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_7250759
_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 H19 N6 O6 Zn, H2 O, 2(C5 H11 N O), 2.375[C5H11N1O2]'
_chemical_formula_sum            'C47.88 H69.12 N10.38 O13.75 Zn'
_chemical_formula_weight         1075.50
_chemical_name_common            UA-1
_chemical_name_systematic
di-Zinc-4,4'-(carbonylbis(azanediyl))dibenzoate;1,3-di(pyridin-4-yl)urea;diethylformamide;water
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   mixed
_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                 110.553(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5503(3)
_cell_length_b                   14.3850(2)
_cell_length_c                   22.7569(4)
_cell_measurement_reflns_used    46808
_cell_measurement_temperature    100.2(6)
_cell_measurement_theta_max      74.3560
_cell_measurement_theta_min      2.1020
_cell_volume                     5686.06(17)
_computing_cell_refinement       'CrysAlisPro 1.171.44.91a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.91a (Rigaku OD, 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)'
_diffrn_ambient_temperature      100.15
_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 0.973
_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   -126.00  -2.00   0.50    3.00    --  -49.21 -17.00  94.00  248
  2  \w      4.00 127.00   0.50    3.00    --   50.46  17.00 -95.00  246
  3  \w    -26.00  32.00   0.50    3.00    --   50.46 -17.00  94.00  116
  4  \w   -169.00 -46.00   0.50   15.00    --  -92.59 -17.00  94.00  246
  5  \w     55.00 178.00   0.50   15.00    --  101.86  17.00 -95.00  246
  6  \w    -26.00  28.00   0.50    3.00    --  -49.21  38.00  30.00  108
  7  \w    -51.00  25.00   0.50    3.00    --  -49.21  57.00 -60.00  152
  8  \w    -51.00 -18.00   0.50   15.00    --  -92.59  57.00-180.00   66
  9  \w   -112.00 -22.00   0.50   15.00    --  -92.59 125.00-150.00  180
 10  \w   -117.00 -25.00   0.50   15.00    --  -92.59  77.00  90.00  184
 11  \w    -60.00 -23.00   0.50   15.00    --  -92.59   0.00 -60.00   74
 12  \w    -51.00 -18.00   0.50   15.00    --  -92.59  57.00-150.00   66
 13  \w    -51.00 -18.00   0.50   15.00    --  -92.59  57.00   0.00   66
 14  \w    -51.00 -18.00   0.50   15.00    --  -92.59  57.00-120.00   66
 15  \w    -51.00 -18.00   0.50   15.00    --  -92.59  57.00 -30.00   66
 16  \w     25.00  56.00   0.50   15.00    --  101.86 -38.00 -90.00   62
 17  \w     25.00  56.00   0.50   15.00    --  101.86 -38.00   0.00   62
 18  \w     35.00 106.00   0.50   15.00    --  101.86 -99.00  30.00  142
 19  \w     25.00  56.00   0.50   15.00    --  101.86 -38.00 -60.00   62
 20  \w     25.00  56.00   0.50   15.00    --  101.86 -38.00 -30.00   62
 21  \w     35.00 106.00   0.50   15.00    --  101.86 -99.00  90.00  142
 22  \w   -116.00 -25.00   0.50    3.00    --  -49.21 -77.00  60.00  182
 23  \w   -116.00 -25.00   0.50    3.00    --  -49.21 -77.00 150.00  182
 24  \w     26.00 118.00   0.50    3.00    --   50.46  77.00 -30.00  184
 25  \w     26.00 118.00   0.50    3.00    --   50.46  77.00-120.00  184
 26  \w    -60.00 -23.00   0.50   15.00    --  -92.59   0.00 -90.00   74
 27  \w   -160.00 -68.00   0.50   15.00    --  -92.59 -77.00-120.00  184
 28  \w   -160.00 -68.00   0.50   15.00    --  -92.59 -77.00 -60.00  184
 29  \w   -170.00 -78.00   0.50   15.00    --  -92.59 -38.00 -30.00  184
 30  \w     28.00  81.00   0.50   15.00    --  101.86 -57.00 120.00  106
 31  \w     35.00  82.00   0.50   15.00    --  101.86 -77.00-150.00   94
 32  \w     78.00 169.00   0.50   15.00    --  101.86  77.00  60.00  182
;
_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      0.0621061000
_diffrn_orient_matrix_UB_12      0.0235172000
_diffrn_orient_matrix_UB_13      0.0638698000
_diffrn_orient_matrix_UB_21      0.0609216000
_diffrn_orient_matrix_UB_22      0.0062144000
_diffrn_orient_matrix_UB_23      -0.0316118000
_diffrn_orient_matrix_UB_31      -0.0173978000
_diffrn_orient_matrix_UB_32      0.1042495000
_diffrn_orient_matrix_UB_33      -0.0122997000
_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  0.0518
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            88080
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.801
_diffrn_reflns_theta_min         2.658
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.169
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76041
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_description       plate
_exptl_crystal_F_000             2276
_exptl_crystal_preparation       'synthesis from diethylformamide'
_exptl_crystal_recrystallization_method 'synthesis from diethylformamide'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.724
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         11510
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0711
_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^)+(0.1014P)^2^+5.9902P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2025
_refine_ls_wR_factor_ref         0.2058
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10367
_reflns_number_total             11510
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ra02649k1.cif
_cod_data_source_block           ua-1-cold_auto
_cod_original_cell_volume        5686.05(17)
_cod_database_code               7250759
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.892
_shelx_estimated_absorpt_t_min   0.721
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C44-C11 \\sim C45-C44
 with sigma of 0.02
 N43-C46 \\sim N43-C44
 with sigma of 0.02
 C1-C8 \\sim C1-C8A
 with sigma of 0.02
 N11-H11 \\sim N8-H8 \\sim N30-H30 \\sim N33-H33
 with sigma of 0.02
 C46-C13 \\sim C44-C11
 with sigma of 0.02
 N49-C22 \\sim N49-C10
 with sigma of 0.02
 C14-C10 \\sim C23-C22
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C8A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C1 \\sim C8: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(C22) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C45) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
4. Others
 Sof(H44A)=Sof(H44B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(H44C)=Sof(H44D)=FVAR(1)
 Sof(H1BC)=Sof(H1BD)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=1-FVAR(2)
 Sof(H1AA)=Sof(H1AB)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(3)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
5.a Free rotating group:
 O40(H40A,H40B)
5.b Secondary CH2 refined with riding coordinates:
 C44(H44C,H44D), C44(H44A,H44B), C46(H46A,H46B), C1(H1AA,H1AB), C1(H1BC,H1BD),
 C10(H10A,H10B), C22(H22A,H22B)
5.c Aromatic/amide H refined with riding coordinates:
 N33(H33), C25(H25), N8(H8), C28(H28), C26(H26), C35(H35), C39(H39), C38(H38),
 C29(H29), C6(H6), C36(H36), C17(H17), C19(H19), C4(H4), C3(H3), C20(H20),
 C7(H7), C42(H42), C48(H48)
5.d Idealised Me refined with riding coordinates:
 C45(H45A,H45B,H45C), C13(H13A,H13B,H13C), C11(H11A,H11B,H11C)
5.e Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C8A(H8AA,H8AB,H8AC), C14(H14A,H14B,H14C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              82818
_shelx_fab_checksum              84813
_platon_squeeze_special_details
;
A solvent mask was calculated and 608 electrons were 
found in a volume of 2203\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2.375[C5H11N1O2] per Asymmetric Unit 
which account for 608 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'