Synergistic ligand–guest engineering for topological and functional control in cobalt(ii)-based metal–organic frameworks
Shi, Huatian; Liao, Yuluan; Li, Lianxiang; Sun, Po; wei, Xianwen; Yu, Weibin; CrystEngComm 27 (2025) 6894–6904; doi:10.1039/D5CE00801H

data_7250871
_publ_section_title
;
 Synergistic ligand--guest engineering for topological and functional
 control in cobalt(ii)-based metal--organic frameworks
;
_journal_issue                   42
_journal_name_full               CrystEngComm
_journal_page_first              6894
_journal_page_last               6904
_journal_paper_doi               10.1039/D5CE00801H
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C66 H40 Co2 N2 O8, 0.5(C16 H10), 8[CH3OH]'
_chemical_formula_sum            'C82 H77 Co2 N2 O16'
_chemical_formula_weight         1464.31
_space_group_crystal_system      tetragonal
_space_group_IT_number           137
_space_group_name_Hall           '-P 4ac 2a'
_space_group_name_H-M_alt        'P 42/n m c :2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-06-17
_audit_creation_method
; 
Olex2 1.5 
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928) 
;
_audit_update_record
;
2025-07-24 deposited with the CCDC.	2025-09-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.243(2)
_cell_length_b                   15.243(2)
_cell_length_c                   45.096(7)
_cell_measurement_reflns_used    3781
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      21.45
_cell_measurement_theta_min      2.25
_cell_volume                     10478(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_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  0.1208
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            43693
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.463
_diffrn_reflns_theta_min         2.094
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.365
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4861
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. 
wR2(int) was 0.0921 before and 0.0588 after correction. 
The Ratio of minimum to maximum transmission is 0.6523. 
The \l/2 correction factor is 0.00150. 
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    0.928
_exptl_crystal_description       block
_exptl_crystal_F_000             3060
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.661
_refine_diff_density_min         -0.695
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         5222
_refine_ls_number_restraints     1369
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.1747
_refine_ls_R_factor_gt           0.1285
_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^+80.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2556
_refine_ls_wR_factor_ref         0.2800
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2898
_reflns_number_total             5222
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00801h2.cif
_cod_data_source_block           Pyrene@T-MOF-1
_cod_depositor_comments
'Adding full bibliography for 7250870--7250873.cif.'
_cod_original_sg_symbol_H-M      'P 42/n m c'
_cod_database_code               7250871
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.914
_olex2_refinement_description
; 
1. Fixed Uiso 
 At 1.2 times of: 
  All C(H) groups 
2. Restrained distances 
 C1A-C1B = C1B-C1C = C1H-C1I = C1I-C1J 
 1.4 with sigma of 0.02 
 C1A-C1N = C1C-C1D = C1G-C1H = C1J-C1K 
 1.41 with sigma of 0.02 
 C1D-C1O = C1D-C1E = C1F-C1G = C1G-C1P = C1K-C1L = C1K-C1P = C1M-C1N = C1N-C1O 
 1.44 with sigma of 0.02 
 C1E-C1F = C1L-C1M 
 1.38 with sigma of 0.02 
 C1O-C1P 
 1.43 with sigma of 0.02 
 C20-C19 = C21-C20 = C22-C21 = C23-C22 = C24-C23 = C24-C19 = C13-C12 = C14-C13 
