Tuning the Structures of Metal‒Organic Frameworks via a Mixed-Linker Strategy for Ethylene/Ethane Kinetic Separation
Lyndon, Richelle; You, Wenqin; Ma, Yao; Bacsa, John; Gong, Yutao; Stangland, Eric E.; Walton, Krista S.; Sholl, David S.; Lively, Ryan P.; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.9b04177

data_4003537
_publ_section_title
;
 Tuning the Structures of Metal--Organic Frameworks via a Mixed-Linker
 Strategy for Ethylene/Ethane Kinetic Separation
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.9b04177
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C63 H43 N27 Zn5, C3 H7 N1 O1'
_chemical_formula_sum            'C66 H50 N28 O Zn5'
_chemical_formula_weight         1578.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-10
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.10.03 svn.r3662 for OlexSys, GUI svn.r5953)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.0260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.96450(10)
_cell_length_b                   15.83910(10)
_cell_length_c                   21.1899(2)
_cell_measurement_reflns_used    15273
_cell_measurement_temperature    104(1)
_cell_measurement_theta_max      76.0420
_cell_measurement_theta_min      3.4700
_cell_volume                     3336.12(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      104(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.963
_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   -117.00 -92.00   0.50    4.00    --  -49.66-125.00 -30.00   50
  2  \w     54.00  86.00   0.50   16.00    --  104.44 -57.00 -60.00   64
  3  \w   -116.00 -71.00   0.50    4.00    --  -49.66-125.00-120.00   90
  4  \w     36.00  65.00   0.50   16.00    --  104.44 -57.00 -30.00   58
  5  \w   -110.00 -74.00   0.50    4.00    --  -49.66-125.00-150.00   72
  6  \w     34.00  87.00   0.50   16.00    --  104.44 -57.00   0.00  106
  7  \w   -138.00-113.00   0.50   16.00    --  -84.25 -57.00 150.00   50
  8  \w     33.00  86.00   0.50   16.00    --  104.44 -57.00 150.00  106
  9  \w     -4.00  21.00   0.50    4.00    --   49.66 -57.00 150.00   50
 10  \w     31.00  82.00   0.50   16.00    --  104.44 -19.00 -60.00  102
 11  \w    -81.00 -37.00   0.50    4.00    --  -49.66 -57.00 150.00   88
 12  \w     87.00 112.00   0.50   16.00    --  104.44 -19.00 -60.00   50
 13  \w     32.00 107.00   0.50   16.00    --  104.44 -19.00  60.00  150
 14  \w     64.00 121.00   0.50    4.00    --   49.66  38.00   0.00  114
 15  \w    110.00 169.00   0.50   16.00    --  104.44  19.00-150.00  118
 16  \w    -59.00  16.00   0.50    4.00    --  -49.66  57.00 -67.00  150
 17  \w     99.00 172.00   0.50   16.00    --  104.44  38.00 -90.00  146
 18  \w    -84.00 -39.00   0.50   16.00    --  -84.25  57.00 -67.00   90
 19  \w     99.00 176.00   0.50   16.00    --  104.44  38.00-120.00  154
 20  \w     86.00 119.00   0.50    4.00    --   49.66  57.00 -67.00   66
 21  \w    135.00 162.00   0.50   16.00    --  104.44  57.00 -67.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0145609000
_diffrn_orient_matrix_UB_12      -0.0488036000
_diffrn_orient_matrix_UB_13      -0.0630074000
_diffrn_orient_matrix_UB_21      0.1362583000
_diffrn_orient_matrix_UB_22      -0.0434827000
_diffrn_orient_matrix_UB_23      0.0164886000
_diffrn_orient_matrix_UB_31      -0.0724219000
_diffrn_orient_matrix_UB_32      -0.0719880000
_diffrn_orient_matrix_UB_33      0.0327501000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0468
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            24553
_diffrn_reflns_point_group_measured_fraction_full 0.779
_diffrn_reflns_point_group_measured_fraction_max 0.729
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.375
_diffrn_reflns_theta_min         3.487
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.552
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_correction_T_min  0.845
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.571
_exptl_crystal_description       prism
_exptl_crystal_F_000             1600
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.085
_exptl_crystal_size_mid          0.057
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 2765 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(2)
_refine_ls_extinction_coef       0.00028(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     920
_refine_ls_number_reflns         10214
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0407
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0391P)^2^+4.3878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0956
_refine_ls_wR_factor_ref         0.0981
_reflns_Friedel_coverage         0.459
_reflns_Friedel_fraction_full    0.541
_reflns_Friedel_fraction_max     0.477
_reflns_number_gt                9517
_reflns_number_total             10214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm9b04177_si_004.cif
_cod_data_source_block           126-6
_cod_database_code               4003537
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C128  H96  N52  O4  Zn10  '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_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
 N1S_1-C3S_1 = N1S_1-C2S_1
 1.459 with sigma of 0.007
 O5S_2-C4S_2
 1.22 with sigma of 0.005
3. Restrained planarity
 C4S_2, O5S_2, N1S_2, C2S_2, C3S_2
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(N1S_1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C2S_1) = Uanis(C2S_2)
Uanis(N1S_1) = Uanis(N1S_2)
Uanis(C3S_1) = Uanis(C3S_2)
Uanis(C4S_1) = Uanis(C4S_2)
Uanis(O5S_1) = Uanis(O5S_2)
5. Rigid body (RIGU) restrains
 N1S_1, O5S_1, C4S_1, C2S_1, C3S_1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
6. Same fragment restrains
{O5S_2, N1S_2, C2S_2, C3S_2, C4S_2}
as
{O5S_1, N1S_1, C2S_1, C3S_1, C4S_1} sigma for 1-2: 0.002 1-3: 0.004
7. Others
 Sof(O5S)=Sof(N1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=Sof(C3S)=Sof(H3SA)=
 Sof(H3SB)=Sof(H3SC)=Sof(C4S)=Sof(H4S)=1-FVAR(1)
 Sof(O5S)=Sof(N1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=Sof(C3S)=Sof(H3SA)=
 Sof(H3SB)=Sof(H3SC)=Sof(C4S)=Sof(H4S)=FVAR(1)
8.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12),
 C14(H14), C15(H15), C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23),
  C26(H26), C27(H27), C28(H28), C29(H29), C31(H31), C33(H33), C34(H34),
 C35(H35), C36(H36), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C48(H48),
  C49(H49), C50(H50), C51(H51), C53(H53), C54(H54), C55(H55), C56(H56),
 C59(H59), C60(H60), C61(H61), C62(H62), C4S(H4S), C4S(H4S)
8.b Idealised Me refined with riding coordinates:
 C2S(H2SA,H2SB,H2SC), C2S(H2SA,H2SB,H2SC)
8.c Idealised Me refined as rotating group:
 C3S(H3SA,H3SB,H3SC), C3S(H3SA,H3SB,H3SC)
;
_shelx_res_checksum              41990
_shelx_hkl_checksum              10062
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id 126-6
_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 1.501
_oxdiff_exptl_absorpt_empirical_full_min 0.605