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_4134922
_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         'C58 H40 Co4.5 N4 O17.5'
_chemical_formula_sum            'C58 H40 Co4.5 N4 O17.5'
_chemical_formula_weight         1338.12
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-23
_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                   21.8598(3)
_cell_length_b                   21.8598(3)
_cell_length_c                   39.3559(11)
_cell_measurement_reflns_used    10642
_cell_measurement_temperature    293.6(4)
_cell_measurement_theta_max      70.7350
_cell_measurement_theta_min      3.6050
_cell_volume                     18806.3(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      air
_diffrn_ambient_temperature      293.6(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.992
_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    -65.00  34.00   1.00    7.50    --  -40.45  38.00 -90.00   99
  2  \w   -117.00  -8.00   1.00    7.50    --  -40.45 -77.00   0.00  109
  3  \w     94.00 176.00   1.00   17.50    --  103.24 125.00-120.00   82
  4  \w     30.00 117.00   1.00   17.50    --  103.24-125.00 -90.00   87
  5  \w     77.00 176.00   1.00   17.50    --  103.24  45.00-180.00   99
  6  \w     71.00 178.00   1.00   17.50    --  103.24  77.00 -60.00  107
  7  \w     94.00 176.00   1.00   17.50    --  103.24 125.00 -30.00   82
  8  \w   -113.00 -12.00   1.00    7.50    --  -40.45 -57.00-120.00  101
  9  \w   -117.00  -8.00   1.00    7.50    --  -40.45 -77.00 150.00  109
;
_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      0.0421267000
_diffrn_orient_matrix_UB_12      -0.0315785000
_diffrn_orient_matrix_UB_13      -0.0259989000
_diffrn_orient_matrix_UB_21      -0.0403048000
_diffrn_orient_matrix_UB_22      0.0241019000
_diffrn_orient_matrix_UB_23      -0.0292280000
_diffrn_orient_matrix_UB_31      0.0394947000
_diffrn_orient_matrix_UB_32      0.0582208000
_diffrn_orient_matrix_UB_33      -0.0020430000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1598
_diffrn_reflns_av_unetI/netI     0.1169
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       48
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            93711
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.760
_diffrn_reflns_theta_min         3.636
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27765
_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    0.945
_exptl_crystal_description       block
_exptl_crystal_F_000             5420
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.717
_refine_diff_density_min         -0.749
_refine_diff_density_rms         0.142
_refine_ls_abs_structure_details
;
 Flack x determined using 3088 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.490(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     711
_refine_ls_number_reflns         18040
_refine_ls_number_restraints     583
_refine_ls_restrained_S_all      1.336
_refine_ls_R_factor_all          0.1795
_refine_ls_R_factor_gt           0.1208
_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          0.3110
_refine_ls_wR_factor_ref         0.3637
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    0.962
_reflns_Friedel_fraction_max     0.932
_reflns_number_gt                9612
_reflns_number_total             18040
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00612_si_002.cif
_cod_data_source_block           FJU-6-Me-INA
_cod_original_cell_volume        18806.2(7)
_cod_original_formula_sum        'C58 H40 Co4.50 N4 O17.50'
