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_1573696
_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, C6 H6, 0.16[C6H6]'
_chemical_formula_sum            'C10.96 H8.96 Br2 N6 Zn'
_chemical_formula_weight         449.91
_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                   16.77190(10)
_cell_length_b                   16.77190(10)
_cell_length_c                   16.77190(10)
_cell_measurement_reflns_used    25278
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.0310
_cell_measurement_theta_min      3.6790
_cell_volume                     4717.88(5)
_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 2014/5 (Sheldrick, 2014)'
_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 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     41.00 122.00   0.50    0.05    --   43.01-179.00 -30.00  162
  2  \w     36.00  62.00   0.50    0.05    --   43.01 -95.00 -60.00   52
  3  \w      5.00  38.00   0.50    0.05    --   43.01 -38.00   0.00   66
  4  \w    -31.00  -6.00   0.50    0.05    --   43.01 -38.00   0.00   50
  5  \w    -27.00   7.00   0.50    0.05    --   43.01 -95.00 -60.00   68
  6  \w    -14.00  23.00   0.50    0.05    --   43.01 -19.00-150.00   74
  7  \w     56.00 103.00   0.50    0.05    --  113.75-125.00-180.00   94
  8  \w     61.00  99.00   0.50    0.05    --  113.75 -95.00-150.00   76
  9  \w     64.00  97.00   0.50    0.05    --  113.75 -95.00 -60.00   66
 10  \w     62.00 104.00   0.50    0.05    --  113.75 -95.00 150.00   84
 11  \w     53.00 105.00   0.50    0.05    --  113.75 -95.00  60.00  104
 12  \w     77.00 102.00   0.50    0.05    --  113.75 -77.00 -60.00   50
 13  \w     42.00 101.00   0.50    0.05    --  113.75 -77.00  30.00  118
 14  \w     41.00  67.00   0.50    0.05    --  113.75 -61.00 -30.00   52
 15  \w     42.00  68.00   0.50    0.05    --  113.75 -77.00 -60.00   52
 16  \w     59.00  85.00   0.50    0.05    --  113.75 -77.00-150.00   52
 17  \w     43.00  68.00   0.50    0.05    --  113.75 -61.00-180.00   50
 18  \w     98.00 170.00   0.50    0.05    --  113.75  45.00 -90.00  144
 19  \w    115.00 173.00   0.50    0.05    --  113.75  30.00  30.00  116
 20  \w     95.00 165.00   0.50    0.05    --  113.75  45.00 150.00  140
 21  \w     83.00 171.00   0.50    0.05    --  113.75  95.00  49.00  176
 22  \w     97.00 122.00   0.50    0.05    --   43.01 179.00  30.00   50
 23  \w     42.00  72.00   0.50    0.05    --   43.01 179.00  30.00   60
 24  \w     12.00  37.00   0.50    0.05    --  -43.01  19.00   0.00   50
 25  \w    -22.00   7.00   0.50    0.05    --  -43.01  19.00   0.00   58
 26  \w    -29.00  37.00   0.50    0.05    --  -43.01  19.00-150.00  132
 27  \w   -124.00 -78.00   0.50    0.05    --  -97.00 -45.00-180.00   92
 28  \w   -173.00 -85.00   0.50    0.05    --  -97.00 -45.00-150.00  176
 29  \w   -147.00 -95.00   0.50    0.05    --  -97.00 -95.00 -60.00  104
 30  \w   -106.00 -75.00   0.50    0.05    --  -97.00 -61.00 150.00   62
 31  \w   -150.00-118.00   0.50    0.05    --  -97.00 -61.00 150.00   64
 32  \w    -73.00 -23.00   0.50    0.05    --  -97.00  61.00  60.00  100
 33  \w    -52.00 -25.00   0.50    0.05    --  -97.00  45.00   0.00   54
 34  \w    -53.00 -28.00   0.50    0.05    --  -97.00  61.00 -30.00   50
 35  \w    -72.00 -24.00   0.50    0.05    --  -97.00  61.00 -90.00   96
 36  \w    -54.00 -29.00   0.50    0.05    --  -97.00  45.00-150.00   50
 37  \w    -52.00 -21.00   0.50    0.05    --  -97.00  45.00-180.00   62
 38  \w    -54.00 -21.00   0.50    0.05    --  -97.00  45.00 -30.00   66
 39  \w    -54.00 -21.00   0.50    0.05    --  -97.00  45.00 150.00   66
 40  \w    -96.00 -71.00   0.50    0.05    --  -97.00  95.00  49.00   50
