A Fluorinated Zirconium Metal-Organic Cage-Based Supramolecular Framework for Efficient Separation of Methanolto-Olefins (MTO) Products
Yang, Tao; Fan, Zhiyuan; Zheng, Jingyang; Zhang, Meng; Zhou, Yuqing; Chen, Tao; Li, Changjiang; Jiang, Yao; Sun, Lin-Bing; Chemical Communications  (2026) –; doi:10.1039/D6CC00359A

data_7135713
_publ_section_title
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 A fluorinated zirconium metal-organic cage-based supramolecular framework
 for efficient separation of methanol-to-olefin (MTO) products.
;
_journal_issue                   35
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9001
_journal_page_last               9005
_journal_paper_doi               10.1039/d6cc00359a
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety
'C48 H12 F24 O40 Zr12, 12(C5 H5), 6(Cl), 2[C4H9NO], 1[H2O]'
_chemical_formula_sum            'C116 H92 Cl6 F24 N2 O43 Zr12'
_chemical_formula_weight         3965.25
_space_group_crystal_system      cubic
_space_group_IT_number           225
_space_group_name_Hall           '-F 4 2 3'
_space_group_name_H-M_alt        'F m -3 m'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2qqfzw
_audit_creation_date             2026-03-16
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2026-03-20 deposited with the CCDC.	2026-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   37.167(3)
_cell_length_b                   37.167(3)
_cell_length_c                   37.167(3)
_cell_measurement_reflns_used    9988
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      56.41
_cell_measurement_theta_min      2.93
_cell_volume                     51342(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX5 V2023.9-2 (Bruker, 2023)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.1188
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            126496
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        52.021
_diffrn_reflns_theta_max         52.021
_diffrn_reflns_theta_min         6.796
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.302
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5769
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1446 before and 0.0907 after correction.
The Ratio of minimum to maximum transmission is 0.7680.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.026
_exptl_crystal_description       block
_exptl_crystal_F_000             15552
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.465
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     180
_refine_ls_number_reflns         2184
_refine_ls_number_restraints     195
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1604
_refine_ls_R_factor_gt           0.1382
_refine_ls_shift/su_max          0.057
_refine_ls_shift/su_mean         0.012
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0100P)^2^+1000.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2328
_refine_ls_wR_factor_ref         0.2429
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1450
_reflns_number_total             2184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc00359a2.cif
_cod_data_source_block           231222lu_lgp071623_0m
_cod_depositor_comments          'Adding full bibliography for 7135713.cif.'
_cod_original_cell_volume        51342(11)
_cod_original_sg_symbol_H-M      Fm-3m
_cod_database_code               7135713
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.778
_shelx_estimated_absorpt_t_min   0.693
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Shared sites
{O7, O5}
3. Restrained distances
 C2-C1 = C8-C5
 1.5 with sigma of 0.01
 F6-C7 = F3-C6 = F2-C4 = F1-C3
 1.4 with sigma of 0.01
 O1-C1 = O2-C1 = O4-C8 = O3-C8
 1.25 with sigma of 0.01
 O1-O2 = O4-O3
 2.2 with sigma of 0.01
 C11-C10 \\sim C11-C11_$1 \\sim C11-C10 \\sim C9-C10_$1 \\sim C9-C10
 with sigma of 0.02
 C11-C10_$1 \\sim C9-C11_$1 \\sim C10-C10_$1 \\sim C9-C11 \\sim C11_$1-C10
 with sigma of 0.02
 F1-C2 \\sim F1-C4 \\sim F2-C3 \\sim F2-C5 \\sim F3-C5 \\sim F3-C7 \\sim F6-C6
\\sim F6-C2
 with sigma of 0.02
 C7-C1 \\sim C3-C1
 with sigma of 0.02
 C8-C6 \\sim C8-C4
 with sigma of 0.02
4. Restrained planarity
 C2, F6, C7, C3, F1, F2, C4, F3, C6, C5, C1, C8
 with sigma of 0.01
 O1, C1, O2, C2
 with sigma of 0.1
 C5, O4, O3, C8
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O7) = Uanis(O5)
6. Others
 Fixed Sof: O1(0.25) C1(0.25) O7(0.083333) O5(0.083333) C2(0.25) C7(0.25)
 C6(0.25) C5(0.25) C4(0.25) C3(0.25) F6(0.25) O2(0.25) F1(0.25) F2(0.25)
 F3(0.25) O4(0.25) O3(0.25) C8(0.25) Cl7(0.125) Cl8(0.125)
7.a Riding coordinates:
 O6(H6), C9(H9), C11(H11), C10(H10)
7.b Fitted hexagon refined as free rotating group:
 C2(C7,C6,C5,C4,C3)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 837 electrons were 
found in a volume of 27748\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2[C4H9NO], 1[H2O] per Unit Cell 
which account for 848 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              40179
_shelx_fab_checksum              33789
_olex2_submission_special_instructions 'No special instructions were received'