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_1565061
_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         'C312 H192 N8 O72 Th12'
_chemical_formula_sum            'C312 H192 N8 O72 Th12'
_chemical_formula_weight         7989.20
_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             2021-02-25
_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                93.359(10)
_cell_angle_beta                 92.771(11)
_cell_angle_gamma                90.421(9)
_cell_formula_units_Z            2
_cell_length_a                   24.163(9)
_cell_length_b                   26.423(9)
_cell_length_c                   36.034(13)
_cell_measurement_reflns_used    9851
_cell_measurement_temperature    120
_cell_measurement_theta_max      17.569
_cell_measurement_theta_min      2.352
_cell_volume                     22939(14)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_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 0.992
_diffrn_measured_fraction_theta_max 0.992
_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  0.2230
_diffrn_reflns_av_unetI/netI     0.2503
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            104257
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        18.848
_diffrn_reflns_theta_max         18.848
_diffrn_reflns_theta_min         1.857
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.925
_exptl_absorpt_correction_T_max  0.7443
_exptl_absorpt_correction_T_min  0.4351
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1356 before and 0.1014 after correction. The Ratio of minimum to maximum transmission is 0.5846. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.157
_exptl_crystal_description       block
_exptl_crystal_F_000             7552
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         4.354
_refine_diff_density_min         -2.769
_refine_diff_density_rms         0.289
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.169
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3037
_refine_ls_number_reflns         35787
_refine_ls_number_restraints     7139
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.3032
_refine_ls_R_factor_gt           0.1935
_refine_ls_shift/su_max          0.060
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.3400P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4924
_refine_ls_wR_factor_ref         0.5742
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13346
_reflns_number_total             35787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03709a2.cif
_cod_data_source_block           Th-SINAP-203_sq
_cod_database_code               1565061
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C161-C164
 1.51 with sigma of 0.02
 C1-C2
 1.51 with sigma of 0.02
 O1-C1
 1.25 with sigma of 0.02
 O2-C1
 1.25 with sigma of 0.02
 C157-C158
 1.51 with sigma of 0.02
 O12-C78 = O11-C78
 1.25 with sigma of 0.02
 O2-C1 = O1-C1
