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_4134926
_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 H33 N4 Ni4.5 O17.5'
_chemical_formula_sum            'C55 H34 N4 Ni4.5 O17.5'
_chemical_formula_weight         1295.05
_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             2019-01-29
_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                   21.6973(5)
_cell_length_b                   21.6973(5)
_cell_length_c                   39.0746(19)
_cell_measurement_reflns_used    3802
_cell_measurement_temperature    292.17(10)
_cell_measurement_theta_max      55.1180
_cell_measurement_theta_min      3.6160
_cell_volume                     18395.3(11)
_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      292.17(10)
_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 0.986
_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   15.00    --  -40.32  38.00-120.00   99
  2  \w     23.00  96.00   1.00   15.00    --   40.32-125.00  90.00   73
  3  \w    -32.00  50.00   1.00   15.00    --   40.32 -57.00 120.00   82
  4  \w     90.00 174.00   1.00   45.00    --  103.24  61.00-120.00   84
  5  \w    153.00 178.00   1.00   45.00    --  103.24  77.00-150.00   25
  6  \w     75.00 101.00   1.00   45.00    --  103.24  77.00-150.00   26
  7  \w     78.00 175.00   1.00   45.00    --  103.24  61.00   0.00   97
  8  \w     70.00 127.00   1.00   45.00    --  103.24 -45.00-150.00   57
;
_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      0.0554475000
_diffrn_orient_matrix_UB_12      -0.0367552000
_diffrn_orient_matrix_UB_13      0.0137784000
_diffrn_orient_matrix_UB_21      0.0048092000
_diffrn_orient_matrix_UB_22      -0.0344918000
_diffrn_orient_matrix_UB_23      -0.0343562000
_diffrn_orient_matrix_UB_31      0.0441296000
_diffrn_orient_matrix_UB_32      0.0499753000
_diffrn_orient_matrix_UB_33      -0.0135662000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1568
_diffrn_reflns_av_unetI/netI     0.1686
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            56558
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.705
_diffrn_reflns_theta_min         3.663
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.409
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79859
_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 greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    0.935
_exptl_crystal_description       block
_exptl_crystal_F_000             5264
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.205
_refine_diff_density_min         -0.887
_refine_diff_density_rms         0.117
_refine_ls_abs_structure_details
;
 Flack x determined using 2023 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.51(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.885
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     695
_refine_ls_number_reflns         17585
_refine_ls_number_restraints     625
_refine_ls_restrained_S_all      0.905
_refine_ls_R_factor_all          0.1853
_refine_ls_R_factor_gt           0.0915
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.1454P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2244
_refine_ls_wR_factor_ref         0.2854
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                6947
_reflns_number_total             17585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c00612_si_002.cif
_cod_data_source_block           FJU-6-Ni
_cod_original_cell_volume        18395.3(12)
_cod_original_formula_sum        'C55 H34 N4 Ni4.50 O17.50'
_cod_database_code               4134926
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C1 H1 O1 N1 Ni1'
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.972
_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
 N2-C29
 2.8 with sigma of 0.02
 C27-C30
 2.8 with sigma of 0.02
 C28-C31
 2.8 with sigma of 0.02
 N2-C31 = N2-C27 = C28-C27 = C28-C29 = C30-C29 = C30-C31
 1.3 with sigma of 0.02
 C15-C24_$1
 2.78 with sigma of 0.02
 C14-C26_$1
 2.78 with sigma of 0.02
 C25_$1-C16
 2.78 with sigma of 0.02
 C16-C15 = C14-C25_$1 = C24_$1-C26_$1
 1.3 with sigma of 0.02
 C15-C14 = C25_$1-C24_$1 = C26_$1-C16
 1.39 with sigma of 0.02
 O14-C55 = O18_$2-C55
 1.35 with sigma of 0.02
 O14-O18_$2
 2.35 with sigma of 0.02
 O15-O16
 2.2 with sigma of 0.02
 C17-C20
 2.78 with sigma of 0.02
 C19-C22
 2.78 with sigma of 0.02
 C18-C21
 2.78 with sigma of 0.02
 C18-C17 = C22-C17 = C22-C21 = C21-C20 = C19-C20 = C19-C18
 1.32 with sigma of 0.02
 C8-C7 = C8-C10 = C8-C9
 1.5 with sigma of 0.02
 C24-C23
 1.5 with sigma of 0.02
 O4-C23 = O5-C23
 1.35 with sigma of 0.02
 O5-C23
 1.32 with sigma of 0.02
 N2-C27 \\sim C28-C29 \\sim C30-C31
 with sigma of 0.02
 C17-C18 \\sim C19-C20 \\sim C21-C22
 with sigma of 0.02
3. Restrained planarity
 N2, C27, C28, C29, C30, C31
 with sigma of 0.1
 C15, C14, C25_$1, C24_$1, C26_$1, C16
 with sigma of 0.1
 O15, C44, O16, C29_$3
 with sigma of 0.1
 C17, C18, C19, C20, C21, C22
 with sigma of 0.1
 O4, C23, C24, O5
 with sigma of 0.1
4. Rigid bond restraints
 C40, C41, N4, C43, C42, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C12, C11, C10, C8, C9, C13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, O16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C14, C15, C16, C26, C24, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C15, C16, C26, C24, C25, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17, C18, C19, C20, C21, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N3, C54, C53, C50, C51, C52
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C40 \\sim C39 \\sim C42 \\sim C43 \\sim N4 \\sim C41: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C11 \\sim C10 \\sim C8 \\sim C9 \\sim C13 \\sim C12: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
O16 \\sim C29: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C29 \\sim C44 \\sim O16: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C16 \\sim C15 \\sim C14 \\sim C25 \\sim C24 \\sim C26: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C14 \\sim C15 \\sim C16 \\sim C26 \\sim C24 \\sim C25: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C15 \\sim C14 \\sim C25 \\sim C24 \\sim C26 \\sim C16: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C28 \\sim C29 \\sim C30 \\sim C31 \\sim C27 \\sim N2: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C30 \\sim C29 \\sim C28 \\sim C27 \\sim N2 \\sim C31: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C21 \\sim C22 \\sim C17 \\sim C18 \\sim C19 \\sim C20: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C54 \\sim N3 \\sim C52 \\sim C51 \\sim C50 \\sim C53: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(O16) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C37) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(N3)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C45) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C32) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C54) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(O6)
\\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C23) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C46) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C36) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(O6) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O9) \\sim Ueq, Uanis(O13) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(C45)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C53) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C3)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C45) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O13) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C39) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O10) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(N4)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(O5) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(N2) \\sim
Ueq, Uanis(C12) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(O11) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C33) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
6.a Aromatic/amide H refined with riding coordinates:
 C51(H51), C52(H52), C34(H34), C47(H47), C4(H4), C6(H6), C5(H5), C3(H3),
 C35(H35), C36(H36), C27(H27), C37(H37), C28(H28), C48(H48), C10(H10), C12(H12),
  C9(H9), C53(H53), C31(H31), C42(H42), C43(H43), C41(H41), C40(H40), C30(H30),
 C26(H26), C25(H25), C16(H16), C14(H14), C54(H54), C22(H22), C21(H21), C19(H19),
  C18(H18)
6.b Fitted hexagon refined as free rotating group:
 C2(C4,C6,C7,C5,C3), C8(C10,C11,C12,C13,C9), C39(C42,C43,N4,C41,C40)
;
_shelx_res_checksum              61890
_shelx_hkl_checksum              6992
_shelx_fab_checksum              13017
_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 1.297
_oxdiff_exptl_absorpt_empirical_full_min 0.730