Integrating pillared-layer strategy and pore-space partition method to construct multicomponent MOFs for C2H2/CO2 separation.
Liu, Lizhen; Yao, Zizhu; Ye, Yingxiang; Yang, Yike; Lin, Quanjie; Zhang, Zhangjing; O'Keeffe, Michael; Xiang, Shengchang; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c00612

data_4134923
_publ_section_title
;
 Integrating pillared-layer strategy and pore-space partition method to
 construct multicomponent MOFs for C2H2/CO2 separation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c00612
_journal_year                    2020
_chemical_formula_moiety         'C55 H23.5 Co4.5 F4 N4 O17.5'
_chemical_formula_sum            'C55 H23.5 Co4.5 F4 N4 O17.5'
_chemical_formula_weight         1361.46
_space_group_crystal_system      tetragonal
_space_group_IT_number           118
_space_group_name_Hall           'P -4 -2n'
_space_group_name_H-M_alt        'P -4 n 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-02-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.8545(3)
_cell_length_b                   21.8545(3)
_cell_length_c                   39.3775(9)
_cell_measurement_reflns_used    6536
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      70.5640
_cell_measurement_theta_min      3.9000
_cell_volume                     18807.4(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_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   -129.00  48.00   1.00   12.50    --  -40.45   0.00-180.00  177
  2  \w     94.00 176.00   1.00   35.00    --  103.24 125.00-180.00   82
  3  \w     21.00 109.00   1.00   35.00    --  103.24 -94.00 150.00   88
  4  \w     74.00 176.00   1.00   35.00    --  103.24  61.00-120.00  102
  5  \w     -1.00  32.00   1.00   12.50    --   40.45  19.00 120.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0135615000
_diffrn_orient_matrix_UB_12      0.0518721000
_diffrn_orient_matrix_UB_13      -0.0253890000
_diffrn_orient_matrix_UB_21      0.0322110000
_diffrn_orient_matrix_UB_22      -0.0459762000
_diffrn_orient_matrix_UB_23      -0.0236337000
_diffrn_orient_matrix_UB_31      -0.0612526000
_diffrn_orient_matrix_UB_32      -0.0126939000
_diffrn_orient_matrix_UB_33      -0.0180885000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0957
_diffrn_reflns_av_unetI/netI     0.1073
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            52415
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.807
_diffrn_reflns_theta_min         4.046
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.562
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73975
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pinkish pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    0.962
_exptl_crystal_description       block
_exptl_crystal_F_000             5432
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.740
_refine_diff_density_min         -1.708
_refine_diff_density_rms         0.143
_refine_ls_abs_structure_details
;
 Flack x determined using 3646 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.497(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         18183
_refine_ls_number_restraints     652
_refine_ls_restrained_S_all      1.380
_refine_ls_R_factor_all          0.1564
_refine_ls_R_factor_gt           0.1049
_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^)+(0.2000P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2766
_refine_ls_wR_factor_ref         0.3256
_reflns_Friedel_coverage         0.867
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                10835
_reflns_number_total             18183
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00612_si_002.cif
_cod_data_source_block           FJU-6-F-INA
_cod_original_cell_volume        18807.4(7)
_cod_original_formula_sum        'C55 H23.50 Co4.50 F4 N4 O17.50'
_cod_database_code               4134923
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 Co1 F1'
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.880
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 N8-C42
 2.8 with sigma of 0.02
 C136-C86
 2.8 with sigma of 0.02
 C93-C66
 2.8 with sigma of 0.02
 N8-C136 = C93-C136 = C93-C42 = C86-C42 = C86-C66 = N8-C66
 1.3 with sigma of 0.02
 C1AA-C0AA
 2.8 with sigma of 0.02
 C12-C4
 2.8 with sigma of 0.02
 N8-C0AA = C12-C0AA = C42-C12 = C42-C1AA = C4-C1AA = N8-C4
 1.3 with sigma of 0.02
 F41-C42
 2.386 with sigma of 0.02
 F41-C136
 2.3 with sigma of 0.02
 F41-C93
 1.34 with sigma of 0.02
 C66-F37
 2.3 with sigma of 0.02
 C42-F37
 2.38 with sigma of 0.02
 F37-C86
 1.344 with sigma of 0.02
 F27-C97 = F0AA-C5AA
 1.344 with sigma of 0.02
 C82-F27
 2.38 with sigma of 0.02
 C82-F0AA
 2.38 with sigma of 0.02
 F0AA-C2AA
 2.3 with sigma of 0.02
 F27-C82
 2.83 with sigma of 0.02
 F27-C4AA = C4AA-C82
 2.39 with sigma of 0.02
 F27-C4AA
 2.32 with sigma of 0.02
 C26-N18_$1
 2.8 with sigma of 0.02
 C63-C35
 2.8 with sigma of 0.02
 C2-C34
 2.8 with sigma of 0.02
 C34-C26 = C63-C26 = C63-C2 = N18_$1-C2 = N18_$1-C35 = C35-C34
 1.3 with sigma of 0.02
 F5-C34
 1.34 with sigma of 0.02
 F5-C35
 2.8 with sigma of 0.02
 F5-C35 = C35-C26
 2.38 with sigma of 0.02
 C35-F5
 2.31 with sigma of 0.02
 F5-C26
 2.39 with sigma of 0.02
 C26-F5
 2.37 with sigma of 0.02
 N7-C23_$2
 2.8 with sigma of 0.02
 C47_$2-C27
 2.8 with sigma of 0.02
 C36_$2-C3
 2.8 with sigma of 0.02
 N7-C36_$2 = C47_$2-C36_$2 = C47_$2-C23_$2 = C3-C23_$2 = C3-C27 = N7-C27
 1.3 with sigma of 0.02
 F40_$2-C23_$2
 2.38 with sigma of 0.02
 F40_$2-C36_$2
 2.3 with sigma of 0.02
 F31-C23_$2
 2.38 with sigma of 0.02
 F31-C27
 2.3 with sigma of 0.02
 F40_$2-C47_$2 = F31-C3
 1.34 with sigma of 0.02
 C23_$2-F31
 2.39 with sigma of 0.02
 C27-F31
 2.3 with sigma of 0.02
 F40_$2-C47_$2
 1.3 with sigma of 0.02
 F6-C12
 1.34 with sigma of 0.02