 = C15-C14 = C16-C15 = C17-C16 = C17-C12 = C34-C29 = C34-C33 = C33-C32 = C32- 
 C31 = C31-C30 = C30-C29 = C29-C28 = C35-C34 = C27-C26 = C26-C25 = C11-C10 = C9- 
 C10 = C8-C7 = C7-C2 = C2-C1 = C3-C2 = C4-C3 = C5-C4 = C6-C5 = C7-C6 
 1.39 with sigma of 0.001 
 C28-C27 
 1.53 with sigma of 0.001 
 C1A-C1C = C1H-C1J 
 2.44 with sigma of 0.04 
 C1A-C1M = C1C-C1E = C1F-C1H = C1J-C1L 
 2.5 with sigma of 0.04 
 C1A-C1O = C1C-C1O = C1D-C1F = C1E-C1G = C1J-C1P = C1K-C1M = C1L-C1N 
 2.46 with sigma of 0.04 
 C1B-C1D = C1G-C1I = C1I-C1K 
 2.45 with sigma of 0.04 
 C1D-C1N = C1D-C1P = C1G-C1K = C1G-C1O = C1K-C1O = C1N-C1P 
 2.49 with sigma of 0.04 
 C1F-C1P = C1M-C1O 
 2.48 with sigma of 0.04 
 C1A-C1B \\sim C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G 
\\sim C1G-C1H \\sim C1H-C1I 
 \\sim C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1N \\sim 
C1N-C1A \\sim C1N-C1O \\sim C1O- 
 C1D \\sim C1O-C1P \\sim C1P-C1G \\sim C1P-C1K 
 with sigma of 0.02 
 C1A-C1C \\sim C1A-C1O \\sim C1D-C1B \\sim C1D-C1N \\sim C1C-C1O \\sim C1B-C1N 
\\sim C1E-C1G \\sim C1E-C1O 
 \\sim C1P-C1F \\sim C1F-C1D \\sim C1D-C1P \\sim C1G-C1O \\sim C1G-C1I \\sim 
C1G-C1K \\sim C1I-C1K \\sim C1H- 
 C1J \\sim C1H-C1P \\sim C1J-C1P \\sim C1L-C1N \\sim C1L-C1P \\sim C1N-C1P 
\\sim C1M-C1O \\sim C1K-C1O ~ 
 C1K-C1M 
 with sigma of 0.04 
3. Restrained planarity 
 C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, C1I, C1J, C1K, C1L, C1M, C1N, C1O, C1P 
 with sigma of 0.1 
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 
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G \\sim C1H \\sim 
C1I \\sim C1J \\sim C1K \\sim C1L \\sim C1M \\sim C1N \\sim C1O \\sim C1P: 
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A 
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C34) 
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C26) \\sim Ueq, 
Uanis(C25) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) 
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02 
Uanis(C1B) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1N) \\sim Ueq, Uanis(C1C) 
\\sim Ueq, Uanis(C1M) \\sim Ueq, Uanis(C1O) \\sim Ueq, Uanis(C1D) \\sim Ueq, 
Uanis(C1L) \\sim Ueq, Uanis(C1P) \\sim Ueq, Uanis(C1E) \\sim Ueq, Uanis(C1K) 
\\sim Ueq, Uanis(C1G) \\sim Ueq, Uanis(C1F) \\sim Ueq, Uanis(C1J) \\sim Ueq, 
Uanis(C1H) \\sim Ueq, Uanis(C1I) \\sim Ueq: with sigma of 0.005 and sigma for 
terminal atoms of 0.01 
6. Rigid body (RIGU) restrains 
 C1A, C1B, C1C, C1D, C1E, C1F, C1G, C1H, C1I, C1J, C1K, C1L, C1M, C1N, C1O, C1P 
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004 
7. Others 
 Fixed Sof: C1A(0.125) H1A(0.125) C1B(0.125) H1B(0.125) C1C(0.125) H1C(0.125) 
 C1D(0.125) C1E(0.125) H1E(0.125) C1F(0.125) H1F(0.125) C1G(0.125) C1H(0.125) 
 H1H(0.125) C1I(0.125) H1I(0.125) C1J(0.125) H1J(0.125) C1K(0.125) C1L(0.125) 
 H1L(0.125) C1M(0.125) H1M(0.125) C1N(0.125) C1O(0.125) C1P(0.125) 
8.a Riding coordinates: 
 C3(H3), C4(H4), C5(H5), C6(H6), C13(H13), C14(H14), C16(H16), C17(H17), 
 C23(H23), C24(H24), C30(H30), C33(H33) 
8.b Aromatic/amide H refined with riding coordinates: 
 C10(H10), C11(H11), C20(H20), C21(H21), C25(H25), C26(H26), C31(H31), 
 C32(H32), C1A(H1A), C1B(H1B), C1C(H1C), C1E(H1E), C1F(H1F), C1H(H1H), C1I(H1I), 
  C1J(H1J), C1L(H1L), C1M(H1M) 
;
_smtbx_masks_special_details
; 
A solvent mask was calculated and 570 electrons were 
found in a volume of 4594\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
16[CH3OH] per formula unit 
which account for 576 electrons 
per unit cell. 
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80732
_shelx_fab_checksum              10459
_olex2_submission_special_instructions 'No special instructions were received'