Unlocking porosity: structural tuning of urea-based MOFs via reaction parameter control
Esrafili, Leili; Cheung, Ocean; Adriaensens, Peter; Derveaux, Elien; Glasby, Lawson T.; Moghadam, Peyman Z.; Vande Velde, Christophe M. L.; RSC Advances 15 (2025) 27531–27543; doi:10.1039/D5RA02649K

data_7250757
_publ_section_title
;
 Unlocking porosity: structural tuning of urea-based MOFs via reaction
 parameter control
;
_journal_issue                   34
_journal_name_full               'RSC Advances'
_journal_page_first              27531
_journal_page_last               27543
_journal_paper_doi               10.1039/D5RA02649K
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety
'C13 H10 N3 O3.25 Zn, 0.583[C7H7N1O2], 0.125[C7H7NO2], 0.125[C7H7NO2]'
_chemical_formula_sum            'C18.84 H15.84 N3.82 O4.92 Zn'
_chemical_formula_weight         439.84
_chemical_name_systematic
di-Zinc-4,4'-(carbonylbis(azanediyl))dibenzoate;1,3-di(pyridin-4-yl)urea;hemioxide
_space_group_crystal_system      hexagonal
_space_group_IT_number           180
_space_group_name_Hall           'P 62 2 (0 0 4)'
_space_group_name_H-M_alt        'P 62 2 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-06-12
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-04 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            12
_cell_length_a                   32.499(2)
_cell_length_b                   32.499(2)
_cell_length_c                   7.7152(4)
_cell_measurement_reflns_used    2260
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      57.2810
_cell_measurement_theta_min      3.1310
_cell_volume                     7057.0(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.76a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.76a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.76a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/3 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Rigaku Synergy R'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.0533
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            8932
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        51.977
_diffrn_reflns_theta_max         51.977
_diffrn_reflns_theta_min         3.140
_exptl_absorpt_coefficient_mu    1.726
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.69236
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_description       needle
_exptl_crystal_F_000             2700
_exptl_crystal_preparation
'dried crystal soaked in molten beta-nitrostyrene'
_exptl_crystal_recrystallization_method
'solvothermal synthesis, drying, solvent exchange with nitrostyrene'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.173
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 660 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     174
_refine_ls_number_reflns         2577
_refine_ls_number_restraints     297
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0468
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0834P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1248
_reflns_Friedel_coverage         0.638
_reflns_Friedel_fraction_full    0.945
_reflns_Friedel_fraction_max     0.945
_reflns_number_gt                2022
_reflns_number_total             2577
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02649k1.cif
_cod_data_source_block           tmu31_ns2_rigsyns_vlc_sq
_cod_original_cell_volume        7056.8(10)
_cod_original_sg_symbol_Hall     'P 62 2c (0 0 1)'
_cod_database_code               7250757
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.545
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. 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 within 2A
3. 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
4.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C3(H3), C4(H4), C6(H6), C7(H7), C52(H52), C53(H53), C55(H55),
 C56(H56), N52(H52A)
4.b Fitted hexagon refined as free rotating group:
 N51(C52,C53,C54,C55,C56)
;
_shelx_res_checksum              80056
_shelx_fab_checksum              11323
_platon_squeeze_special_details
;
A solvent mask was calculated and 745 electrons were 
found in a volume of 3614\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.583[C7H7N1O2], 0.125[C7H7NO2], 0.125[C7H7NO2] per Unit Cell 
which account for 720 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'