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_4134925
_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 H31 Br0.5 Co4.5 N4 O17.5'
_chemical_formula_sum            'C55 H31 Br0.5 Co4.5 N4 O17.5'
_chemical_formula_weight         1332.98
_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             2019-04-14
_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                   21.9081(4)
_cell_length_b                   21.9081(4)
_cell_length_c                   39.4769(13)
_cell_measurement_reflns_used    4019
_cell_measurement_temperature    294.1(6)
_cell_measurement_theta_max      58.9620
_cell_measurement_theta_min      3.5920
_cell_volume                     18947.5(8)
_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      294.1(6)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5148
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.998
_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   -115.00 -16.00   1.00   12.50    --  -40.45 -38.00-180.00   99
  2  \w    -92.00  -2.00   1.00   12.50    --  -40.45 125.00 -30.00   90
  3  \w    -36.00  33.00   1.00   12.50    --   40.45 -19.00-120.00   69
  4  \w     31.00 119.00   1.00   35.00    --  103.24 -61.00-150.00   88
  5  \w     97.00 134.00   1.00   35.00    --  103.24 125.00 -30.00   37
  6  \w    135.00 161.00   1.00   35.00    --  103.24 125.00 -30.00   26
  7  \w    101.00 126.00   1.00   35.00    --  103.24 125.00  90.00   25
  8  \w     47.00 125.00   1.00   35.00    --  103.24 -61.00 -60.00   78
  9  \w    147.00 176.00   1.00   35.00    --  103.24 125.00-150.00   29
;
_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      0.0345851000
_diffrn_orient_matrix_UB_12      0.0507708000
_diffrn_orient_matrix_UB_13      -0.0189946000
_diffrn_orient_matrix_UB_21      0.0217080000
_diffrn_orient_matrix_UB_22      -0.0469322000
_diffrn_orient_matrix_UB_23      -0.0264338000
_diffrn_orient_matrix_UB_31      -0.0572717000
_diffrn_orient_matrix_UB_32      0.0128046000
_diffrn_orient_matrix_UB_33      -0.0215113000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1478
_diffrn_reflns_av_unetI/netI     0.1767
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            55131
_diffrn_reflns_point_group_measured_fraction_full 0.920
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.627
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.679
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69006
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   pinkish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    0.935
_exptl_crystal_description       block
_exptl_crystal_F_000             5344
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         2.134
_refine_diff_density_min         -1.106
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Flack x determined using 1599 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.503(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         15790
_refine_ls_number_restraints     551
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.2280
_refine_ls_R_factor_gt           0.1278
_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          0.3130
_refine_ls_wR_factor_ref         0.4049
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.849
_reflns_Friedel_fraction_max     0.862
_reflns_number_gt                6317
_reflns_number_total             15790
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00612_si_002.cif
_cod_data_source_block           FJU-6-BrBDC
_cod_original_cell_volume        18947.5(9)
_cod_original_formula_sum        'C55 H31 Br0.50 Co4.50 N4 O17.50'
_cod_database_code               4134925
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 CO1 Br1'
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 99.92
_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
 N9-C34
 2.72 with sigma of 0.02
 C71-C50
 2.72 with sigma of 0.02
 C62-C37
 2.72 with sigma of 0.02
 N9-C37 = N9-C71 = C71-C62 = C62-C34 = C50-C34 = C50-C37
 1.4 with sigma of 0.02
 C31-N15_$1
 2.7 with sigma of 0.02
 C73-C30
 2.7 with sigma of 0.02
 C41-C122_$1
 2.7 with sigma of 0.02
 C41-C31 = C73-C31 = C73-C122_$1 = N15_$1-C122_$1 = N15_$1-C30 = C41-C30
 1.4 with sigma of 0.02
 C7AA-C22 = C65-C22
 1.4 with sigma of 0.02
 C7AA-C65
 2.4 with sigma of 0.02
 C25-N5_$2
 2.7 with sigma of 0.02
 C43-C6AA
 2.7 with sigma of 0.02
 C44-C38
 2.7 with sigma of 0.02
 C44-C25 = C43-C25 = C43-C38 = N5_$2-C38 = N5_$2-C6AA = C6AA-C44
 1.4 with sigma of 0.02
 C2AA-C47_$3
 2.7 with sigma of 0.02
 C68-C86
 2.7 with sigma of 0.02
 C89-C54
 2.7 with sigma of 0.02
 C54-C2AA = C68-C2AA = C89-C68 = C89-C47_$3 = C86-C47_$3 = C86-C54
 1.4 with sigma of 0.02
 C5AA-C19 = C60-C47
