Collapse or capture? Guest-induced response of two structurally distinct pillared-MOFs upon exposure to pyridines and quinolines.
Giovanardi, Dario; Cagossi, Giorgio; Zolotarev, Pavel N.; Mazzeo, Paolo P.; Bacchi, Alessia; Carlucci, Lucia; Proserpio, Davide M.; Pelagatti, Paolo; Dalton transactions (Cambridge, England : 2003) 54 (2025) 13540–13548; doi:10.1039/d5dt01321f

data_1575407
_publ_section_title
;
 Collapse or capture? Guest-induced response of two structurally distinct
 pillared-MOFs upon exposure to pyridines and quinolines.
;
_journal_issue                   36
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13540
_journal_page_last               13548
_journal_paper_doi               10.1039/d5dt01321f
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety
'1.5(C52 H34 N4 O10 Zn2), 5.5(C9 H7 N), C3 H7 N O, [+ solvents]'
_chemical_formula_sum            'C141.75 H105.25 N13.75 O16 Zn3'
_chemical_formula_weight         2453.25
_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             2025-05-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-05-13 deposited with the CCDC.	2025-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                96.3530(10)
_cell_angle_beta                 98.1620(10)
_cell_angle_gamma                90.3930(10)
_cell_formula_units_Z            2
_cell_length_a                   15.2374(3)
_cell_length_b                   15.2428(3)
_cell_length_c                   27.0220(5)
_cell_measurement_reflns_used    26740
_cell_measurement_temperature    200.00
_cell_measurement_theta_max      70.066
_cell_measurement_theta_min      2.918
_cell_volume                     6172.8(2)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      200.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker Avance D8 Venture'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            146003
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.066
_diffrn_reflns_theta_min         2.918
_exptl_absorpt_coefficient_mu    1.261
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6183
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0850 before and 0.0676 after correction.
The Ratio of minimum to maximum transmission is 0.8205.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             2540
_exptl_crystal_size_max          0.025
_exptl_crystal_size_mid          0.022
_exptl_crystal_size_min          0.018
_refine_diff_density_max         0.962
_refine_diff_density_min         -0.936
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1696
_refine_ls_number_reflns         23360
_refine_ls_number_restraints     1134
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0933
_refine_ls_R_factor_gt           0.0789
_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^)+(0.1442P)^2^+13.5081P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2335
_refine_ls_wR_factor_ref         0.2503
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18578
_reflns_number_total             23360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01321f2.cif
_cod_data_source_block           pum168@(quino)7
_cod_depositor_comments
'Adding full bibliography for 1575404--1575407.cif.'
_cod_database_code               1575407
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.969
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C102-C101
 1.38 with sigma of 0.01
 N4B-C30B
 1.36 with sigma of 0.02
 N4A-C29A
 1.45 with sigma of 0.01
 C98-C99
 1.38 with sigma of 0.01
 N4A-C30A
 1.39 with sigma of 0.01
 N4B-C29B
 1.48 with sigma of 0.02
 C28B-N4B
 1.48 with sigma of 0.02
 C102-C103
 1.38 with sigma of 0.01
 C100-C101
 1.38 with sigma of 0.01
 C29B-C30B
 2.44 with sigma of 0.02
 N4A-C30A \\sim N4A-C30B
 with sigma of 0.02
 C30A-H30a \\sim C30B-H30a
 with sigma of 0.02
 C30A-H30b \\sim C30B-H30b
 with sigma of 0.02
 C30A-H30c \\sim C30B-H30c
 with sigma of 0.02
 N4A-C28A \\sim N4B-C28B
 with sigma of 0.02
 C9A-C4A \\sim C9B-C4B
 with sigma of 0.02
 C9A-N1A \\sim C9B-N1B
 with sigma of 0.02
 C9A-C8A \\sim C9B-C8B
 with sigma of 0.02
