Metal-organic framework with pore contraction and modification by diethylammonium cations for record SO<sub>2</sub>/CO<sub>2</sub> separation.
Yang, Mei; Yuan, Wenke; Li, Xiu-Yuan; Liu, Bo; Zhou, Huifang; Chemical communications (Cambridge, England) 60 (2024) 12754–12757; doi:10.1039/d4cc04382k

data_7133935
_publ_section_title
;
 Metal-organic framework with pore contraction and modification by
 diethylammonium cations for record SO<sub>2</sub>/CO<sub>2</sub>
 separation.
;
_journal_issue                   87
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              12754
_journal_page_last               12757
_journal_paper_doi               10.1039/d4cc04382k
_journal_volume                  60
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety
'C56 H24 N4 O24 Zn5.5, 2(H O0.5), C4 H12 N, 11.6[H2O], 1.6[H2O], 2.6[H2O]'
_chemical_formula_sum            'C60 H38 N5 O25 Zn5.5'
_chemical_formula_weight         1588.49
_space_group_crystal_system      tetragonal
_space_group_IT_number           122
_space_group_name_Hall           'I -4 2bw'
_space_group_name_H-M_alt        'I -4 2 d'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-07-26 deposited with the CCDC.	2024-10-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   38.8022(8)
_cell_length_b                   38.8022(8)
_cell_length_c                   12.8725(4)
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    220.00(10)
_cell_measurement_theta_max      73.575
_cell_measurement_theta_min      3.221
_cell_volume                     19381.0(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_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  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      220.00(10)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1074
_diffrn_reflns_av_unetI/netI     0.0542
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -48
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            79762
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.742
_diffrn_reflns_theta_min         3.221
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.001
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.5767
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.2047 before and 0.1169 after correction.
The Ratio of minimum to maximum transmission is 0.7651.
The \l/2 correction factor is Not present.
;
_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    1.089
_exptl_crystal_description       needle
_exptl_crystal_F_000             6384
_exptl_crystal_recrystallization_method
'The crystals were growth by means of evaporation of a mixture of n-hexane and toluene at RT.'
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.599
_refine_diff_density_rms         0.128
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.46(4)
_refine_ls_extinction_coef       0.00023(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     537
_refine_ls_number_reflns         9688
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0517
_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^)+(0.0985P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1385
_refine_ls_wR_factor_ref         0.1482
_reflns_Friedel_coverage         0.831
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                7924
_reflns_number_total             9688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04382k2.cif
_cod_data_source_block           1
_cod_original_cell_volume        19381.0(10)
_cod_original_formula_sum        'C60 H38 N5 O25 Zn5.50'
_cod_database_code               7133935
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.604
_exptl_crystal_mounting_method
'Crystals were removed from the crystallisation vial and immediately coated with polybutenes oil (CAS: 9003-29-6) on a glass slide. A suitable single crystal coated with polybutenes oil as less as possible was sealed in capillary tube filled with argon. The capillary tube with single crystal was mounted on copper pin with solid paraffin.'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.54(4)
 0.46(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 N3-C28 = N3-C30
 1.47 with sigma of 0.01
 C31-C30 = C29-C28
 1.52 with sigma of 0.01
 N4-C34 = N4-C32
 1.47 with sigma of 0.01
 C33-C32 = C35-C34
 1.52 with sigma of 0.01
 C30-C28
 2.401 with sigma of 0.02
 N3-C29 = N3-C31
 2.434 with sigma of 0.02
 N4-C33 = N4-C35
 2.434 with sigma of 0.02
 C34-C32
 2.401 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
N3 \\sim C28 \\sim C30 \\sim C29 \\sim C31: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C21 \\sim C26 \\sim O9 \\sim O10 \\sim C26A \\sim O9A \\sim O10A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C34 \\sim C32 \\sim N4 \\sim C33 \\sim C35: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(N3) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29)
\\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C34) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Same fragment restrains
{C21, C26A, O9A, O10A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C21, C26, O9, O10}
6. Others
 Sof(C26A)=Sof(O9A)=Sof(O10A)=1-FVAR(1)
 Sof(C26)=Sof(O9)=Sof(O10)=FVAR(1)
 Fixed Sof: Zn4(0.25) O13(0.25) H13(0.5) N3(0.25) H3A(0.25) H3B(0.25)
 C31(0.25) H31A(0.25) H31B(0.25) H31C(0.25) C28(0.25) H28A(0.25) H28B(0.25)
 C29(0.25) H29A(0.25) H29B(0.25) H29C(0.25) C30(0.25) H30A(0.25) H30B(0.25)
 C32(0.25) H32A(0.25) H32B(0.25) N4(0.25) H4A(0.25) H4B(0.25) C34(0.25)
 H34A(0.25) H34B(0.25) C35(0.25) H35A(0.25) H35B(0.25) H35C(0.25) C33(0.25)
 H33A(0.25) H33B(0.25) H33C(0.25) O14(0.25) H14A(0.5)
7.a Riding coordinates:
 O13(H13), O14(H14A)
7.b Secondary CH2 refined with riding coordinates:
 N3(H3A,H3B), C28(H28A,H28B), C30(H30A,H30B), C32(H32A,H32B), N4(H4A,H4B),
 C34(H34A,H34B)
7.c Me refined with riding coordinates:
 C31(H31A,H31B,H31C), C29(H29A,H29B,H29C), C35(H35A,H35B,H35C), C33(H33A,H33B,
 H33C)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C9(H9), C10(H10), C12(H12), C14(H14), C16(H16),
 C18(H18), C22(H22), C23(H23), C25(H25)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1264 electrons were 
found in a volume of 5120\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
11.6[H2O], 1.6[H2O], 2.6[H2O] per Asymmetric Unit 
which account for 1264 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              37576
_shelx_hkl_checksum              41759
_shelx_fab_checksum              46886
_olex2_submission_special_instructions 'No special instructions were received'