 1.4 with sigma of 0.02
 C31-C18
 1.35 with sigma of 0.02
 H49-H74
 2 with sigma of 0.02
 C41-C31 \\sim C73-C122_$1 \\sim N15_$1-C30
 with sigma of 0.02
 C6AA-C44 \\sim C25-C43 \\sim C38-N5_$2
 with sigma of 0.02
 C54-C86 \\sim C47_$3-C89 \\sim C68-C2AA
 with sigma of 0.02
3. Restrained planarity
 C37, N9, C71, C62, C34, C50
 with sigma of 0.1
 C31, C73, C122_$1, N15_$1, C30, C41
 with sigma of 0.1
 C6AA, N5_$2, C38, C43, C25, C44
 with sigma of 0.1
 C2AA, C68, C89, C47_$3, C86, C54
 with sigma of 0.1
4. Rigid bond restraints
 C1AA, C72, N10, C6, C4, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O6, C27, O11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C65, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C65, C7AA, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C25, C44, C43, C38, N5, C6AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O5, C3, O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3AA, C11, C49, C1, C36, C0AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C65, C7AA, C22, C21, C65, C7AA, C22, C21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2AA, C68, C89, C47, C86, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5AA, C5, C130, C83, C82, C97
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O52, C8AA, O2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C65, C22, C7AA
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C71, C62, C34, C50, C37, N9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C65
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C4AA, C53, C98, C40, C60, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Br8, C65, C22, C7AA, C65, C7AA, Br1, Br1, Br8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C1AA \\sim C72 \\sim C42 \\sim C4 \\sim C6 \\sim N10: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C27 \\sim O6 \\sim O11: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C22 \\sim C65 \\sim C7AA: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C44 \\sim C6AA \\sim N5 \\sim C38 \\sim C43 \\sim C25: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C3 \\sim O5 \\sim O3: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C3AA \\sim C49 \\sim C11 \\sim C1 \\sim C36 \\sim C0AA: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C65 \\sim C7AA \\sim C22 \\sim C65 \\sim C7AA \\sim C22 \\sim C21 \\sim C21:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C2AA \\sim C68 \\sim C89 \\sim C86 \\sim C47 \\sim C54: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
C5AA \\sim C5 \\sim C130 \\sim C83 \\sim C82 \\sim C97: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.04
O52 \\sim C8AA \\sim O2: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C65 \\sim C22: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C65 \\sim C22 \\sim C7AA: within 1.7A with sigma of 0.001 and sigma for
terminal atoms of 0.002
C62 \\sim C34 \\sim C50 \\sim C37 \\sim N9 \\sim C71: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C4AA \\sim C53 \\sim C74 \\sim C60 \\sim C40 \\sim C98: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C65: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Br8 \\sim C65 \\sim C7AA \\sim Br1 \\sim Br1 \\sim C7AA \\sim Br8 \\sim C65
\\sim C22 \\sim C22: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C22) \\sim Ueq, Uanis(C65) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C65) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5AA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N15) \\sim Ueq, Uanis(C122) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8AA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O7) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C73)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C53) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C30) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O8) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
6. Others
 Fixed Sof: Br1(0.25) Br8(0.25)
7.a Aromatic/amide H refined with riding coordinates:
 C30(H30), C37(H37), C38(H38), C41(H41), C72(H72), C1AA(H1AA), C6(H6), C4(H4),
 C43(H43), C44(H44), C50(H50), C54(H54), C62(H62), C68(H68), C71(H71), C73(H73),
  C86(H86), C122(H122), C11(H11), C49(H49), C36(H36), C0AA(H0AA), C74(H74),
 C40(H40), C53(H53), C5(H5), C97(H97), C82(H82), C130(H130), C6AA(H6AA),
 C89(H89)
7.b Fitted hexagon refined as free rotating group:
 C42(C72,C1AA,N10,C6,C4), C3AA(C11,C49,C1,C36,C0AA), C4AA(C74,C60,C40,C98,C53),
  C5(C5AA,C97,C82,C83,C130)
;
_shelx_res_checksum              28164
_shelx_hkl_checksum              33265
_shelx_fab_checksum              75922
_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 1.511
_oxdiff_exptl_absorpt_empirical_full_min 0.701