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_7249920
_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_absolute_configuration unk
_chemical_formula_moiety         'C20 H22 Cu F6 N6 Zr, 5(H2 O), C2 H3 N'
_chemical_formula_sum            'C22 H35 Cu F6 N7 O5 Zr'
_chemical_formula_weight         746.33
_chemical_name_common            ZRFSIX-21-Cu-Alpha
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-02-04
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-04 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                   15.4735(4)
_cell_length_b                   13.2070(4)
_cell_length_c                   14.6062(3)
_cell_measurement_reflns_used    6213
_cell_measurement_temperature    119.99(10)
_cell_measurement_theta_max      76.1660
_cell_measurement_theta_min      4.3860
_cell_volume                     2984.90(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.00
_diffrn_detector_area_resol_mean 10.6501
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -64.00  30.00   1.00   15.44    --  -38.50  57.00  60.00   94
  2  \w   -107.00 -13.00   1.00   15.44    --  -38.50 -57.00 -90.00   94
  3  \w     89.00 178.00   1.00   61.74    --  111.00  45.00  30.00   89
  4  \w     38.00 113.00   1.00   61.74    --  111.00-111.00  90.00   75
  5  \w     41.00 133.00   1.00   61.74    --  111.00 -45.00 -90.00   92
  6  \w     38.00 113.00   1.00   61.74    --  111.00-111.00 150.00   75
  7  \w     71.00 178.00   1.00   61.74    --  111.00  15.00 -60.00  107
  8  \w    -29.00  19.00   1.00   15.44    --   41.88 -37.00 150.00   48
  9  \w     12.00 113.00   1.00   15.44    --   41.88  77.00  90.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0442
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            12941
_diffrn_reflns_point_group_measured_fraction_full 0.865
_diffrn_reflns_point_group_measured_fraction_max 0.829
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.197
_diffrn_reflns_theta_min         4.401
_exptl_absorpt_coefficient_mu    4.488
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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 violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.661
_exptl_crystal_description       block
_exptl_crystal_F_000             1516
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.067
_refine_diff_density_max         1.466
_refine_diff_density_min         -1.286
_refine_diff_density_rms         0.121
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.17(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         5245
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0507
_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^)+(0.1089P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1318
_refine_ls_wR_factor_ref         0.1371
_reflns_Friedel_coverage         0.614
_reflns_Friedel_fraction_full    0.718
_reflns_Friedel_fraction_max     0.657
_reflns_number_gt                4789
_reflns_number_total             5245
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01250j2.cif
_cod_data_source_block           zrfsix-21-cu-alpha
_cod_depositor_comments
'Adding full bibliography for 7249920--7249921.cif.'
_cod_database_code               7249920
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.753
_shelx_estimated_absorpt_t_min   0.638
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.83(2)
 0.17(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All N(H,H,H,H,H,H) groups, All O(H,H) groups
3. Restrained distances
 O1-H1A
 0.84 with sigma of 0.02
 O3-H3A
 0.84 with sigma of 0.02
 O1-H1B
 0.84 with sigma of 0.02
 H5B-O5
 0.84 with sigma of 0.02
 H5C-H5B
 1.36 with sigma of 0.02
 O3-H3B
 0.84 with sigma of 0.02
 H3A-H3B
 1.3 with sigma of 0.02
 H1B-H1A
 1.36 with sigma of 0.02
 H1A-H5B
 2.45 with sigma of 0.02
 H4A-H2B
 2.6 with sigma of 0.02
 H4B-F2
 1.9 with sigma of 0.02
 O5-H5C
 0.9 with sigma of 0.02
4.a Free rotating group:
 O2(H2B,H2C), O4(H4A,H4B)
4.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C17(H17), C18(H18), C19(H19), C20(H20),
 N2(H2A), N5(H5A)
4.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C)
;
_shelx_res_checksum              70921
_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
;