=1-FVAR(5)
 Sof(N4)=FVAR(5)
7.a Me refined with riding coordinates:
 C160(H16A,H16B,H16C), C161(H16D,H16E,H16F)
7.b Aromatic/amide H refined with riding coordinates:
 C120(H120), C121(H121), C123(H123), C124(H124), C14B(H14B), C14C(H14C),
 C14E(H14E), C14F(H14F), C3(H3), C4(H4), C6(H6), C7(H7), C157(H157), C113(H113),
  C112(H112), C116(H116), C115(H115), C22(H22), C21(H21), C25(H25), C24(H24),
 C61(H61), C60(H60), C64(H64), C63(H63), C76A(H76A), C77A(H77A), C73A(H73A),
 C74A(H74A), C154(H154), C155(H155), C151(H151), C152(H152), C37(H37), C38(H38),
  C34(H34), C35(H35), C9(H9), C10(H10), C12(H12), C13(H13), C18(H18), C19(H19),
 C15(H15), C16(H16), C46(H46), C45(H45), C43(H43), C42(H42), C81(H81), C82(H82),
  C84(H84), C85(H85), C51(H51), C49(H49), C48(H48), C52(H52), C28A(H28A),
 C29A(H29A), C31A(H31A), C32A(H32A), C55(H55), C54(H54), C58(H58), C57(H57),
 C12B(H12B), C12C(H12C), C12E(H12E), C12F(H12F), C87(H87), C88(H88), C90(H90),
 C91(H91), C67(H67), C68(H68), C70(H70), C71(H71), C15F(H15F), C15E(H15E),
 C15C(H15C), C15B(H15B), C13E(H13E), C13F(H13F), C13B(H13B), C13C(H13C),
 C93(H93), C94(H94), C96(H96), C97(H97), C109(H109), C107(H107), C106(H106),
 C110(H110), C102(H102), C103(H103), C99(H99), C100(H100), C158(H158),
 C159(H159), C0AA(H0AA), C3AA(H3AA), C99A(H99A), C10A(H10A), C28(H28), C29(H29),
  C31(H31), C32(H32), C77(H77), C76(H76), C74(H74), C73(H73), C126(H126),
 C127(H127), C129(H129), C130(H130), C132(H132), C133(H133), C135(H135),
 C136(H136), C142(H142), C138(H138), C139(H139), C141(H141), C149(H149),
 C148(H148), C146(H146), C145(H145)
7.c Fitted hexagon refined as free rotating group:
 C14B(C14C,C14D,C14E,C14F,C14A), C12A(C12B,C12C,C12D,C12E,C12F), C15F(C15E,
 C15D,C15C,C15B,C15A), C13E(C13F,C13A,C13B,C13C,C13D), C101(C102,C103,C98,C99,
 C100), C0AA(C3AA,C98A,C99A,C10A,C11A), C126(C127,C128,C129,C130,C125),
 C131(C132,C133,C134,C135,C136), C142(C137,C138,C139,C140,C141), C149(C148,C147,
 C146,C145,C144)
;
_shelx_res_checksum              1756
_shelx_hkl_checksum              44645
_shelx_fab_checksum              21001
_olex2_submission_special_instructions 'No special instructions were received'