 1.25 with sigma of 0.02
 C75-C78
 1.51 with sigma of 0.02
 N7-C248 = N7-C245 = N7-C261
 1.48 with sigma of 0.02
 C242-C239
 1.5 with sigma of 0.02
 C264-C267
 1.51 with sigma of 0.02
 C101-C104
 1.51 with sigma of 0.02
 O15-C104 = O16-C104
 1.25 with sigma of 0.02
 O43-C274 = O44-C274
 1.25 with sigma of 0.02
 C275-C274
 1.51 with sigma of 0.02
 C111-C108
 1.51 with sigma of 0.02
 C41-C40
 1.51 with sigma of 0.02
 C192-C195
 1.51 with sigma of 0.02
 C235-C236
 1.51 with sigma of 0.02
 O38-C235 = O37-C235
 1.25 with sigma of 0.02
 O27-C182 = O28-C182
 1.25 with sigma of 0.02
 C182-C179
 1.51 with sigma of 0.02
 C117-C114
 1.51 with sigma of 0.02
 O6-C39
 1.25 with sigma of 0.02
 O5-C39
 1.25 with sigma of 0.02
 O48-C312 = O47-C312
 1.25 with sigma of 0.02
 C62-C65
 1.51 with sigma of 0.02
 O46-C299 = O45-C299
 1.25 with sigma of 0.02
 O26-C157 = O25-C157
 1.25 with sigma of 0.02
 C221-C218
 1.51 with sigma of 0.02
 O23-C156 = O24-C156
 1.25 with sigma of 0.02
 C156-C153
 1.51 with sigma of 0.02
 C143-C140
 1.51 with sigma of 0.02
 Th11-O3_$1
 2.4 with sigma of 0.02
 Th3-O56 = Th6-O56 = Th2-O56
 2.45 with sigma of 0.02
 Th4-O51 = Th1-O51 = Th5-O51
 2.45 with sigma of 0.02
 Th10-O63 = Th12-O63 = Th9-O63
 2.45 with sigma of 0.02
 Th7-O58 = Th8-O58 = Th12-O58
 2.45 with sigma of 0.02
 Th7-O60 = Th10-O60 = Th11-O60
 2.45 with sigma of 0.02
 Th3-O53 = Th6-O53 = Th4-O53
 2.45 with sigma of 0.02
 Th7-O57 = Th8-O57 = Th11-O57
 2.45 with sigma of 0.02
 N2-C66 = N2-C53 = N2-C50
 1.48 with sigma of 0.02
 C260-C257
 1.51 with sigma of 0.02
 O40-C260 = O39-C260
 1.25 with sigma of 0.02
 C118-C119
 1.51 with sigma of 0.02
 O19-C118 = O20-C118
 1.25 with sigma of 0.02
 C125-C122
 1.51 with sigma of 0.02
 N5-C167 = N5-C170 = N5-C183
 1.48 with sigma of 0.02
 C137-C134
 1.51 with sigma of 0.02
 C150-C147 = C137-C134 = C143-C140 = C156-C153 = C125-C122 = C118-C119
 1.51 with sigma of 0.02
 O20-C118 = O19-C118
 1.25 with sigma of 0.02
 O13-C79 = O14-C79
 1.25 with sigma of 0.02
 Th2-O66
 2.5 with sigma of 0.02
 C26-C23
 1.51 with sigma of 0.02
 O3-C26 = O4-C26
 1.25 with sigma of 0.02
 C231-C234
 1.51 with sigma of 0.02
 O30-C195 = O29-C195
 1.25 with sigma of 0.02
 O30-O29
 2.35 with sigma of 0.02
 O36-C234
 1.25 with sigma of 0.02
 O35-O36
 2.35 with sigma of 0.02
 O35-C234
 1.25 with sigma of 0.02
 O31-C196 = O32-C196
 1.25 with sigma of 0.02
 C309-C312
 1.51 with sigma of 0.02
 O33-C221 = O34-C221
 1.25 with sigma of 0.02
 N3-C89 = N3-C92 = N3-C105
 1.48 with sigma of 0.02
 C196-C197 = C200-C203 = C215-C212 = C221-C218 = C228-C225
 1.51 with sigma of 0.02
 N1-C27 = N1-C11 = N1-C14
 1.48 with sigma of 0.02
 C117-O18
 1.25 with sigma of 0.02
 O21-C143
 1.25 with sigma of 0.02
 N6-C222 = N6-C209 = N6-C206
 1.48 with sigma of 0.02
 C176-C173 = C186-C189 = C195-C192 = C164-C161 = C182-C179 = C79-C80 = C86-C83
 = C95-C98 = C104-C101 = C111-C108 = C117-C114 = C75-C78 = C69-C72 = C59-C56 =
