Hysteresis in the gas sorption isotherms of metal-organic cages accompanied by subtle changes in molecular packing.
Craig, Gavin A.; Larpent, Patrick; Urabe, Hinano; Legrand, Alexandre; Bonneau, Mickaele; Kusaka, Shinpei; Furukawa, Shuhei; Chemical communications (Cambridge, England) 56 (2020) 3689–3692; doi:10.1039/d0cc00932f

data_7126335
_publ_section_title
;
 Hysteresis in the gas sorption isotherms of metal-organic cages
 accompanied by subtle changes in molecular packing.
;
_journal_issue                   25
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              3689
_journal_page_last               3692
_journal_paper_doi               10.1039/d0cc00932f
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C108.5 H79 Cu4 N2 O24, 1.4(C4 H9 N O)'
_chemical_formula_sum            'C128.5 H124 Cu4 N7 O29'
_chemical_formula_weight         2484.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-10-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-18 deposited with the CCDC.	2020-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 111.254(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.2345(3)
_cell_length_b                   29.3603(5)
_cell_length_c                   16.5980(4)
_cell_measurement_reflns_used    28687
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.5460
_cell_measurement_theta_min      2.0990
_cell_volume                     6465.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.43c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.43c (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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.916
_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   -110.00  67.00   0.30   16.00    --  -20.60  45.00 -18.92  590
  2  \w   -110.00  67.00   0.30   16.00    --  -20.60  45.00 -18.92  590
  3  \w     18.00  67.20   0.30   16.00    --  -20.60  45.00  -6.80  164
  4  \w    -86.00 -60.20   0.30   16.00    --  -20.60  45.00  60.00   86
  5  \w    -19.00  63.20   0.30   16.00    --  -20.60  45.00  60.00  274
  6  \w   -109.00  67.10   0.30   16.00    --  -20.60  45.00 179.59  587
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0086064000
_diffrn_orient_matrix_UB_12      0.0147329000
_diffrn_orient_matrix_UB_13      0.0358596000
_diffrn_orient_matrix_UB_21      0.0072802000
_diffrn_orient_matrix_UB_22      0.0184840000
_diffrn_orient_matrix_UB_23      -0.0246376000
_diffrn_orient_matrix_UB_31      -0.0522509000
_diffrn_orient_matrix_UB_32      0.0049703000
_diffrn_orient_matrix_UB_33      -0.0145318000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.916
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            78471
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.916
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.075
_diffrn_reflns_theta_min         1.912
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.723
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92561
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.43c (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             2584
_exptl_crystal_preparation       'Gas sorption measurements'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.979
_refine_diff_density_min         -0.598
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     737
_refine_ls_number_reflns         15871
_refine_ls_number_restraints     112
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0602
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0784P)^2^+9.0344P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1634
_refine_ls_wR_factor_ref         0.1746
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12704
_reflns_number_total             15871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc00932f2.cif
_cod_data_source_block           gac354_sq
_cod_original_formula_sum        'C128.50 H124 Cu4 N7 O29'
_cod_database_code               7126335
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu4 C100 H65 O10 N2'
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.899
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_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, All O(H,H) groups
2. Restrained distances
 O60-H60A = O60-H60B
 0.88 with sigma of 0.01
 H60A-H60B
 1.33 with sigma of 0.02
 C80-N82 = N2S-C5S
 1.35 with sigma of 0.01
 N82-C83 = N2S-C8S = N2S-C7S
 1.46 with sigma of 0.01
 N82-C84
 1.46 with sigma of 0.01
 C81-C84
 2.88 with sigma of 0.02
 C83-C84
 2.5 with sigma of 0.02
 C5S-C6S
 1.5 with sigma of 0.01
3. Rigid bond restraints
 O70, C71, N72, C74, C75, C73
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O1S, N1S, C3S, C2S, C4S, C1S
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O70 \\sim C71 \\sim N72 \\sim C74 \\sim C75 \\sim C73: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.02
O1S \\sim N1S \\sim C3S \\sim C2S \\sim C4S \\sim C1S: within 1.7A with sigma
of 0.02 and sigma for terminal atoms of 0.02
Uanis(N72) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C75) \\sim Ueq: with sigma of
0.007 and sigma for terminal atoms of 0.014
Uanis(O70) = Uanis(O80)
Uanis(N82) = Uanis(N72)
Uanis(C80) = Uanis(C71)
Uanis(C81) = Uanis(C73)
Uanis(C83) = Uanis(C74)
Uanis(C84) = Uanis(C75)
5. Others
 Sof(O80)=Sof(C80)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C83)=Sof(H83A)=
 Sof(H83B)=Sof(H83C)=Sof(N82)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=1-FVAR(1)
 Sof(O70)=Sof(C71)=Sof(N72)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=
 Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(1)
 Fixed Sof: H60A(0.75) O1S(0.5) N1S(0.5) C3S(0.5) H3SA(0.5) H3SB(0.5)
 H3SC(0.5) C2S(0.5) H2SA(0.5) H2SB(0.5) H2SC(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5)
 H4SC(0.5) C1S(0.5) C61(0.25) H61A(0.25) H61B(0.25) H61C(0.25) O4S(0.2)
 C5S(0.2) N2S(0.2) C7S(0.2) H7SA(0.2) H7SB(0.2) H7SC(0.2) C6S(0.2) H6SA(0.2)
 H6SB(0.2) H6SC(0.2) C8S(0.2) H8SA(0.2) H8SB(0.2) H8SC(0.2)
6.a Fixed occupancy and ADP/Uiso:
 H60A, H60B
6.b Riding coordinates:
 C81(H81A,H81B,H81C), C83(H83A,H83B,H83C)
6.c Me refined with riding coordinates:
 C74(H74A,H74B,H74C), C84(H84A,H84B,H84C), C7S(H7SA,H7SB,H7SC), C6S(H6SA,H6SB,
 H6SC), C8S(H8SA,H8SB,H8SC)
6.d Aromatic/amide H refined with riding coordinates:
 C6(H6), C14(H14), C23(H23), C21(H21), C48(H48), C20(H20), C12(H12), C2(H2),
 C10(H10), C37(H37), C39(H39), C4(H4), C19(H19), C27(H27), C35(H35), C45(H45),
 C44(H44), C11(H11), C46(H46), C36(H36), C31(H31), C29(H29)
6.e Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C50(H50A,H50B,H50C), C75(H75A,H75B,H75C), C73(H73A,H73B,
 H73C), C3S(H3SA,H3SB,H3SC), C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C61(H61A,
 H61B,H61C)
;
_shelx_res_checksum              82856
_shelx_fab_checksum              46773
_platon_squeeze_void_probe_radius 1.20
_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 1.084
_oxdiff_exptl_absorpt_empirical_full_min 0.923