Introducing halogen-bonded gates into zeolitic frameworks for efficient benzene/cyclohexene/cyclohexane separation.
Liang, Zi-Jun; Dong, Fang-Di; Ye, Le; Zheng, Kai; Hu, Ding-Yi; Feng, Xi; Su, Wen-Yu; Wang, Zhi-Shuo; Zhou, Mu-Yang; Fang, Zi-Luo; Zhou, Dong-Dong; Zhang, Jie-Peng; Chen, Xiao-Ming; Chemical science 16 (2025) 3307–3312; doi:10.1039/d4sc06624c

data_1573695
_publ_section_title
;
 Introducing halogen-bonded gates into zeolitic frameworks for efficient
 benzene/cyclohexene/cyclohexane separation.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              3307
_journal_page_last               3312
_journal_paper_doi               10.1039/d4sc06624c
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C4 H2 Br2 N6 Zn, C3 H7 N O'
_chemical_formula_sum            'C7 H9 Br2 N7 O Zn'
_chemical_formula_weight         432.40
_chemical_name_systematic        MAF-78
_space_group_crystal_system      cubic
_space_group_IT_number           217
_space_group_name_Hall           'I -4 2 3'
_space_group_name_H-M_alt        'I -4 3 m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-09-25
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-09-26 deposited with the CCDC.	2025-01-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   16.77164(5)
_cell_length_b                   16.77164(5)
_cell_length_c                   16.77164(5)
_cell_measurement_reflns_used    27172
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.5200
_cell_measurement_theta_min      3.6930
_cell_volume                     4717.66(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -25.00  23.00   0.50    0.05    --   43.01 -19.00  90.00   96
  2  \w    -36.00  13.00   0.50    0.05    --   43.01 -19.00  30.00   98
  3  \w    -37.00  23.00   0.50    0.05    --   43.01 -19.00 -30.00  120
  4  \w    -33.00   2.00   0.50    0.05    --   43.01 -38.00-150.00   70
  5  \w     12.00  39.00   0.50    0.05    --   43.01 -38.00-150.00   54
  6  \w     60.00 105.00   0.50    0.05    --  113.75 -95.00 -90.00   90
  7  \w     79.00 104.00   0.50    0.05    --  113.75-131.00 -35.00   50
  8  \w     22.00  72.00   0.50    0.05    --   43.01-131.00 -35.00  100
  9  \w     85.00 112.00   0.50    0.05    --  113.75-125.00  30.00   54
 10  \w     42.00  78.00   0.50    0.05    --  113.75-125.00  30.00   72
 11  \w     47.00 110.00   0.50    0.05    --  113.75-125.00  90.00  126
 12  \w     83.00 122.00   0.50    0.05    --  113.75-139.00 149.00   78
 13  \w     40.00 105.00   0.50    0.05    --  113.75 -95.00  90.00  130
 14  \w     41.00  66.00   0.50    0.05    --   43.01-139.00 149.00   50
 15  \w     51.00 103.00   0.50    0.05    --  113.75 -95.00 150.00  104
 16  \w     43.00 111.00   0.50    0.05    --  113.75-125.00 -60.00  136
 17  \w     42.00  87.00   0.50    0.05    --  113.75-125.00 -90.00   90
 18  \w     80.00 105.00   0.50    0.05    --  113.75 -95.00-150.00   50
 19  \w     80.00 105.00   0.50    0.05    --  113.75 -95.00-180.00   50
 20  \w     51.00  77.00   0.50    0.05    --  113.75 -95.00-150.00   52
 21  \w     78.00 103.00   0.50    0.05    --  113.75 -95.00 -60.00   50
 22  \w     77.00 105.00   0.50    0.05    --  113.75 -95.00   0.00   56
 23  \w     41.00 105.00   0.50    0.05    --  113.75 -95.00 120.00  128
 24  \w     43.00  68.00   0.50    0.05    --  113.75 -61.00   0.00   50
 25  \w     48.00  73.00   0.50    0.05    --  113.75 -77.00   0.00   50
 26  \w     77.00 102.00   0.50    0.05    --  113.75 -77.00   0.00   50
 27  \w     41.00  81.00   0.50    0.05    --  113.75 -77.00 -60.00   80
 28  \w     41.00  66.00   0.50    0.05    --  113.75 -61.00 -30.00   50
 29  \w     43.00  95.00   0.50    0.05    --  113.75 -77.00 -90.00  104
 30  \w     41.00  67.00   0.50    0.05    --  113.75 -61.00-180.00   52
 31  \w     90.00 168.00   0.50    0.05    --  113.75  30.00 -90.00  156
 32  \w    135.00 175.00   0.50    0.05    --  113.75  61.00-180.00   80
 33  \w     91.00 123.00   0.50    0.05    --  113.75  61.00-180.00   64
 34  \w    117.00 160.00   0.50    0.05    --  113.75  45.00  60.00   86
 35  \w     92.00 175.00   0.50    0.05    --  113.75  61.00  90.00  166
 36  \w     92.00 132.00   0.50    0.05    --  113.75  45.00 150.00   80
 37  \w     85.00 163.00   0.50    0.05    --  113.75  77.00 150.00  156
 38  \w     96.00 165.00   0.50    0.05    --  113.75  61.00 120.00  138
 39  \w    134.00 172.00   0.50    0.05    --  113.75  30.00   0.00   76
 40  \w     93.00 118.00   0.50    0.05    --  113.75  30.00   0.00   50