 C62-C65 = C41-C40 = C44-C47 = C254-C251 = C260-C257 = C264-C267 = C273-C270 =
 C242-C239 = C235-C236 = C1-C2 = C8-C5 = C33-C30 = C39-C36 = C26-C23 = C20-C17 =
  C275-C274 = C278-C281 = C290-C293 = C299-C296 = C306-C303 = C312-C309
 1.51 with sigma of 0.02
 N8-C284 = N8-C300 = N8-C287
 1.48 with sigma of 0.02
 Th12_$2-O22
 2.4 with sigma of 0.02
 O41-C273 = O42-C273
 1.25 with sigma of 0.02
 O17-C117
 1.25 with sigma of 0.02
 Th4-O50 \\sim Th6-O50 \\sim O50-Th1
 with sigma of 0.02
 Th3-O55 \\sim Th2-O55 \\sim Th5-O55
 with sigma of 0.02
 Th6-O49 \\sim Th2-O49 \\sim O49-Th1
 with sigma of 0.02
 Th12-O59 \\sim Th10-O59 \\sim Th7-O59
 with sigma of 0.02
 Th4-O54 \\sim Th5-O54 \\sim O54-Th3
 with sigma of 0.02
 C165-C161 \\sim C161-C169
 with sigma of 0.02
 C160-C164 \\sim C164-C162
 with sigma of 0.02
 C244-N7 \\sim N7-C246
 with sigma of 0.02
 C247-C239 \\sim C239-C243
 with sigma of 0.02
 C238-C242 \\sim C242-C240
 with sigma of 0.02
 C266-N7 \\sim N7-C262
 with sigma of 0.02
 C253-N7 \\sim N7-C249
 with sigma of 0.02
 C265-C267 \\sim C267-C263
 with sigma of 0.02
 C272-C264 \\sim C264-C268
 with sigma of 0.02
 C109-C111 \\sim C111-C107
 with sigma of 0.02
 C193-C195 \\sim C195-C191
 with sigma of 0.02
 C60-C56 \\sim C56-C64
 with sigma of 0.02
 C55-C59 \\sim C59-C57
 with sigma of 0.02
 C252-C254 \\sim C254-C250
 with sigma of 0.02
 C259-C251 \\sim C251-C255
 with sigma of 0.02
 Th11-O61 \\sim Th9-O61 \\sim Th8-O61
 with sigma of 0.02
 Th9-O62 \\sim Th12-O62 \\sim Th8-O62
 with sigma of 0.02
 C180-C182 \\sim C182-C178
 with sigma of 0.02
 C115-C117 \\sim C117-C113
 with sigma of 0.02
 C38-C30 \\sim C30-C34
 with sigma of 0.02
 C31-C33 \\sim C33-C29
 with sigma of 0.02
 C37-C39 \\sim C39-C35
 with sigma of 0.02
 C63-C65 \\sim C65-C61
 with sigma of 0.02
 C42-C40 \\sim C40-C46
 with sigma of 0.02
 C181-C173 \\sim C173-C177
 with sigma of 0.02
 C174-C176 \\sim C176-C172
 with sigma of 0.02
 C163-C157 \\sim C157-C159
 with sigma of 0.02
 C217-C221 \\sim C221-C219
 with sigma of 0.02
 C141-C143 \\sim C143-C139
 with sigma of 0.02
 C154-C156 \\sim C156-C152
 with sigma of 0.02
 C237-C235 \\sim C235-C241
 with sigma of 0.02
 C258-C260 \\sim C260-C256
 with sigma of 0.02
 C120-C118 \\sim C118-C124
 with sigma of 0.02
 C166-N5 \\sim N5-C168
 with sigma of 0.02
 C175-N5 \\sim N5-C171
 with sigma of 0.02
 C188-N5 \\sim N5-C184
 with sigma of 0.02
 C81-C79 \\sim C79-C85
 with sigma of 0.02
 C22-C26 \\sim C26-C24
 with sigma of 0.02
 C297-C299 \\sim C299-C295
 with sigma of 0.02
 C289-C293 \\sim C293-C291
 with sigma of 0.02
 C294-C290 \\sim C290-C298
 with sigma of 0.02
 C226-C228 \\sim C228-C224
 with sigma of 0.02
 C233-C225 \\sim C225-C229
 with sigma of 0.02
 C230-C234 \\sim C234-C232
 with sigma of 0.02
 O36-C231 \\sim C231-O35
 with sigma of 0.02
 C310-C312 \\sim C312-C308
 with sigma of 0.02
 C103-C95 \\sim C95-C99
 with sigma of 0.02
 C96-C98 \\sim C98-C94
 with sigma of 0.02
