Thiazolothiazole-based metal–organic frameworks for photocatalytic coupling of benzylamine and degradation of organic dyes
Li, Jun-Fei; Xu, Jing-Wen; Feng, Hui-Jun; Liu, Qiao-Yun; Wang, Jun-Wen; New Journal of Chemistry 49 (2025) 6838–6845; doi:10.1039/D5NJ00340G

data_7063720
_publ_section_title
;
 Thiazolothiazole-based metal--organic frameworks for photocatalytic
 coupling of benzylamine and degradation of organic dyes
;
_journal_issue                   16
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              6838
_journal_page_last               6845
_journal_paper_doi               10.1039/D5NJ00340G
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C112 H64 Cd4 N16 O16 S8, 5[C3H7N]'
_chemical_formula_sum            'C127 H99 Cd4 N21 O16 S8'
_chemical_formula_weight         2881.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-27
_audit_creation_method
; 
Olex2 1.5 
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817) 
;
_audit_update_record
;
2024-11-13 deposited with the CCDC.	2025-03-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.105(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.2315(9)
_cell_length_b                   24.0207(13)
_cell_length_c                   17.5271(9)
_cell_measurement_reflns_used    9792
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      66.43
_cell_measurement_theta_min      4.33
_cell_volume                     6895.5(6)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX2'
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0662
_diffrn_reflns_av_unetI/netI     0.1294
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            27463
_diffrn_reflns_point_group_measured_fraction_full 0.818
_diffrn_reflns_point_group_measured_fraction_max 0.818
_diffrn_reflns_theta_full        65.068
_diffrn_reflns_theta_max         65.068
_diffrn_reflns_theta_min         2.698
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.547
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       block
_exptl_crystal_F_000             2912
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.712
_refine_diff_density_min         -1.487
_refine_diff_density_rms         0.165
_refine_ls_abs_structure_details
; 
 Refined as an inversion twin. 
;
_refine_ls_abs_structure_Flack   0.473(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.889
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1245
_refine_ls_number_reflns         19216
_refine_ls_number_restraints     2554
_refine_ls_restrained_S_all      0.906
_refine_ls_R_factor_all          0.1289
_refine_ls_R_factor_gt           0.0885
_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^)+(0.0100P)^2^+140.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1959
_refine_ls_wR_factor_ref         0.2267
_reflns_Friedel_coverage         0.645
_reflns_Friedel_fraction_full    0.659
_reflns_Friedel_fraction_max     0.659
_reflns_number_gt                12271
_reflns_number_total             19216
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00340g2.cif
_cod_data_source_block           p21m
_cod_depositor_comments
'Adding full bibliography for 7063718--7063720.cif.'
_cod_database_code               7063720
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.695
_olex2_refinement_description
; 
1. Twinned data refinement 
 Scales: 0.527(11) 
 0.473(11) 
2. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups 
3. Restrained distances 
 S2-C98 
 1.72 with sigma of 0.02 
 N7-C101 = N7-C98 = C25-C98 = C25-N16 = C51-N16 
 1.32 with sigma of 0.02 
 S5-C101 = S5-C25 = S2-C98 = S2-C51 
 1.72 with sigma of 0.02 
 C101-C98 = C51-C25 
 2.4 with sigma of 0.02 
 Cd6-N3 
 2.3 with sigma of 0.02 
 N11-C76 = C103-N11 = C103-C31 = C31-N4 = C19-N4 
 1.32 with sigma of 0.02 
 S7-C19 = S7-C103 = S8-C76 = S8-C31 
 1.72 with sigma of 0.02 
 C19-C31 
 2.4 with sigma of 0.02 
 C103-C76 
 2.4 with sigma of 0.02 
 C112-N10 = C13-N10 = C13-C52 = C52-N12 = C69-N12 
 1.32 with sigma of 0.02 
 S1-C112 = S1-C52 = S4-C13 = S4-C69 
 1.72 with sigma of 0.02 
 C13-C112 = C69-C52 
 2.4 with sigma of 0.02 
 S6-C90 = S6-C36 = S3-C105 = S3-C38 
 1.72 with sigma of 0.02 
 C90-N8 = C105-N8 = C105-C36 = N13-C36 = N13-C38 
 1.32 with sigma of 0.02 
 C105-C90 = C38-C36 
 2.4 with sigma of 0.02 
 S6-C105 
 2.6 with sigma of 0.02 
 Cd8-C64 
 3.1 with sigma of 0.02 
 C72-Cd8 
 3.1 with sigma of 0.02 
 N15-Cd4 
 2.2 with sigma of 0.02 
 C31-C76 
 2.4 with sigma of 0.02 
 S5-N7 
 2.6 with sigma of 0.02 
 C98-N16 
 2.2 with sigma of 0.02 
 C4-C112 
 2.4 with sigma of 0.02 
 C112-C8 
 2.4 with sigma of 0.02 
 C63-C22 
 1.53 with sigma of 0.01 
4. Rigid bond restraints 
 All non-hydrogen atoms 
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01 
5. Uiso/Uaniso restraints and constraints 
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma 
for terminal atoms of 0.02 within 2A 
Uanis(Cd4) \\sim Ueq, Uanis(Cd1) \\sim Ueq, Uanis(Cd2) \\sim Ueq, Uanis(O5) 
\\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O13) \\sim Ueq, Uanis(O9) \\sim Ueq, 
Uanis(N14) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C22) 
