Noninvasive Substitution of K<sup>+</sup> Sites in Cyclodextrin Metal-Organic Frameworks by Li<sup>+</sup> Ions.
Patel, Hasmukh A.; Islamoglu, Timur; Liu, Zhichang; Nalluri, Siva Krishna Mohan; Samanta, Avik; Anamimoghadam, Ommid; Malliakas, Christos D.; Farha, Omar K.; Stoddart, J. Fraser; Journal of the American Chemical Society 139 (2017) 11020–11023; doi:10.1021/jacs.7b06287

data_4131521
_publ_section_title
;
 Noninvasive Substitution of K<sup>+</sup> Sites in Cyclodextrin
 Metal-Organic Frameworks by Li<sup>+</sup> Ions.
;
_journal_issue                   32
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11020
_journal_page_last               11023
_journal_paper_doi               10.1021/jacs.7b06287
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C48 H80 K1.23 O40, 0.77(Li)'
_chemical_formula_sum            'C48 H80 K1.23 Li0.77 O40'
_chemical_formula_weight         1350.66
_space_group_crystal_system      trigonal
_space_group_IT_number           155
_space_group_name_Hall           'R 3 2"'
_space_group_name_H-M_alt        'R 3 2 :H'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-01-23
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   43.069(3)
_cell_length_b                   43.069(3)
_cell_length_c                   27.998(3)
_cell_measurement_reflns_used    9992
_cell_measurement_temperature    100
_cell_measurement_theta_max      62.772
_cell_measurement_theta_min      3.372
_cell_volume                     44977(7)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'QuazarTM optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0731
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            110303
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        63.496
_diffrn_reflns_theta_max         63.496
_diffrn_reflns_theta_min         1.973
_diffrn_source                   microsource
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.126
_exptl_absorpt_correction_T_max  0.7107
_exptl_absorpt_correction_T_min  0.6318
_exptl_absorpt_correction_type   psi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1263 before and 0.1022 after correction.
The Ratio of minimum to maximum transmission is 0.8890.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.898
_exptl_crystal_description       irregular
_exptl_crystal_F_000             12847
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.403
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.276(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     844
_refine_ls_number_reflns         15624
_refine_ls_number_restraints     704
_refine_ls_restrained_S_all      9.084
_refine_ls_R_factor_all          0.1147
_refine_ls_R_factor_gt           0.0998
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2625
_refine_ls_wR_factor_ref         0.2791
_reflns_Friedel_coverage         0.914
_reflns_Friedel_fraction_full    0.973
_reflns_Friedel_fraction_max     0.973
_reflns_number_gt                9899
_reflns_number_total             15624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b06287_si_002.cif
_cod_data_source_block           cx0662_0m
_cod_original_cell_volume        44975(8)
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               4131521
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.724(19) 0.276(19)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
3. Shared sites
{K1, Li1}
4. Restrained distances
 C5-C1 = C6-C5 = C2-C1 = C3-C2 = C4-C3 = C12-C11 = C7-C11 = C8-C7 = C9-C8 = C9-
 C10 = C18-C17 = C17-C13 = C14-C13 = C15-C14 = C16-C15 = C24-C23 = C23-C19 =
 C20-C19 = C21-C20 = C22-C21 = C30-C29 = C29-C25 = C26-C25 = C27-C26 = C28-C27 =
  C36-C35 = C35-C31 = C32-C31 = C33-C32 = C34-C33 = C42-C41 = C41-C37 = C38-C37
 = C39-C38 = C40-C39 = C48-C47 = C47-C43 = C44-C43 = C45-C44 = C46-C45
 1.50726 with sigma of 0.02
 O26-O27
 2.6 with sigma of 0.02
 O26-O25
 2.9 with sigma of 0.02
 O4-C6 = O9-C12 = O19-C24 = O24-C30 = O29-C36 = O34-C42 = O39-C48
 1.4432 with sigma of 0.005
 O17-H17
 0.88821 with sigma of 0.01
 O6-H6
 0.87 with sigma of 0.01
 O7-H7
 0.87 with sigma of 0.01
 O36-H36
 0.87 with sigma of 0.01
 O16-H16
 0.84 with sigma of 0.02
 C4-H4A
 1 with sigma of 0.02
 H4A-O3 = H4A-C3 = H4A-O5
 1.9 with sigma of 0.02
 O4-H4
 0.87 with sigma of 0.01
 O34-H34
 0.87 with sigma of 0.01
 O37-H37
 0.87 with sigma of 0.01
 O34-H34 = O4-H4
 0.84 with sigma of 0.02
 C45-H45
 1 with sigma of 0.02
 O37-H45
 2 with sigma of 0.02
 H45-C44
 2 with sigma of 0.02
 H45-C46
 2 with sigma of 0.02
 C4-H4A
 1 with sigma of 0.02
 O3-H4A
 2 with sigma of 0.02
 H4A-O5
 2 with sigma of 0.02
 H4A-C3
 2 with sigma of 0.02
 O14-H14
 0.84 with sigma of 0.02
 H18A-H14
 2.2 with sigma of 0.02
 C21-H21A
 1 with sigma of 0.02
 H21A-C22
 2 with sigma of 0.02
 H21A-C20
 2 with sigma of 0.02
 H21A-O17
 2 with sigma of 0.02
 H18B-H14
 2.2 with sigma of 0.02
