Cage-Interconnected Metal-Organic Framework with Tailored Apertures for Efficient C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub> Separation under Humid Conditions.
Zeng, Heng; Xie, Xiao-Jing; Xie, Mo; Huang, Yong-Liang; Luo, Dong; Wang, Ting; Zhao, Yifang; Lu, Weigang; Li, Dan; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b10923

data_4133766
_publ_section_title
;
 Cage-Interconnected Metal-Organic Framework with Tailored Apertures for
 Efficient C<sub>2</sub>H<sub>6</sub>/C<sub>2</sub>H<sub>4</sub>
 Separation under Humid Conditions.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b10923
_journal_year                    2019
_chemical_formula_moiety         '0.01(C1536 H1440 Cu288 N960 O480)'
_chemical_formula_sum            'C16 H15 Cu3 N10 O5'
_chemical_formula_weight         618.00
_space_group_crystal_system      cubic
_space_group_IT_number           226
_space_group_name_Hall           '-F 4a 2 3'
_space_group_name_H-M_alt        'F m -3 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-19
_audit_creation_method
;
Olex2 1.2-beta
(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            96
_cell_length_a                   43.54745(12)
_cell_length_b                   43.54745(12)
_cell_length_c                   43.54745(12)
_cell_measurement_reflns_used    11611
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      77.3080
_cell_measurement_theta_min      4.5060
_cell_volume                     82582.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.982
_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     21.00  46.00   0.50    5.98    --   -0.90  69.00  -5.00   50
  2  \w    136.00 162.00   0.50   23.93    --  105.10  53.00-107.00   52
  3  \w      3.00  32.00   0.50    5.98    --    0.90  82.00-150.00   58
  4  \w     82.00 162.00   0.50   23.93    --  105.10  82.00-180.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0269291000
_diffrn_orient_matrix_UB_12      0.0211177000
_diffrn_orient_matrix_UB_13      -0.0089551000
_diffrn_orient_matrix_UB_21      -0.0224989000
_diffrn_orient_matrix_UB_22      0.0269709000
_diffrn_orient_matrix_UB_23      -0.0040348000
_diffrn_orient_matrix_UB_31      0.0043667000
_diffrn_orient_matrix_UB_32      0.0087599000
_diffrn_orient_matrix_UB_33      0.0340218000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0222
_diffrn_reflns_av_unetI/netI     0.0188
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       54
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            21935
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.915
_diffrn_reflns_theta_min         4.541
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    2.454
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dull dark red'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.193
_exptl_crystal_description       block
_exptl_crystal_F_000             29568
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.365
_refine_diff_density_min         -1.097
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     216
_refine_ls_number_reflns         3785
_refine_ls_number_restraints     235
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0474
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0814P)^2^+579.5682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1349
_refine_ls_wR_factor_ref         0.1377
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3433
_reflns_number_total             3785
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b10923_si_002.cif
_cod_data_source_block           As-synthesized_JNU-2
_cod_original_cell_volume        82582.5(7)
_cod_original_sg_symbol_Hall     '-F 4c 2 3'
_cod_database_code               4133766
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.887
_shelx_estimated_absorpt_t_min   0.867
_reflns_odcompleteness_completeness 99.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C4_1-N9_1
 1.365 with sigma of 0.007
 C8_1-N9_1
 1.352 with sigma of 0.013
 C8_1-N7_1
 1.318 with sigma of 0.009
 C5_1-N7_1
 1.387 with sigma of 0.007
 C4_1-C5_1
 1.389 with sigma of 0.009
 C5_1-C6_1
 1.409 with sigma of 0.01
 C6_1-N1_1
 1.35 with sigma of 0.01
 C6_1-N6_1
 1.337 with sigma of 0.014
 C2_1-N1_1
 1.334 with sigma of 0.011
 C2_1-N3_1
 1.334 with sigma of 0.011
 C4_1-N3_1
 1.343 with sigma of 0.013
 C4_1-C8_1
 2.176 with sigma of 0.014
 N7_1-N9_1
 2.239 with sigma of 0.015
 C5_1-C8_1
 2.128 with sigma of 0.012
 C4_1-N7_1
 2.28 with sigma of 0.013
 C6_1-N7_1
 2.555 with sigma of 0.016
 C4_1-C6_1
 2.382 with sigma of 0.04
 C5_1-N1_1
 2.36 with sigma of 0.017
 C5_1-N6_1
 2.419 with sigma of 0.02
 N1_1-N6_1
 2.306 with sigma of 0.021
 C2_1-C6_1
 2.308 with sigma of 0.018
 N1_1-N3_1
 2.405 with sigma of 0.017
 C2_1-C4_1
 2.267 with sigma of 0.04
 C5_1-N9_1
 2.197 with sigma of 0.012
 N3_1-N9_1
 2.418 with sigma of 0.02
 C5_1-N3_1
 2.441 with sigma of 0.017
 N4-C5 \\sim N4-C6
 with sigma of 0.02
3. Restrained planarity
 C4_1, N9_1, C5_1, N3_1
 with sigma of 0.1
 C6_1, C5_1, N6_1, N1_1
 with sigma of 0.1
 C5_1, N7_1, C6_1, C4_1
 with sigma of 0.1
 N9_1, C8_1, N7_1, C5_1
 with sigma of 0.1
 C8_1, N7_1, C5_1, C4_1
 with sigma of 0.1
 N7_1, C5_1, C4_1, N9_1
 with sigma of 0.1
 C5_1, C4_1, N9_1, C8_1
 with sigma of 0.1
 C4_1, N9_1, C8_1, N7_1
 with sigma of 0.1
 C5_1, C6_1, N1_1, C2_1
 with sigma of 0.1
 C6_1, N1_1, C2_1, N3_1
 with sigma of 0.1
 N1_1, C2_1, N3_1, C4_1
 with sigma of 0.1
 C2_1, N3_1, C4_1, C5_1
 with sigma of 0.1
 N3_1, C4_1, C5_1, C6_1
 with sigma of 0.1
 C4_1, C5_1, C6_1, N1_1
 with sigma of 0.1
 C2, O3, N4, C5, C6
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N9_1 \\sim C8_1 \\sim N7_1 \\sim C5_1 \\sim C6_1 \\sim N6_1 \\sim N1_1 \\sim
C2_1 \\sim N3_1 \\sim C4_1: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C2 \\sim O3 \\sim N4 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 N9_1, C8_1, N7_1, C5_1, C6_1, N6_1, N1_1, C2_1, N3_1, C4_1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, O3, N4, C5, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
7. Others
 Fixed Sof: C2(0.5) H2(0.5) O3(0.5) N4(0.5) C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5)
 C6(0.5) H6A(0.5) H6B(0.5) H6C(0.5) N9(0.5) C8(0.5) H8(0.5) N7(0.5) C5(0.5)
 C6(0.5) N6(0.5) H6A(0.5) H6B(0.5) N1(0.5) C2(0.5) H2(0.5) N3(0.5) C4(0.5)
8.a Free rotating group:
 C2(O3,N4,C5,C6)
8.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00B(H00B), C2(H2), C8(H8), C2(H2)
8.c X=CH2 refined with riding coordinates:
 N6(H6A,H6B)
8.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              91744
_shelx_hkl_checksum              11853
_shelx_fab_checksum              64101
_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 1.204
_oxdiff_exptl_absorpt_empirical_full_min 0.905