 41  \w    110.00 136.00   0.50    0.05    --  113.75  45.00 -60.00   52
 42  \w    101.00 127.00   0.50    0.05    --  113.75  30.00-120.00   52
 43  \w     77.00 155.00   0.50    0.05    --  113.75 125.00   0.00  156
 44  \w    114.00 140.00   0.50    0.05    --  113.75 131.00  35.00   52
 45  \w     68.00  98.00   0.50    0.05    --   43.01 139.00-150.00   60
 46  \w     96.00 121.00   0.50    0.05    --  113.75 139.00-150.00   50
 47  \w      9.00  34.00   0.50    0.05    --  -43.01  38.00 120.00   50
 48  \w    -45.00   4.00   0.50    0.05    --  -43.01  38.00 120.00   98
 49  \w    -95.00 -67.00   0.50    0.05    --  -43.01 139.00-150.00   56
 50  \w    -91.00 -55.00   0.50    0.05    --  -43.01 131.00  35.00   72
 51  \w   -107.00 -73.00   0.50    0.05    --  -97.00 106.00 128.57   68
 52  \w   -127.00-102.00   0.50    0.05    --  -97.00 147.00 150.99   50
 53  \w    -95.00 -69.00   0.50    0.05    --  -97.00 131.00  35.00   52
 54  \w    -52.00 -24.00   0.50    0.05    --  -97.00 106.00 128.57   56
 55  \w   -108.00 -75.00   0.50    0.05    --  -97.00 110.00 -81.66   66
 56  \w    -55.00 -30.00   0.50    0.05    --  -97.00 139.00-150.00   50
 57  \w   -122.00 -87.00   0.50    0.05    --  -97.00 139.00-150.00   70
 58  \w   -116.00 -20.00   0.50    0.05    --  -43.01 -57.00 -30.00  192
 59  \w   -134.00-105.00   0.50    0.05    --  -97.00-131.00 -35.00   58
 60  \w   -159.00-101.00   0.50    0.05    --  -97.00 -61.00  30.00  116
 61  \w   -146.00-121.00   0.50    0.05    --  -97.00-139.00 149.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0026111000
_diffrn_orient_matrix_UB_12      0.0918127000
_diffrn_orient_matrix_UB_13      0.0013282000
_diffrn_orient_matrix_UB_21      -0.0570904000
_diffrn_orient_matrix_UB_22      -0.0005551000
_diffrn_orient_matrix_UB_23      -0.0719951000
_diffrn_orient_matrix_UB_31      -0.0719032000
_diffrn_orient_matrix_UB_32      -0.0028969000
_diffrn_orient_matrix_UB_33      0.0570325000
_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  0.0339
_diffrn_reflns_av_unetI/netI     0.0076
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33076
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.196
_diffrn_reflns_theta_min         3.727
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.150
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75871
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.826
_exptl_crystal_description       block
_exptl_crystal_F_000             2496
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.645
_refine_diff_density_min         -1.299
_refine_diff_density_rms         0.196
_refine_ls_abs_structure_details
;
 Flack x determined using 374 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     80
_refine_ls_number_reflns         843
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0857
_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^)+(0.2500P)^2^+3.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2615
_refine_ls_wR_factor_ref         0.2616
_reflns_Friedel_coverage         0.801
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                841
_reflns_number_total             843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06624c2.cif
_cod_data_source_block           1g
_cod_depositor_comments
'Adding full bibliography for 1573695--1573696.cif.'
_cod_original_cell_volume        4717.66(4)
_cod_database_code               1573695
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     CHNFeAg
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-C6 = N4-C5
 1.46 with sigma of 0.02
 C3-O3
 1.22 with sigma of 0.02
 C3-N4
 1.36 with sigma of 0.02
 C3-C6 = C3-C5
 2.45 with sigma of 0.04
 N2-N1 = C2-C1
 2.2 with sigma of 0.01
 N4-O3
 2.23 with sigma of 0.04
3. Restrained planarity
 C3, O3, N4, C5, C6
 with sigma of 0.1
 C2, N1, C1, N2, Br1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C3 \\sim O3 \\sim N4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C1) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) = Uanis(N2)
Uanis(C6) = Uanis(C5)
5. Rigid body (RIGU) restrains
 C3, O3, N4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Br1(0.5) C1(0.5) N2(0.5) C3(0.25) H3(0.25) O3(0.25) N4(0.25)
 C5(0.25) H5A(0.25) H5B(0.25) H5C(0.25) C6(0.25) H6A(0.25) H6B(0.25) H6C(0.25)
7.a Me refined with riding coordinates:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
;
_shelx_res_checksum              90512
_shelx_hkl_checksum              29078
_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 1.287
_oxdiff_exptl_absorpt_empirical_full_min 0.805