 F1AA-C42
 2.38 with sigma of 0.02
 F1AA-C4
 2.3 with sigma of 0.02
 F1AA-C1AA
 1.32 with sigma of 0.02
 C82-C39
 1.45 with sigma of 0.02
 N8-C0AA \\sim C12-C42 \\sim C1AA-C4
 with sigma of 0.02
 C136-C93 \\sim C86-C66
 with sigma of 0.02
 F27-C82 \\sim C97-C4AA
 with sigma of 0.02
 C82-F0AA \\sim F0AA-C2AA
 with sigma of 0.02
 C26-C34 \\sim C35-N18_$1 \\sim C2-C63
 with sigma of 0.02
 C26-C34 \\sim F5-C35
 with sigma of 0.02
 N7-C36_$2 \\sim C47_$2-F40_$2 \\sim C23_$2-F31 \\sim C3-C27
 with sigma of 0.02
 C27-F31 \\sim C23_$2-C3
 with sigma of 0.02
3. Restrained planarity
 C42, C86, C66, F37
 with sigma of 0.1
 F27, C97, C82, C4AA
 with sigma of 0.1
 C82, C5AA, F0AA, C2AA
 with sigma of 0.1
 C26, C34, C35, N18_$1, C2, C63
 with sigma of 0.1
 F5, C34, C26, C35
 with sigma of 0.1
 C26, C34, F5, C35
 with sigma of 0.1
 N7, C36_$2, C47_$2, F40_$2, C23_$2, C3, C27, F31
 with sigma of 0.1
 C27, F31, C3, C23_$2
 with sigma of 0.1
 F1AA, C4, C1AA, C42
 with sigma of 0.1
4. Rigid bond restraints
 N8, C0AA, C136, C12
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F41, C93, C136, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C86, F37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C66, F37, C86, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C82, C97, F27, C4AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C82, C5AA, C2AA, F0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C26, C34, C35, F5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C23, F31, C3, C27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C36, C47, F40, C23, F31, C3, C27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N7, C27, C3, F31, C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C44, C58, C65, C56, C116, C105
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F1AA, C1AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C42, C1AA, C4, F1AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C42, C12, C0AA, F6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C55, C83, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
N8 \\sim C0AA \\sim C136 \\sim C12: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
F41 \\sim C93 \\sim C136 \\sim C42: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
C86 \\sim F37: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04
C66 \\sim C86 \\sim F37 \\sim C42: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
F27 \\sim C97 \\sim C82 \\sim C4AA: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
C82 \\sim C5AA \\sim F0AA \\sim C2AA: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
F5 \\sim C26 \\sim C34 \\sim C35: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C23 \\sim F31 \\sim C3 \\sim C27: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C27 \\sim C3 \\sim F31 \\sim C23 \\sim C47 \\sim F40 \\sim C36: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
N7 \\sim C27 \\sim C3 \\sim F31 \\sim C23: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C44 \\sim C58 \\sim C65 \\sim C56 \\sim C116 \\sim C105: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
F1AA \\sim C1AA: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
F1AA \\sim C1AA \\sim C4 \\sim C42: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
F6 \\sim C12 \\sim C0AA \\sim C42: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C83 \\sim C55 \\sim C57: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
N3AA \\sim C2AA \\sim C4AA: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C2AA \\sim N3AA \\sim C4AA: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
O9 \\sim C21: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Uanis(F41) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C0AA)
\\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C1AA) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(F37) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5AA) \\sim Ueq, Uanis(F0AA) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C63) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C3AA)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C44) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C75) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C116) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq, Uanis(C21) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C21) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C16) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O15) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C51) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F1AA) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N3AA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6AA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O15) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O11) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O9) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
6. Others
 Fixed Sof: C136(0.5) C93(0.5) C86(0.5) C66(0.5) F40(0.5) C4(0.5) C1AA(0.5)
 C12(0.5) C0AA(0.5) F41(0.25) F37(0.25) F27(0.5) F0AA(0.5) H27(0.5) F31(0.5)
 F1AA(0.25) F6(0.25)
7.a Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C37(H37), C41(H41), C38(H38), C32(H32), C51(H51),
 C58(H58), C63(H63), C65(H65), C2AA(H2AA), C4AA(H4AA), C105(H105), C116(H116),
 C3AA(H3AA), C18(H18), C9(H9), C16(H16), C2(H2), C27(H27), C96(H96), C83(H83),
 C57(H57), C75(H75)
7.b Fitted hexagon refined as free rotating group:
 N8(C136,C93,C42,C86,C66), C41(C64,C38,C54,C32,C6AA), C82(C5AA,C2AA,N3AA,C4AA,
 C97), C133(C3AA,C18,C11,C9,C16), C96(C55,C83,C57,C30,C75)
;
_shelx_res_checksum              12314
_shelx_hkl_checksum              52039
_shelx_fab_checksum              80012
_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 1.180
_oxdiff_exptl_absorpt_empirical_full_min 0.843