_cod_database_code               4134922
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 Co1'
_shelx_estimated_absorpt_t_max   0.881
_shelx_estimated_absorpt_t_min   0.829
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C13-C8
 1.506 with sigma of 0.02
 C13-C4
 2.3 with sigma of 0.02
 C8-C13
 1.5 with sigma of 0.02
 C7-C13
 2.75 with sigma of 0.02
 C4-C13
 2 with sigma of 0.02
 N14-C25_$1
 2.78 with sigma of 0.02
 C96-C1AA
 2.78 with sigma of 0.02
 C82-C6AA_$1
 2.78 with sigma of 0.02
 C6AA_$1-C25_$1
 1.32 with sigma of 0.02
 C25-N14_$2
 2.8 with sigma of 0.02
 C96_$2-C1AA_$2
 2.8 with sigma of 0.02
 C6AA-C82_$2
 2.8 with sigma of 0.02
 C6AA-C25 = C25-C1AA_$2 = C82_$2-C1AA_$2 = N14_$2-C82_$2 = N14_$2-C96_$2 =
 C96_$2-C6AA
 1.35 with sigma of 0.02
 C2AA_$2-C23_$2
 2.78 with sigma of 0.02
 C19_$2-C8AA_$2
 2.78 with sigma of 0.02
 C7AA_$2-C2AA_$2 = C7AA_$2-C19_$2 = C23_$2-C19_$2 = C8AA_$2-C2AA_$2
 1.35 with sigma of 0.02
 C72_$3-C1BA_$3
 1.5 with sigma of 0.02
 C9AA-C1BA_$3
 2.5 with sigma of 0.02
 C1BA_$3-C22_$3
 2.6 with sigma of 0.02
 C22-N6_$4
 2.78 with sigma of 0.02
 C49-C9AA_$4
 2.78 with sigma of 0.02
 C0BA_$4-C72
 2.78 with sigma of 0.02
 C9AA_$4-C72 = C72-C22 = C49-C22 = C49-C0BA_$4 = N6_$4-C0BA_$4 = N6_$4-C9AA_$4
 1.32 with sigma of 0.02
 C3BA-C19_$2
 2.5 with sigma of 0.02
 C0AA_$2-C3BA
 2.5 with sigma of 0.02
 O4BA-O3
 2.2 with sigma of 0.02
 O4BA-C3BA = O3-C3BA
 1.2 with sigma of 0.02
 C0AA-C19
 2.365 with sigma of 0.02
 C8AA-C2AA = C7AA-C2AA = C7AA-C19 = C23-C19 = C23-C0AA = C8AA-C0AA
 1.32 with sigma of 0.02
 C2AA-C23
 2.78 with sigma of 0.02
 C7AA-C0AA
 2.78 with sigma of 0.02
 C19-C8AA
 2.78 with sigma of 0.02
 C88-C5
 1.6 with sigma of 0.02
 C88-C1
 2.8 with sigma of 0.02
 C88-C10
 3 with sigma of 0.02
 C1-C88
 2.4 with sigma of 0.02
 C6AA_$1-C24_$1
 1.51 with sigma of 0.02
 C25_$1-C24_$1
 2.6 with sigma of 0.02
 C24_$1-C96
 2.5 with sigma of 0.02
 C23_$2-C19_$2
 1.3 with sigma of 0.02
 C3BA-C23_$2
 1.1 with sigma of 0.02
 H88C-H0BA
 1.7 with sigma of 0.02
 H0BA-H88C
 1.8 with sigma of 0.02
 H0BA-H88A
 1.8 with sigma of 0.02
 C4-C8 \\sim C7-C13
 with sigma of 0.02
 C82-N14 \\sim C96-C6AA_$1 \\sim C25_$1-C1AA
 with sigma of 0.02
 C25-C6AA \\sim C96_$2-N14_$2 \\sim C82_$2-C1AA_$2
 with sigma of 0.02
 C2AA_$2-C8AA_$2 \\sim C19_$2-C7AA_$2
 with sigma of 0.02
 C72-C22 \\sim C49-C0BA_$4 \\sim N6_$4-C9AA_$4
 with sigma of 0.02
 C3BA-C23_$2 \\sim C19_$2-C0AA_$2
 with sigma of 0.02
 O4BA-C3BA \\sim C3BA-O3
 with sigma of 0.02
 C8AA-C2AA \\sim C7AA-C19 \\sim C23-C0AA
 with sigma of 0.02
 C1-C5 \\sim C88-C10
 with sigma of 0.02
 C24_$1-C6AA_$1 \\sim C25_$1-C96
 with sigma of 0.02
3. Restrained planarity
 C4, C8, C7, C13
 with sigma of 0.1
 N14, C82, C1AA, C25_$1, C6AA_$1, C96
 with sigma of 0.1
 C2AA_$2, C7AA_$2, C19_$2, C23_$2, C8AA_$2
 with sigma of 0.1
 C72, C22, C49, C0BA_$4, N6_$4, C9AA_$4, C1BA
 with sigma of 0.1
 C3BA, C23_$2, C19_$2, C0AA_$2
 with sigma of 0.1
 C2AA, C7AA, C19, C23, C0AA, C8AA
 with sigma of 0.1
 C1, C5, C88, C10, N100, C4AA, C5AA
 with sigma of 0.1
 C1, C5, C10, C88
 with sigma of 0.1
 C25_$1, C6AA_$1, C24_$1, C96
 with sigma of 0.1
 C25, C6AA, C96_$2, N14_$2, C82_$2, C1AA_$2, C24
 with sigma of 0.1
4. Rigid bond restraints
 C62, C142, C44, C67, C50, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N13, C3, C4, C8, C7, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4, C8, C7, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5, C1, C5AA, C4AA, N100, C10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C31, C32, C84, C53, C58, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C23, C19, C0AA, C8AA, C2AA, C7AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1BA, C72, C22, C49, C0BA, N6, C9AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O4, C2BA, O27