 C208-C200 \\sim C200-C204
 with sigma of 0.02
 C201-C203 \\sim C203-C199
 with sigma of 0.02
 C28-N1 \\sim N1-C32
 with sigma of 0.02
 C210-N6 \\sim N6-C214
 with sigma of 0.02
 C227-N6 \\sim N6-C223
 with sigma of 0.02
 C207-N6 \\sim N6-C205
 with sigma of 0.02
 C283-N8 \\sim N8-C285
 with sigma of 0.02
 C292-N8 \\sim N8-C288
 with sigma of 0.02
 C311-C303 \\sim C303-C307
 with sigma of 0.02
 C304-C306 \\sim C306-C302
 with sigma of 0.02
 C305-N8 \\sim N8-C301
 with sigma of 0.02
3. Restrained planarity
 C236, C237, C238, C239, C240, C241
 with sigma of 0.1
 C42, C41, C46, C45, C44, C43, C47, C50
 with sigma of 0.1
 C42, C41, C46, C45, C44, C43, C40
 with sigma of 0.1
 N7, C251, C250, C249, C248, C253, C252
 with sigma of 0.1
 C215, C216, C217, C218, C219, C220, C221
 with sigma of 0.1
 C236, C237, C238, C239, C240, C241, C235
 with sigma of 0.1
 N4, C136, C131, C132, C133, C134, C135
 with sigma of 0.1
 C20, C23, O3, O4, C26
 with sigma of 0.1
 C295, C294, C293, C298, C297, C296, C290, C287, C299
 with sigma of 0.1
 C293, C296, C290, C289, C288, C287, C292, C291
 with sigma of 0.1
 C101, C100, C99, C98, C103, C102, C95, C92
 with sigma of 0.1
 N1, C19, C18, C17, C16, C15, C14, C20, C23
 with sigma of 0.1
 C203, C204, C205, C206, C207, C208, N6
 with sigma of 0.1
 C277, C278, C279, C280, C275, C276, C284, C281
 with sigma of 0.1
 C278, C275, C282, C283, C284, C285, C286, C281
 with sigma of 0.1
 C290, C289, C288, C287, C292, C291, N8
 with sigma of 0.1
 C282, C283, C284, C285, C286, C281, N8
 with sigma of 0.05
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O9) \\sim Ueq, Uanis(O10) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O41) \\sim Ueq, Uanis(O17) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O9) = Uanis(O10)
Uanis(O33) = Uanis(O34)
Uanis(O17) = Uanis(O18)
Uanis(O45) = Uanis(O46)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Aromatic/amide H refined with riding coordinates:
 C237(H237), C238(H238), C240(H240), C241(H241), C171(H171), C175(H175),
 C174(H174), C172(H172), C7(H7), C6(H6), C4(H4), C3(H3), C160(H160), C162(H162),
  C163(H163), C159(H159), C188(H188), C187(H187), C185(H185), C184(H184),
 C262(H262), C263(H263), C265(H265), C266(H266), C246(H246), C244(H244),
 C243(H243), C247(H247), C42(H42), C46(H46), C45(H45), C43(H43), C165(H165),
 C166(H166), C168(H168), C169(H169), C13(H13), C12(H12), C10(H10), C9(H9),
 C87(H87), C88(H88), C90(H90), C91(H91), C277(H277), C279(H279), C280(H280),
 C276(H276), C54(H54), C55(H55), C57(H57), C58(H58), C77(H77), C73(H73),
 C74(H74), C76(H76), C63(H63), C64(H64), C60(H60), C61(H61), C68(H68), C70(H70),
  C71(H71), C67(H67), C51(H51), C52(H52), C48(H48), C49(H49), C282(H282),
 C283(H283), C285(H285), C286(H286), C81(H81), C82(H82), C84(H84), C85(H85),
 C250(H250), C249(H249), C253(H253), C252(H252), C271(H271), C272(H272),
 C268(H268), C269(H269), C31(H31), C32(H32), C28(H28), C29(H29), C37(H37),