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C40) \\sim Ueq, 
Uanis(O14) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C63) 
\\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C42) \\sim Ueq, 
Uanis(C50) \\sim Ueq, Uanis(Cd5) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C20) 
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C58) \\sim Ueq, 
Uanis(C44) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(N6) 
\\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C18) \\sim Ueq, 
Uanis(C65) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C46) 
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C34) \\sim Ueq, 
Uanis(C28) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(S4) 
\\sim Ueq, Uanis(N12) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C107) \\sim Ueq, 
Uanis(C109) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C83) 
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C52) \\sim Ueq, 
Uanis(C3) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C90) 
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C57) \\sim Ueq, 
Uanis(C61) \\sim Ueq, Uanis(N10) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(C95) 
\\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(S6) \\sim Ueq, Uanis(N8) \\sim Ueq, 
Uanis(C85) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C15) 
\\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C36) \\sim Ueq, 
Uanis(C105) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C6) 
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(N13) \\sim Ueq, Uanis(S3) \\sim Ueq, 
Uanis(C94) \\sim Ueq, Uanis(C100) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C8) 
\\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C38) \\sim Ueq, 
Uanis(O7) \\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O12) 
\\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(Cd8) \\sim Ueq, 
Uanis(Cd6) \\sim Ueq, Uanis(Cd3) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(N2) 
\\sim Ueq, Uanis(N5) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(N3) \\sim Ueq, 
Uanis(C89) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C64) 
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(Cd7) \\sim Ueq, Uanis(C102) \\sim Ueq, 
Uanis(C110) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C35) 
\\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C104) \\sim Ueq, 
Uanis(C108) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C75) 
\\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C76) \\sim Ueq, 
Uanis(C9) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(S8) 
\\sim Ueq, Uanis(N11) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(S5) \\sim Ueq, 
Uanis(N7) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C77) 
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(N4) \\sim Ueq, 
Uanis(S7) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(N16) 
\\sim Ueq, Uanis(S2) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C79) \\sim Ueq, 
Uanis(C81) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C5) 
\\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C88) \\sim Ueq, 
Uanis(C78) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O2) 
\\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms 
of 0.02 
Uanis(N1) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006 
Uanis(Cd1) = Uanis(Cd2) 
Uanis(Cd4) = Uanis(Cd5) 
Uanis(Cd3) = Uanis(Cd6) 
6. Others 
 Sof(Cd2)=Sof(Cd3)=Sof(Cd5)=Sof(Cd7)=1-FVAR(1) 
 Sof(Cd1)=Sof(Cd4)=Sof(Cd6)=Sof(Cd8)=FVAR(1) 
7.a Aromatic/amide H refined with riding coordinates: 
 C64(H64), C66(H66), C70(H70), C72(H72), C89(H89), C45(H45), C23(H23), 
 C93(H93), C102(H102), C104(H104), C108(H108), C110(H110), C26(H26), C28(H28), 
 C32(H32), C34(H34), C78(H78), C80(H80), C84(H84), C86(H86), C54(H54), C56(H56), 
  C60(H60), C62(H62), C53(H53), C107(H107), C109(H109), C55(H55), C1(H1), 
 C4(H4), C57(H57), C29(H29), C15(H15), C61(H61), C8(H8), C12(H12), C14(H14), 
 C18(H18), C20(H20), C71(H71), C9(H9), C37(H37), C75(H75), C42(H42), C44(H44), 
 C48(H48), C50(H50), C95(H95), C3(H3), C49(H49), C99(H99), C2(H2), C65(H65), 
 C67(H67), C17(H17), C39(H39), C79(H79), C81(H81), C41(H41), C21(H21), C85(H85), 
  C87(H87), C11(H11), C111(H111) 
7.b Fitted hexagon refined as free rotating group: 
 N2(C64,C66,C68,C70,C72), N3(C89,C45,C91,C23,C93), N5(C102,C104,C106,C108, 
 C110), N6(C26,C28,C30,C32,C34), N9(C78,C80,C82,C84,C86), N14(C54,C56,C58,C60, 
 C62), N15(C53,C107,C27,C109,C55), C7(C57,C29,C59,C15,C61), C10(C12,C14,C16,C18, 
 C20), C35(C71,C9,C73,C37,C75), C40(C42,C44,C46,C48,C50), C47(C95,C3,C97,C49, 
 C99), C63(C2,C65,C33,C67,C17), C77(C39,C79,C5,C81,C41), C83(C21,C85,C43,C87, 
 C11) 
;
_smtbx_masks_special_details
; 
A solvent mask was calculated and 290 electrons were 
found in a volume of 2404\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
10[C3H7N] per Asymmetric Unit 
which account for 320 electrons 
per unit cell. 
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              8338
_shelx_fab_checksum              14069
_olex2_submission_special_instructions 'No special instructions were received'