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O4BA, C3BA, O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C88, C5, C10, N100, C4AA, C5AA, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C24, C6AA, C25, C96
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C24, C6AA, C25, C1AA, C82, N14, C96
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C38, C48, C40, C79, C30, C3AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1AA, C25, C6AA, C24, C96, N14, C82
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C62 \\sim C142 \\sim C44 \\sim C45 \\sim C50 \\sim C67: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C14 \\sim C3 \\sim C7 \\sim C8 \\sim C4 \\sim N13: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C4 \\sim C8 \\sim C13 \\sim C7: within 1.7A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C5 \\sim C1 \\sim C5AA \\sim C4AA \\sim N100 \\sim C10: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C53 \\sim C32 \\sim C31 \\sim C42 \\sim C58: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C31 \\sim C32 \\sim C84 \\sim C53 \\sim C58 \\sim C42: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C19 \\sim C23 \\sim C0AA \\sim C8AA \\sim C2AA \\sim C7AA: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C1BA \\sim C72 \\sim C22 \\sim C9AA \\sim N6 \\sim C0BA \\sim C49: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
O4 \\sim C2BA \\sim O27: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
O4BA \\sim C3BA \\sim O3: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C88 \\sim C5 \\sim C1 \\sim C10 \\sim N100 \\sim C4AA \\sim C5AA: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
C25 \\sim C96 \\sim N14 \\sim C82 \\sim C1AA \\sim C6AA \\sim C24: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C24 \\sim C6AA \\sim C25 \\sim C96: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
C40 \\sim C79 \\sim C30 \\sim C3AA \\sim C48 \\sim C38: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C24 \\sim C6AA \\sim C25 \\sim C1AA \\sim C82 \\sim N14 \\sim C96: within 1.7A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq, Uanis(C2AA) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C88) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O12) \\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(N6) \\sim Ueq, Uanis(C0BA)
\\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Others
 Fixed Sof: C82(0.5) H82(0.5) C96(0.5) H96(0.5)
7.a Rotating group:
 C88(H88A,H88B,H88C)
7.b Aromatic/amide H refined with riding coordinates:
 C34(H34), C38(H38), C30(H30), C40(H40), C41(H41), C49(H49), C62(H62),
 C142(H142), C50(H50), C67(H67), C82(H82), C96(H96), C4(H4), C3(H3), C14(H14),
 C0AA(H0AA), C1AA(H1AA), C5AA(H5AA), C4AA(H4AA), C10(H10), C32(H32), C84(H84),
 C58(H58), C42(H42), C19(H19), C8AA(H8AA), C7AA(H7AA), C9AA(H9AA), C0BA(H0BA)
7.c Fitted hexagon refined as free rotating group:
 C38(C3AA,C30,C79,C40,C48), C62(C142,C45,C50,C67,C44), C7(C8,C4,N13,C3,C14),
 C1(C5AA,C4AA,N100,C10,C5), C31(C32,C84,C53,C58,C42)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C24(H24A,H24B,H24C), C1BA(H1BA,H1BB,H1BC)
;
_shelx_res_checksum              61734
_shelx_hkl_checksum              91970
_shelx_fab_checksum              42544
_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 2.260
_oxdiff_exptl_absorpt_empirical_full_min 0.466