 C4A-C3A \\sim C4B-C3B
 with sigma of 0.02
 C4A-C5A \\sim C4B-C5B
 with sigma of 0.02
 N1A-C1A \\sim N1B-C1B
 with sigma of 0.02
 C3A-C2A \\sim C3B-C2B
 with sigma of 0.02
 C7A-C8A \\sim C7B-C8B
 with sigma of 0.02
 C7A-C6A \\sim C7B-C6B
 with sigma of 0.02
 C1A-C2A \\sim C1B-C2B
 with sigma of 0.02
 C5A-C6A \\sim C5B-C6B
 with sigma of 0.02
 C9A-C3A \\sim C9B-C3B
 with sigma of 0.04
 C9A-C7A \\sim C9B-C7B
 with sigma of 0.04
 C9A-C1A \\sim C9B-C1B
 with sigma of 0.04
 C9A-C5A \\sim C9B-C5B
 with sigma of 0.04
 C4A-N1A \\sim C4B-N1B
 with sigma of 0.04
 C4A-C2A \\sim C4B-C2B
 with sigma of 0.04
 C4A-C8A \\sim C4B-C8B
 with sigma of 0.04
 C4A-C6A \\sim C4B-C6B
 with sigma of 0.04
 N1A-C2A \\sim N1B-C2B
 with sigma of 0.04
 N1A-C8A \\sim N1B-C8B
 with sigma of 0.04
 C3A-C1A \\sim C3B-C1B
 with sigma of 0.04
 C3A-C5A \\sim C3B-C5B
 with sigma of 0.04
 C7A-C5A \\sim C7B-C5B
 with sigma of 0.04
 C8A-C6A \\sim C8B-C6B
 with sigma of 0.04
3. Restrained planarity
 C97, C105, N9, C104, C100, C103, C99, C101, C98, C102
 with sigma of 0.1
 C21A, C20A, C19A, C26A, C25A, C24A, N3A, C27A, C23A, C22A
 with sigma of 0.1
 C82, C87, N7, C86, C79, C85, C83, C81, C80, C84
 with sigma of 0.1
 C8B, N1B, C9B, C1B, C4B, C2B, H1B, H8B, C7B, C5B, C3B, H2B, C6B, H7B, H5B,
 H3B, H6B
 with sigma of 0.1
 C102, C103, C104, C105, C100, C101, C99, C98, C97, N9
 with sigma of 0.1
4. Rigid bond restraints
 N4B, C28B, C29B, C30B, O1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28A, N4A, C29A, C30A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C97, C105, N9, C104, C100, C103, C99, C101, C98, C102
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C80, C81, C79, C87, N7, C86, C82, C85, C83, C84
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C25A, C21A, C20A, C22A, C19A, C27A, C23A, N3A, C26A, C24A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19B, N3B, C27B, C20B, C22B, C26B, C21B, C23B, C25B, C24B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C30B \\sim C29B \\sim N4B \\sim C28B \\sim O1A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C28A \\sim N4A \\sim C29A \\sim C30A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C97 \\sim C105 \\sim N9 \\sim C104 \\sim C100 \\sim C103 \\sim C99 \\sim C101
\\sim C98 \\sim C102: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
C14B \\sim C17B \\sim C18B \\sim C16B \\sim C13B \\sim C15B \\sim N2B \\sim
C12B \\sim C10B \\sim C11B: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C17A \\sim C10A \\sim C11A \\sim N2A \\sim C12A \\sim C15A \\sim C14A \\sim
C16A \\sim C13A \\sim C18A: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C14B \\sim C17A \\sim C10A \\sim C11A \\sim N2A \\sim C12A \\sim C15A \\sim
C14A \\sim C16A \\sim C13A \\sim C18A \\sim C18B \\sim C17B \\sim C16B \\sim
C13B \\sim C15B \\sim N2B \\sim C12B \\sim C10B \\sim C11B: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C80 \\sim C81 \\sim C79 \\sim C87 \\sim N7 \\sim C86 \\sim C82 \\sim C85 \\sim
C83 \\sim C84: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C25A \\sim C21A \\sim C20A \\sim C22A \\sim C19A \\sim C27A \\sim C23A \\sim
N3A \\sim C26A \\sim C24A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
N8 \\sim C96 \\sim C91 \\sim C89 \\sim C90 \\sim C95 \\sim C94 \\sim C93 \\sim
C92 \\sim C88: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
C19B \\sim N3B \\sim C27B \\sim C20B \\sim C22B \\sim C26B \\sim C21B \\sim
C23B \\sim C25B \\sim C24B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C1A \\sim C9A \\sim C4A \\sim N1A \\sim C8A \\sim C3A \\sim C5A \\sim C7A \\sim
C2A \\sim C6A: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
C1B \\sim N1B \\sim C9B \\sim C8B \\sim C4B \\sim C2B \\sim C7B \\sim C5B \\sim
C3B \\sim C6B: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
Uanis(C28B) \\sim Ueq, Uanis(N4B) \\sim Ueq, Uanis(C29B) \\sim Ueq, Uanis(C30B)
\\sim Ueq, Uanis(O1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.002
