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_7250760
_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, 0.083[C2H2I2], 0.167[C2H2I2]'
_chemical_formula_sum            'C13.71 H11.42 I1.42 N3 O3.25 Zn'
_chemical_formula_weight         515.32
_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
;
2025-06-18 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                   32.480(3)
_cell_length_b                   32.480(3)
_cell_length_c                   7.6920(5)
_cell_measurement_reflns_used    4188
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      48.3170
_cell_measurement_theta_min      4.1050
_cell_volume                     7027.5(10)
_computing_cell_refinement       'CrysAlisPro 1.171.43.76a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.76a 64-bit (release 21-06-2023))'
_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_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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     46.00 102.00   0.25   30.00    --   59.49  15.00-150.00  224
  2  \w     23.00  77.00   0.25   30.00    --   59.49-125.00-120.00  216
  3  \w    -77.00 -28.00   0.25   30.00    --  -61.55 125.00-150.00  196
  4  \w    -78.00 -24.00   0.25   30.00    --  -61.55 125.00 -90.00  216
  5  \w     34.00  89.00   0.25   30.00    --   73.04-125.00 150.00  220
  6  \w     60.00 113.00   0.25   30.00    --   73.63  15.00 120.00  212
  7  \w     60.00 113.00   0.25   30.00    --   73.63  15.00 -30.00  212
  8  \w   -109.00 -66.00   0.25   30.00    --  -75.12 -15.00 150.00  172
  9  \w   -117.00 -77.00   0.25   30.00    --  -75.12 -15.00 120.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54187
_diffrn_reflns_av_R_equivalents  0.1480
_diffrn_reflns_av_unetI/netI     0.0698
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       6
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            10814
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        38.988
_diffrn_reflns_theta_max         38.988
_diffrn_reflns_theta_min         4.158
_exptl_absorpt_coefficient_mu    16.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.00776
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.76a (Rigaku Oxford Diffraction, 2023)
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    1.461
_exptl_crystal_description       needle
_exptl_crystal_F_000             2949
_exptl_crystal_recrystallization_method
'solvothermal synthesis in DEF, drying, refilling with diiodomethane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.391
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.3(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.281
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         1356
_refine_ls_number_restraints     306
_refine_ls_restrained_S_all      1.176
_refine_ls_R_factor_all          0.1291
_refine_ls_R_factor_gt           0.1125
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2554
_refine_ls_wR_factor_ref         0.2747
_reflns_Friedel_coverage         0.607
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                1127
_reflns_number_total             1356
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02649k1.cif
_cod_data_source_block           tmu31_dim_rigsynr_vlc_sq_rev
_cod_original_cell_volume        7027.5(13)
_cod_original_sg_symbol_Hall     'P 62 2c (0 0 1)'
_cod_database_code               7250760
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         CHNOZn
_shelx_estimated_absorpt_t_max   0.498
_shelx_estimated_absorpt_t_min   0.140
_diffrn_oxdiff_digest_hkl
;
0138cb1f723315df9352570466287568f7e48d
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7(3)
 0.3(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
3. Restrained distances
 N1-C8 \\sim N52-C58
 with sigma of 0.02
 N52-C54 \\sim N1-C5
 with sigma of 0.02
 O2-C1 \\sim O1-C1
 with sigma of 0.02
4. 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
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. 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
6.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C6(H6), C4(H4), C3(H3), C7(H7), N52(H52), C56(H56), C52(H52A),
 C53(H53), C55(H55)
6.b Fitted hexagon refined as free rotating group:
 C6(C5,C4,C3,C2,C7), C56(N51,C52,C53,C54,C55)
;
_shelx_res_checksum              54593
_platon_squeeze_special_details
;
A solvent mask was calculated and 982 electrons were 
found in a volume of 3614\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
6.16[C2H2I2], 1.22[C2H2I2], 1.22[C2H2I2] per Unit Cell 
which account for 980 electrons 
per unit cell.
;
_shelx_fab_checksum              55110
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 65.776
_oxdiff_exptl_absorpt_empirical_full_min 0.586