Fine-tuning of gas uptake and selectivity in a hexafluorozirconate pillared coordination network that features two porous phases
Harvey-Reid, Nathan C.; Scott, Hayley S.; Patil, Komal M.; Kumar, Naveen; Healy, Colm; Zaworotko, Michael J.; Mukherjee, Soumya; Kruger, Paul E.; CrystEngComm 27 (2025) 1736–1741; doi:10.1039/D4CE01250J

data_7249921
_publ_section_title
;
 Fine-tuning of gas uptake and selectivity in a hexafluorozirconate
 pillared coordination network that features two porous phases
;
_journal_issue                   12
_journal_name_full               CrystEngComm
_journal_page_first              1736
_journal_page_last               1741
_journal_paper_doi               10.1039/D4CE01250J
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C20 H22 Cu F6 N6 Zr 3[CH4O], 2[C2H6O2]'
_chemical_formula_sum            'C20 H22 Cu F6 N6 Zr'
_chemical_formula_weight         615.19
_chemical_name_common            ZRFSIX-21-Cu-Beta
_space_group_crystal_system      orthorhombic
_space_group_IT_number           52
_space_group_name_Hall           '-P 2a 2bc'
_space_group_name_H-M_alt        'P n n a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-07 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6449(17)
_cell_length_b                   16.654(3)
_cell_length_c                   14.6352(15)
_cell_measurement_reflns_used    1259
_cell_measurement_temperature    120.00(11)
_cell_measurement_theta_max      64.0690
_cell_measurement_theta_min      4.0170
_cell_volume                     3569.5(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120
_diffrn_detector_area_resol_mean 10.6501
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.968
_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    -62.00  22.00   1.00   25.00    --  -38.50  19.00-120.00   84
  2  \w     -8.00  52.00   1.00   25.00    --   42.00 -37.00  30.00   60
  3  \w     73.00 107.00   1.00  100.00    --  103.81 -45.00 150.00   34
  4  \w     99.00 166.00   1.00  100.00    --  103.81 125.00 -30.00   67
  5  \w     95.00 177.00   1.00  100.00    --  103.81  30.00 120.00   82
  6  \w     35.00  86.00   1.00  100.00    --  103.81-125.00  30.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0880
_diffrn_reflns_av_unetI/netI     0.1039
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8539
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.333
_diffrn_reflns_theta_min         4.020
_exptl_absorpt_coefficient_mu    3.542
_exptl_absorpt_correction_T_max  0.884
_exptl_absorpt_correction_T_min  0.544
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.145
_exptl_crystal_description       block
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          0.141
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.049
_refine_diff_density_max         1.421
_refine_diff_density_min         -2.430
_refine_diff_density_rms         0.185
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3612
_refine_ls_number_restraints     435
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1729
_refine_ls_R_factor_gt           0.1131
_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          0.2864
_refine_ls_wR_factor_ref         0.3335
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2125
_reflns_number_total             3612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01250j2.cif
_cod_data_source_block           ZRFSIX-21-Cu-Beta
_cod_depositor_comments
'Adding full bibliography for 7249920--7249921.cif.'
_cod_original_cell_volume        3569.6(8)
_cod_database_code               7249921
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.61348
 0.38652
2. Restrained distances
 C2-C1
 1.35 with sigma of 0.02
 C4-C5
 1.35 with sigma of 0.02
 C10A-C9A
 1.35 with sigma of 0.02
 C7A-C8A
 1.35 with sigma of 0.02
3. Restrained planarity
 C1, C3, C4, N2, N1
 with sigma of 0.1
 C10_$1, C7_$1, C6_$1, N3_$1
 with sigma of 0.1
 N3A, C1A, C2A, C3A, C4A, C5A
 with sigma of 0.1
 C8, C10, N3, C6, C7, C9
 with sigma of 0.1
 N1A, N2A, C9A, C6A, C7A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N3 \\sim N1A \\sim N2A \\sim C6 \\sim C9A \\sim C7 \\sim C8 \\sim C6A \\sim C7A
\\sim C10 \\sim C8A \\sim C9 \\sim C10A: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 2A
N1 \\sim N3A \\sim C1A \\sim C2A \\sim C3A \\sim C4 \\sim N2 \\sim C5A \\sim
C4A \\sim C3 \\sim C1 \\sim C2 \\sim C5: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 2A
F3A \\sim F3 \\sim F4 \\sim F4A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.01 within 2A
Uanis(F2A) = Uanis(F2)
Uanis(F4) = Uanis(F4A) = Uanis(F3) = Uanis(F3A)
5. Others
 Sof(F3A)=1-FVAR(1)
 Sof(F2A)=Sof(F4A)=0.5*(1-FVAR(2))
 Sof(F2)=Sof(F4)=0.5*FVAR(2)
 Sof(F3)=FVAR(1)
 Fixed Sof: C1(0.5) N1(0.5) N2(0.5) H2(0.5) C4(0.5) C3(0.5) N3A(0.5) C5A(0.5)
 H5A(0.5) C4A(0.5) H4A(0.5) C3A(0.5) C2A(0.5) H2A(0.5) C1A(0.5) H1A(0.5)
 C5(0.5) H5B(0.5) H5C(0.5) H5D(0.5) C2(0.5) H2B(0.5) H2C(0.5) H2D(0.5) C8(0.5)
 C7(0.5) H7(0.5) C6(0.5) H6(0.5) N3(0.5) C10(0.5) H10(0.5) C9(0.5) H9(0.5)
 C7A(0.5) C6A(0.5) C9A(0.5) N2A(0.5) H2AA(0.5) N1A(0.5) C8A(0.5) H8AA(0.5)
 H8AB(0.5) H8AC(0.5) C10A(0.5) H10A(0.5) H10B(0.5) H10C(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 N2(H2), C5A(H5A), C4A(H4A), C2A(H2A), C1A(H1A), C7(H7), C6(H6), C10(H10),
 C9(H9), N2A(H2AA)
6.b Fitted pentagon refined as free rotating group:
 C1(N1,N2,C4,C3), C7A(C6A,C9A,N2A,N1A)
6.c Fitted hexagon refined as free rotating group:
 N3A(C5A,C4A,C3A,C2A,C1A), C8(C7,C6,N3,C10,C9)
6.d Idealised Me refined as rotating group:
 C5(H5B,H5C,H5D), C2(H2B,H2C,H2D), C8A(H8AA,H8AB,H8AC), C10A(H10A,H10B,H10C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              93915
_shelx_fab_checksum              46378
_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
;