Uanis(C105) \\sim Ueq, Uanis(N9) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C100)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C99) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C102) \\sim Ueq, : with
sigma of 0.05 and sigma for terminal atoms of 0.005
Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C13A) \\sim Ueq,
Uanis(C16A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C12A) \\sim Ueq,
Uanis(C14B) \\sim Ueq, Uanis(C15B) \\sim Ueq, Uanis(C16B) \\sim Ueq,
Uanis(C17B) \\sim Ueq, Uanis(C13B) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(N2A)
\\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12B) \\sim Ueq, Uanis(C11B) \\sim Ueq,
Uanis(N2B) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(C18B)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.05
6. Others
 Sof(N1B)=Sof(C9B)=Sof(C8B)=Sof(H8B)=Sof(C6B)=Sof(H6B)=Sof(C5B)=Sof(H5B)=
 Sof(C4B)=Sof(C3B)=Sof(H3B)=Sof(C2B)=Sof(H2B)=Sof(C1B)=Sof(H1B)=Sof(C7B)=
 Sof(H7B)=1-FVAR(1)
 Sof(C9A)=Sof(C4A)=Sof(N1A)=Sof(C3A)=Sof(H3Aa)=Sof(C7A)=Sof(H7A)=Sof(C1A)=
 Sof(H1A)=Sof(C2A)=Sof(H2Aa)=Sof(C5A)=Sof(H5A)=Sof(C8A)=Sof(H8A)=Sof(C6A)=
 Sof(H6A)=FVAR(1)
 Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=
 Sof(H17B)=Sof(C18B)=Sof(C13B)=Sof(C12B)=Sof(H12B)=Sof(C11B)=Sof(H11B)=
 Sof(C10B)=Sof(H10B)=Sof(N2B)=1-FVAR(2)
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=
 Sof(H17A)=Sof(C18A)=Sof(C13A)=Sof(C12A)=Sof(H12A)=Sof(C11A)=Sof(H11A)=
 Sof(C10A)=Sof(H10A)=Sof(N2A)=FVAR(2)
 Fixed Sof: N4A(0.5) C28A(0.5) H28A(0.5) C30A(0.5) H30a(0.5) H30b(0.5)
 H30c(0.5) C29A(0.5) H29a(0.5) H29b(0.5) H29c(0.5) C21A(0.5) H21A(0.5)
 C20A(0.5) H20A(0.5) C19A(0.5) H19A(0.5) N3A(0.5) C27A(0.5) C22A(0.5) C23A(0.5)
 H23A(0.5) C24A(0.5) H24A(0.5) C25A(0.5) H25A(0.5) C26A(0.5) H26A(0.5) N3B(0.5)
 C19B(0.5) H19B(0.5) C20B(0.5) H20B(0.5) C21B(0.5) H21B(0.5) C22B(0.5)
 C27B(0.5) C26B(0.5) H26B(0.5) C25B(0.5) H25B(0.5) C24B(0.5) H24B(0.5)
 C23B(0.5) H23B(0.5) N4B(0.5) C28B(0.5) H28B(0.5) C105(0.5) N9(0.5) C98(0.5)
 H98(0.5) C97(0.5) H97(0.5) C99(0.5) H99(0.5) C104(0.5) H104(0.5) C100(0.5)
 C102(0.5) H102(0.5) C103(0.5) H103(0.5) C101(0.5) H101(0.5) C29B(0.5)
 H29d(0.5) H29e(0.5) H29f(0.5) C30B(0.5) H30d(0.5) H30e(0.5) H30f(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C2(H2), N6(H6), C68(H68), C27(H27), C54(H54), C1(H1), N2(H2a), C67(H67),
 C56(H56), C29(H29), C53(H53), C28(H28), C55(H55), C3(H3), C4(H4), C30(H30),
 C47(H47), C48(H48), C49(H49), C75(H75), C76(H76), C50(H50), C70(H70), C69(H69),
  C41(H41), C24(H24), C77(H77), C43(H43), C33(H33), C74(H74), C44(H44), N3(H3a),
  C23(H23), C34(H34), C62(H62), C42(H42), C8(H8), C63(H63), C60(H60), C9(H9),
 C35(H35), C36(H36), C3A(H3Aa), C15(H15), C14(H14), C61(H61), C11(H11),
 C10(H10), C7A(H7A), C1A(H1A), C17(H17), C2A(H2Aa), C5A(H5A), C8A(H8A),
 C16(H16), C21(H21), C22(H22), C6A(H6A), C14A(H14A), C15A(H15A), C16A(H16A),
 C17A(H17A), C12A(H12A), C11A(H11A), C10A(H10A), C86(H86), C83(H83), C88(H88),
 C89(H89), C90(H90), C95(H95), C94(H94), C93(H93), C92(H92), C80(H80), C79(H79),
  C81(H81), C85(H85), C84(H84), C8B(H8B), C6B(H6B), C5B(H5B), C3B(H3B),
 C2B(H2B), C1B(H1B), C7B(H7B), C14B(H14B), C15B(H15B), C16B(H16B), C17B(H17B),
 C12B(H12B), C11B(H11B), C10B(H10B), C28A(H28A), C21A(H21A), C20A(H20A),
 C19A(H19A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A), C19B(H19B),
 C20B(H20B), C21B(H21B), C26B(H26B), C25B(H25B), C24B(H24B), C23B(H23B),
 C28B(H28B), C98(H98), C97(H97), C99(H99), C104(H104), C102(H102), C103(H103),
 C101(H101)
7.b Naphthalene refined as free rotating group:
 C14A(C15A,C16A,C17A,C18A,C13A,C12A,C11A,C10A,N2A), N8(C88,C89,C90,C91,C96,C95,
 C94,C93,C92), C14B(C15B,C16B,C17B,C18B,C13B,C12B,C11B,C10B,N2B), C21A(C20A,
 C19A,N3A,C27A,C22A,C23A,C24A,C25A,C26A), N3B(C19B,C20B,C21B,C22B,C27B,C26B,
 C25B,C24B,C23B)
7.c Idealised Me refined as rotating group:
 C30A(H30a,H30b,H30c), C29A(H29a,H29b,H29c), C29B(H29d,H29e,H29f), C30B(H30d,
 H30e,H30f)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              90760
_shelx_fab_checksum              12740
_olex2_submission_special_instructions 'No special instructions were received'