 C16-H16A
 1 with sigma of 0.02
 H16A-O13
 2 with sigma of 0.02
 H16A-O15
 2 with sigma of 0.02
 H16A-C15
 2 with sigma of 0.02
 H1A-H4
 2.5 with sigma of 0.02
 H34-H42A
 2.3 with sigma of 0.02
 H34-H42B
 2.3 with sigma of 0.02
 C42-H34
 1.9 with sigma of 0.02
 H34-H34A
 2.2 with sigma of 0.02
 H37A-H34
 3.2 with sigma of 0.02
 H44-H36
 2.3 with sigma of 0.02
 H7-H11
 2.3 with sigma of 0.02
 O12-H16
 2.4 with sigma of 0.02
 C20-H16
 2.1 with sigma of 0.02
 O1-C2 = O2-C3 = O3-C5 = O3-C4 = O5-C4 = O5-C7 = O6-C8 = O7-C9 = O8-C11 = O8-
 C10 = O10-C10 = O10-C13 = O11-C14 = O12-C15 = O13-C17 = O13-C16 = O15-C16 =
 O15-C19 = O16-C20 = O17-C21 = O18-C23 = O18-C22 = O20-C22 = O20-C25 = O21-C26 =
  O22-C27 = O23-C29 = O23-C28 = O25-C28 = O25-C31 = O26-C32 = O27-C33 = O28-C35
 = O28-C34 = O30-C34 = O30-C37 = O31-C38 = O32-C39 = O33-C41 = O33-C40 = O35-
 C40 = O35-C43 = O36-C44 = O37-C45 = O38-C47 = O38-C46 = O40-C46 = O40-C1
 1.42866 with sigma of 0.02
 O32-H32
 0.84 with sigma of 0.02
 H32-H32_$1
 2.6 with sigma of 0.02
 H17-H21
 2.4 with sigma of 0.02
 H21-H31_$2
 2.4 with sigma of 0.02
 H14_$3-H19_$4
 2.4 with sigma of 0.02
 H36-H32
 2.4 with sigma of 0.02
 H11_$3-H11
 2.4 with sigma of 0.02
 H28-H26_$5
 2.4 with sigma of 0.02
 H26-H27
 2.4 with sigma of 0.02
 C21-H17
 1.929918 with sigma of 0.02
 K2-H17
 3.489183 with sigma of 0.02
 C8-H6
 1.920938 with sigma of 0.02
 K1-H6
 3.789422 with sigma of 0.02
 C9-H7
 1.935867 with sigma of 0.02
 K1-H7
 3.903483 with sigma of 0.02
 C44-H36
 1.89566 with sigma of 0.02
 K2-H36
 3.564861 with sigma of 0.02
 C6-H4
 1.909787 with sigma of 0.02
 K2-H4
 3.460084 with sigma of 0.02
 C42-H34
 1.907846 with sigma of 0.02
 K2-H34
 3.475017 with sigma of 0.02
 C45-H37
 1.887575 with sigma of 0.02
 K2-H37
 3.495726 with sigma of 0.02
5. Restrained planarity
 O26, C32, C33, C34
 with sigma of 0.01
6. Uiso/Uaniso restraints and constraints
Uanis(O39) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(O40) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C6)
\\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C4) \\sim Ueq,
Uanis(O2) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(O38)
\\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(O37) \\sim Ueq,
Uanis(C47) \\sim Ueq, Uanis(Li3) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(O36) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(O35) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(O6)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(C40) \\sim Ueq,
Uanis(C10) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(K1) \\sim Ueq, Uanis(O9) \\sim
Ueq, Uanis(C39) \\sim Ueq, Uanis(O33) \\sim Ueq, Uanis(O10) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(O32) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(O31) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C14) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(O30) \\sim Ueq, Uanis(O34)
\\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(O13) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(O12)
\\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(O28) \\sim Ueq, Uanis(O15) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(O27) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(C36) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(O25) \\sim Ueq, Uanis(O29)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(O18) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(K2)
\\sim Ueq, Uanis(O17) \\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(O23) \\sim Ueq, Uanis(O20) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(O22)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(O21) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(O24) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(K1) = Uanis(Li1)
Uanis(O27) = Uanis(O26)
Uanis(O22) = Uanis(O26) = Uanis(O32)
7. Others
 Sof(Li1)=0.5*(1-FVAR(2))
 Sof(K1)=0.5*FVAR(2)
 Fixed Uiso: H14(0.2)
8.a Fixed occupancy and ADP/Uiso:
 O29, C36
8.b Ternary CH refined with riding coordinates:
 C1(H1A), C2(H2A), C3(H3), C5(H5), C7(H7A), C8(H8), C9(H9A), C10(H10),
 C11(H11A), C13(H13), C14(H14A), C15(H15), C17(H17A), C19(H19A), C20(H20),
 C22(H22A), C23(H23), C25(H25), C26(H26A), C27(H27A), C28(H28), C29(H29A),
 C31(H31A), C32(H32A), C33(H33), C34(H34A), C35(H35), C37(H37A), C38(H38),
 C39(H39A), C40(H40), C41(H41), C43(H43), C44(H44), C46(H46), C47(H47)
8.c Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C12(H12A,H12B), C18(H18A,H18B), C24(H24A,H24B), C30(H30A,H30B),
 C36(H36A,H36B), C42(H42A,H42B), C48(H48A,H48B)
8.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O9(H9), O11(H11), O12(H12), O19(H19), O21(H21), O22(H22),
 O24(H24), O26(H26), O27(H27), O29(H29), O31(H31), O39(H39)
;
_shelx_res_checksum              91980
_shelx_hkl_checksum              41970
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'