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_7250758
_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         'C26 H20 N6 O6 Zn, 3.925[C5H11N1O1]'
_chemical_formula_sum            'C45.62 H63.17 N9.92 O9.92 Zn'
_chemical_formula_weight         974.64
_chemical_name_common            UA-2
_chemical_name_systematic
di-Zinc-4,4'-(carbonylbis(azanediyl))dibenzoate;1,3-di(pyridin-4-yl)urea
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-07-22
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-22 deposited with the CCDC.	2025-07-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   27.5833(3)
_cell_length_b                   27.5833(3)
_cell_length_c                   14.4559(3)
_cell_measurement_reflns_used    33437
_cell_measurement_temperature    294
_cell_measurement_theta_max      74.0290
_cell_measurement_theta_min      2.2440
_cell_volume                     10998.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.91a 64-bit (release 23-01-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_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    'olex2.solve 1.5-alpha (Bourhis et al., 2015)'
_diffrn_ambient_temperature      294(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -94.00  -2.00   0.50    3.00    --  -48.61 111.00-139.00  184
  2  \w   -108.00 -22.00   0.50   12.00    --  -92.86 111.00-139.00  172
  3  \w     79.00 171.00   0.50   12.00    --  102.84  88.00 136.00  184
  4  \w     -5.00  30.00   0.50    3.00    --  -48.61  19.00  60.00   70
  5  \w     74.00 122.00   0.50    3.00    --   50.11 125.00  90.00   96
  6  \w    -58.00 -18.00   0.50   12.00    --  -92.86  61.00-150.00   80
  7  \w    -58.00 -18.00   0.50   12.00    --  -92.86  61.00  30.00   80
  8  \w    -60.00 -20.00   0.50   12.00    --  -92.86   0.00  60.00   80
  9  \w    -60.00 -20.00   0.50   12.00    --  -92.86   0.00-180.00   80
 10  \w     29.00  88.00   0.50   12.00    --  102.84 -61.00 -60.00  118
 11  \w     -5.00  30.00   0.50    3.00    --  -48.61  19.00 150.00   70
 12  \w     24.00 119.00   0.50    3.00    --   50.11  77.00  90.00  190
 13  \w     24.00 119.00   0.50    3.00    --   50.11  77.00   0.00  190
 14  \w    -60.00 -20.00   0.50   12.00    --  -92.86   0.00 150.00   80
 15  \w    -60.00 -20.00   0.50   12.00    --  -92.86   0.00-120.00   80
 16  \w   -172.00 -72.00   0.50   12.00    --  -92.86 -30.00  60.00  200
 17  \w    -60.00 -20.00   0.50   12.00    --  -92.86   0.00 120.00   80
 18  \w    -58.00 -18.00   0.50   12.00    --  -92.86  61.00 150.00   80
 19  \w     25.00  65.00   0.50   12.00    --  102.84 -45.00  30.00   80
 20  \w     24.00  49.00   0.50    3.00    --   50.11  77.00-120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0079746000
_diffrn_orient_matrix_UB_12      -0.0540682000
_diffrn_orient_matrix_UB_13      -0.0219711000
_diffrn_orient_matrix_UB_21      0.0263752000
_diffrn_orient_matrix_UB_22      0.0065228000
_diffrn_orient_matrix_UB_23      -0.0931233000
_diffrn_orient_matrix_UB_31      0.0486128000
_diffrn_orient_matrix_UB_32      -0.0124288000
_diffrn_orient_matrix_UB_33      0.0468003000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            84059
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.498
_diffrn_reflns_theta_min         2.265
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.103
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77950
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.91a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       plate
_exptl_crystal_F_000             4126
_exptl_crystal_preparation       'solvothermal synthesis from diethylformamide'
_exptl_crystal_recrystallization_method 'from diethylformamide'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.364
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         10989
_refine_ls_number_restraints     358
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0646
_refine_ls_R_factor_gt           0.0558
_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^)+(0.1304P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1942
_refine_ls_wR_factor_ref         0.2040
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7869
_reflns_number_total             10989
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02649k1.cif
_cod_data_source_block           ua-2_new
_cod_original_cell_volume        10998.6(4)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_database_code               7250758
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         'Zn C15 H10 O4 N4'
_chemical_oxdiff_usercomment     'rt!!, CSD: QAZFUS'
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.810
_diffrn_oxdiff_digest_hkl
;
436e812ff90dc9d89d2c2b2a1ad4168132384f
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N10-H10A = N2-H2 = N-H = N1-H1
 0.94 with sigma of 0.02
 H-N
 0.94 with sigma of 0.01
 H10A-C13 \\sim H2-C14
 with sigma of 0.02
3. Restrained planarity
 H10A, N10, C1I, N2, H2
 with sigma of 0.1
 C1A, C14, N2, C1I
 with sigma of 0.1
 H, N, C1J, N1, H1
 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 0.04 and sigma
for terminal atoms of 0.08 within 2A
6.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C16(H16), C17(H17), C18(H18), C1A(H1A), C1B(H1B),
 C1C(H1C), C1D(H1D), C1E(H1E), C1F(H1F), C1H(H1H), C1K(H1K), C1L(H1L), C1M(H1M)
;
_shelx_res_checksum              96850
_shelx_fab_checksum              3700
_platon_squeeze_special_details
;
A solvent mask was calculated and 1761 electrons were 
found in a volume of 6755\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3.925[C5H11N1O1] per asymmetric unit 
which account for 1758 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_exptl_crystal_mounting_method 'kapton loop'
_olex2_submission_original_sample_id UA-2
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.410
_oxdiff_exptl_absorpt_empirical_full_min 0.691