 C38(H38), C34(H34), C35(H35), C19(H19), C18(H18), C16(H16), C15(H15),
 C110(H110), C109(H109), C107(H107), C106(H106), C191(H191), C190(H190),
 C194(H194), C193(H193), C100(H100), C99(H99), C103(H103), C102(H102), C96(H96),
  C97(H97), C93(H93), C94(H94), C259(H259), C255(H255), C256(H256), C258(H258),
 C116(H116), C115(H115), C113(H113), C112(H112), C21(H21), C22(H22), C24(H24),
 C25(H25), C301(H301), C302(H302), C304(H304), C305(H305), C295(H295),
 C294(H294), C298(H298), C297(H297), C289(H289), C288(H288), C292(H292),
 C291(H291), C307(H307), C308(H308), C310(H310), C311(H311), C180(H180),
 C178(H178), C177(H177), C181(H181), C204(H204), C205(H205), C207(H207),
 C208(H208), C201(H201), C202(H202), C198(H198), C199(H199), C223(H223),
 C224(H224), C226(H226), C227(H227), C214(H214), C213(H213), C211(H211),
 C210(H210), C233(H233), C229(H229), C230(H230), C232(H232), C216(H216),
 C217(H217), C219(H219), C220(H220), C123(H123), C124(H124), C120(H120),
 C121(H121), C136(H136), C132(H132), C133(H133), C135(H135), C149(H149),
 C148(H148), C146(H146), C145(H145), C151(H151), C155(H155), C154(H154),
 C152(H152), C138(H138), C139(H139), C141(H141), C142(H142), C129(H129),
 C130(H130), C126(H126), C127(H127)
6.b Fitted hexagon refined as free rotating group:
 C236(C237,C238,C239,C240,C241), C171(C170,C175,C174,C173,C172), C7(C6,C5,C4,
 C3,C2), C160(C161,C162,C163,C158,C159), C183(C188,C187,C186,C185,C184),
 C261(C262,C263,C264,C265,C266), C246(C245,C244,C243,C242,C247), C42(C41,C46,
 C45,C44,C43), C165(C166,C167,C168,C169,C164), C8(C13,C12,C11,C10,C9), C87(C88,
 C89,C90,C91,C86), C277(C278,C279,C280,C275,C276), C53(C54,C55,C56,C57,C58),
 C77(C72,C73,C74,C75,C76), C63(C64,C59,C60,C61,C62), C68(C69,C70,C71,C66,C67),
 C51(C52,C47,C48,C49,C50), C282(C283,C284,C285,C286,C281), C80(C81,C82,C83,C84,
 C85), C251(C250,C249,C248,C253,C252), C270(C271,C272,C267,C268,C269), C31(C32,
 C27,C28,C29,C30), C36(C37,C38,C33,C34,C35), C19(C18,C17,C16,C15,C14),
 C105(C110,C109,C108,C107,C106), C192(C191,C190,C189,C194,C193), C101(C100,C99,
 C98,C103,C102), C95(C96,C97,C92,C93,C94), C259(C254,C255,C256,C257,C258),
 C111(C116,C115,C114,C113,C112), C20(C21,C22,C23,C24,C25), C300(C301,C302,C303,
 C304,C305), C295(C294,C293,C298,C297,C296), C290(C289,C288,C287,C292,C291),
 C306(C307,C308,C309,C310,C311), C180(C179,C178,C177,C176,C181), C203(C204,C205,
 C206,C207,C208), C200(C201,C202,C197,C198,C199), C222(C223,C224,C225,C226,
 C227), C214(C213,C212,C211,C210,C209), C233(C228,C229,C230,C231,C232),
 C215(C216,C217,C218,C219,C220), C123(C124,C119,C120,C121,C122), C136(C131,C132,
 C133,C134,C135), C149(C148,C147,C146,C145,C144), C151(C150,C155,C154,C153,
 C152), C138(C139,C140,C141,C142,C137), C128(C129,C130,C125,C126,C127)
;
_shelx_res_checksum              67958
_shelx_hkl_checksum              8872
_shelx_fab_checksum              7941
_olex2_submission_special_instructions 'No special instructions were received'