 41  \w   -112.00 -76.00   0.50    0.05    --  -97.00 125.00   0.00   72
 42  \w   -112.00 -85.00   0.50    0.05    --  -97.00 125.00  60.00   54
 43  \w    -80.00 -29.00   0.50    0.05    --  -97.00 125.00  60.00  102
 44  \w    -62.00 -27.00   0.50    0.05    --  -97.00 125.00   0.00   70
 45  \w    -65.00  21.00   0.50    0.05    --  -43.01  95.00  49.00  172
 46  \w    -58.00 -25.00   0.50    0.05    --  -97.00 111.00 -48.20   66
 47  \w   -108.00 -77.00   0.50    0.05    --  -97.00 111.00 -48.20   62
 48  \w   -126.00 -79.00   0.50    0.05    --  -97.00 144.00-148.51   94
;
_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      0.0330447000
_diffrn_orient_matrix_UB_12      -0.0851694000
_diffrn_orient_matrix_UB_13      -0.0093884000
_diffrn_orient_matrix_UB_21      -0.0056932000
_diffrn_orient_matrix_UB_22      0.0078162000
_diffrn_orient_matrix_UB_23      -0.0913843000
_diffrn_orient_matrix_UB_31      0.0854841000
_diffrn_orient_matrix_UB_32      0.0334541000
_diffrn_orient_matrix_UB_33      -0.0024592000
_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  0.0525
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            29166
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.750
_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    8.119
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55427
_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_density_diffrn    1.900
_exptl_crystal_description       block
_exptl_crystal_F_000             2601
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.280
_refine_diff_density_min         -0.546
_refine_diff_density_rms         0.122
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(10)
_refine_ls_extinction_coef       0.00029(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     43
_refine_ls_number_reflns         969
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0468
_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^)+(0.0741P)^2^+32.9356P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1300
_refine_ls_wR_factor_ref         0.1300
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                969
_reflns_number_total             969
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06624c2.cif
_cod_data_source_block           1bz
_cod_depositor_comments
'Adding full bibliography for 1573695--1573696.cif.'
_cod_original_cell_volume        4717.88(8)
_cod_database_code               1573696
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.687
_shelx_estimated_absorpt_t_min   0.642
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.97(10)
 0.03(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 Br1-N2 \\sim Br1-N1
 with sigma of 0.02
4. Restrained planarity
 Br1, C1, N2, C2, N1
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C8) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C1) = Uanis(N2) = Uanis(N1) = Uanis(C2)
Uanis(C8) = Uanis(C4) = Uanis(C5) = Uanis(C3) = Uanis(C6) = Uanis(C7)
6. Rigid body (RIGU) restrains
 N1, Zn1, C2, C1, Br1, N2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
7. Others
 Fixed Sof: Br1(0.5) C1(0.5) N2(0.5) C6(0.25) H6(0.25) C5(0.25) H5(0.25)
 C4(0.25) H4(0.25) C3(0.25) H3(0.25) C8(0.25) H8(0.25) C7(0.25) H7(0.25)
8.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C5(H5), C4(H4), C3(H3), C8(H8), C7(H7)
8.b Fitted hexagon refined as free rotating group:
 C6(C5,C4,C3,C8,C7)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              16022
_shelx_hkl_checksum              22586
_shelx_fab_checksum              23548
_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 2.104
_oxdiff_exptl_absorpt_empirical_full_min 0.645