Precision pore engineering <i>via</i> fit-topology assembly in a Zn-porphyrin MOF for selective C<sub>2</sub>H<sub>2</sub> capture.
Zhu, Zhenliang; Xiao, Jianfei; Zhang, Min; Huang, Yaoqi; Yuan, Shaojun; Chemical science 16 (2025) 22638–22646; doi:10.1039/d5sc07319g

data_1576053
_publ_section_title
;
 Precision pore engineering <i>via</i> fit-topology assembly in a
 Zn-porphyrin MOF for selective C<sub>2</sub>H<sub>2</sub> capture.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22638
_journal_page_last               22646
_journal_paper_doi               10.1039/d5sc07319g
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety
'C104 N14 O18 Zn7, 0.25[], 0.25[], 0.25[], 0.25[]'
_chemical_formula_sum            'C108 H80 N16 O18 Zn7'
_chemical_formula_weight         2347.47
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-12-13 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.660(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.6765(19)
_cell_length_b                   25.6910(19)
_cell_length_c                   22.0059(17)
_cell_measurement_reflns_used    9843
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      56.82
_cell_measurement_theta_min      2.58
_cell_volume                     14216.7(19)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2019)'
_computing_data_collection       'APEX5 V2023.9-2 (Bruker, 2023)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE MetalJet PHOTON II'
_diffrn_measurement_method       '\w and \f shutterless scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_monochromator  'Helios Multi-layer Optic'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_unetI/netI     0.0647
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            25132
_diffrn_reflns_point_group_measured_fraction_full 0.503
_diffrn_reflns_point_group_measured_fraction_max 0.503
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.907
_diffrn_reflns_theta_min         1.783
_diffrn_source                   MetalJet
_diffrn_source_current           2.86
_diffrn_source_power             0.19931339999999997
_diffrn_source_type              'Liquid Metal source'
_diffrn_source_voltage           69.69
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.147
_exptl_absorpt_correction_T_max  0.751210
_exptl_absorpt_correction_T_min  0.570221
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0928 before and 0.0571 after correction.
 
For component 2:
 wR2(int) was 0.1089 before and 0.0689 after correction.
 
For component 3:
 wR2(int) was 0.0978 before and 0.0661 after correction.
 The Ratio of minimum to maximum transmission is 0.76.

Final HKLF 4 output contains 100378 reflections, Rint = 0.1572
 (43037 with I > 3sig(I), Rint = 0.1515)
;
_exptl_crystal_density_diffrn    1.097
_exptl_crystal_description       block
_exptl_crystal_F_000             4776
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.159
_refine_diff_density_min         -0.815
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
No quotients, so Flack parameter determined by classical intensity fit
;
_refine_ls_abs_structure_Flack   0.00(9)
_refine_ls_extinction_coef       0.00059(9)
_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   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1324
_refine_ls_number_reflns         25132
_refine_ls_number_restraints     1722
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1267
_refine_ls_R_factor_gt           0.1135
_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^)+(0.1700P)^2^+210.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2987
_refine_ls_wR_factor_ref         0.3116
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    0.000
_reflns_Friedel_fraction_max     0.000
_reflns_number_gt                21432
_reflns_number_total             25132
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07319g2.cif
_cod_data_source_block           240724lu_lgpz044800_0m_5_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1576053.cif.
;
_cod_database_code               1576053
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.914
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.355(4)
 0.351(3) 0.294(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 C98-C97 = C54-C53 = C84-C83 = C90-C93 = C24-C27 = C47-C50 = C6-C5 = C41-C40
 1.5 with sigma of 0.01
 N16-C107 = N16-C108
 1.5 with sigma of 0.01
 O6-C27 = O5-C27 = O3-C50 = O4-C50 = O2-C5 = O1-C5 = O7-C41 = O8-C41 = O10-C53
 = O11-C53 = O17-C84 = O16-C84 = O15-C93 = O14-C93 = O12-C98 = O13-C98
 1.25 with sigma of 0.01
 C3-C4 = C1-C2 = C101-C102 = C104-C103
 1.5 with sigma of 0.01
 N15-C105 = N15-C106
 1.5 with sigma of 0.01
 O5A-C27A = O6A-C27A
 1.25 with sigma of 0.01
 C107-C108
 2.55 with sigma of 0.01
 C105-C106
 2.55 with sigma of 0.01
 C25-C27 \\sim C27-C23
 with sigma of 0.02
 C27A-C24A \\sim C27-C24
 with sigma of 0.02
 C21-C20 \\sim C21A-C20
 with sigma of 0.02
4. Restrained planarity
 N1, N2, N3, C1, C2, C3, C4
 with sigma of 0.1
 N12, N13, N14, C101, C102, C103, C104
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
N16 \\sim C107 \\sim C108: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N15 \\sim C105 \\sim C106: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O5 \\sim O6 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim
C27 \\sim O5A \\sim O6A \\sim C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A
\\sim C26A \\sim C27A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C108) \\sim Ueq, Uanis(N16) \\sim Ueq, Uanis(C107) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C106) \\sim Ueq, Uanis(N15) \\sim Ueq, Uanis(C105) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C101) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7. Others
 Sof(O5A)=Sof(O6A)=Sof(C21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=1-FVAR(1)
 Sof(O5)=Sof(O6)=Sof(C21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C27)=FVAR(1)
8.a Riding coordinates:
 C105(H10G,H10H,H10I), C106(H10J,H10K,H10L), C107(H10M,H10N,H10O)
8.b Ternary CH refined with riding coordinates:
 O18(H18), O9(H9)
8.c Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C13(H13A,H13B), N15(H15A,H15B), N16(H16A,H16B)
8.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C7(H7), C52(H52), C51(H51), C17(H17), C18(H18A), C29(H29), C30(H30),
 C34(H34), C35(H35), C38(H38), C39(H39), C42(H42), C43(H43), C45(H45), C46(H46),
  C48(H48), C49(H49), C55(H55), C56(H56), C58(H58), C59(H59), C62(H62),
 C63(H63), C67(H67), C68(H68), C72(H72), C73(H73), C77(H77), C78(H78), C81(H81),
  C82(H82), C85(H85), C86(H86), C88(H88), C92(H92), C91(H91), C89(H89),
 C95(H95), C96(H96), C99(H99), C100(H100), C22(H22), C23(H23), C25(H25),
 C26(H26), C22A(H22A), C23A(H23A), C25A(H25A), C26A(H26A)
8.e Fitted hexagon refined as free rotating group:
 C9(C8,C7,C6,C52,C51), C37(C38,C39,C40,C42,C43), C44(C45,C46,C47,C48,C49),
 C55(C56,C57,C58,C59,C54), C81(C82,C83,C85,C86,C80), C88(C87,C92,C91,C90,C89),
 C95(C96,C97,C99,C100,C94), C21(C22,C23,C24,C25,C26), C21A(C22A,C23A,C24A,C25A,
 C26A)
8.f Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C101(H10A,H10B,H10C), C104(H10D,H10E,H10F),
 C108(H10P,H10Q,H10R)
;
_shelx_res_checksum              91636
_shelx_fab_checksum              27616
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'
_site                            XU