Adsorptive Separation of Cyclohexanol and Cyclohexanone by Nonporous Adaptive Crystals of RhombicArene
Zhao, Yong-Ye; xiao, hongyan; Tung, Chen-Ho; Wu, Li-Zhu; Cong, Huan; Chemical Science  (2021) –; doi:10.1039/D1SC04728K

data_1565346
_publ_section_title
;
 Adsorptive Separation of Cyclohexanol and Cyclohexanone by Nonporous
 Adaptive Crystals of RhombicArene
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC04728K
_journal_year                    2021
_chemical_formula_moiety         '0.5(C74 H76 O12), 0.5(C74 H74 O12), C2 H3 N'
_chemical_formula_sum            'C76 H78 N O12'
_chemical_formula_weight         1197.39
_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             2020-06-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-05-17 deposited with the CCDC.	2021-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.9620(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.06780(10)
_cell_length_b                   15.89110(10)
_cell_length_c                   25.6047(2)
_cell_measurement_reflns_used    62384
_cell_measurement_temperature    170.00(13)
_cell_measurement_theta_max      74.9900
_cell_measurement_theta_min      2.4310
_cell_volume                     7722.23(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_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      170.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.981
_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    -85.00  -8.00   0.50    0.20    --  -47.20 110.00 -85.00  154
  2  \w    -57.00 -31.00   0.50    2.00    --  -99.00  61.00 -60.00   52
  3  \w    -19.00  21.00   0.50    0.20    --  -47.20  19.00-150.00   80
  4  \w     -9.00  20.00   0.50    0.20    --  -47.20  19.00-180.00   58
  5  \w   -101.00 -75.00   0.50    0.20    --  -47.20-125.00 -30.00   52
  6  \w   -113.00 -75.00   0.50    0.20    --  -47.20-125.00 -90.00   76
  7  \w   -119.00 -83.00   0.50    0.20    --  -47.20-125.00 -60.00   72
  8  \w   -112.00 -86.00   0.50    2.00    --  -99.00 -61.00-150.00   52
  9  \w   -168.00 -97.00   0.50    2.00    --  -99.00 -45.00-180.00  142
 10  \w   -168.00-141.00   0.50    2.00    --  -99.00 -61.00-150.00   54
 11  \w   -102.00 -27.00   0.50    2.00    --  -99.00  77.00 -90.00  150
 12  \w   -102.00 -26.00   0.50    2.00    --  -99.00 110.00 -85.00  152
 13  \w    -68.00 -27.00   0.50    2.00    --  -99.00  61.00  60.00   82
 14  \w    -68.00 -42.00   0.50    2.00    --  -99.00  61.00 120.00   52
 15  \w    -68.00 -29.00   0.50    2.00    --  -99.00  61.00  90.00   78
 16  \w    -20.00  23.00   0.50    0.20    --  -47.20  38.00  90.00   86
 17  \w     23.00  49.00   0.50    0.20    --   47.20-110.00 179.00   52
 18  \w     75.00 105.00   0.50    2.00    --  103.25-110.00 179.00   60
 19  \w     38.00  75.00   0.50    2.00    --  103.25 -61.00 150.00   74
 20  \w     90.00 156.00   0.50    2.00    --  103.25  15.00  30.00  132
 21  \w     93.00 169.00   0.50    2.00    --  103.25 110.00 -85.00  152
 22  \w    107.00 157.00   0.50    2.00    --  103.25  61.00-120.00  100
 23  \w     56.00 104.00   0.50    2.00    --  103.25 -94.00-180.00   96
 24  \w     36.00  71.00   0.50    2.00    --  103.25 -61.00-150.00   70
 25  \w     40.00 104.00   0.50    2.00    --  103.25-125.00 -60.00  128
 26  \w   -139.00-114.00   0.50    2.00    --  -99.00-110.00 179.00   50
 27  \w    104.00 129.00   0.50    2.00    --  103.25 110.00 -85.00   50
 28  \w    -34.00   6.00   0.50    0.20    --  -47.20  38.00 -30.00   80
 29  \w    -61.00  24.00   0.50    0.20    --  -47.20  57.00-120.00  170
 30  \w   -120.00 -94.00   0.50    0.20    --  -47.20-125.00  60.00   52
 31  \w    -31.00  25.00   0.50    0.20    --  -47.20  38.00 150.00  112
 32  \w     -6.00  28.00   0.50    0.20    --   47.20 -19.00 150.00   68
 33  \w    -89.00 -63.00   0.50    2.00    --  -99.00  77.00-180.00   52
 34  \w   -124.00 -98.00   0.50    2.00    --  -99.00 142.00 -69.27   52
 35  \w    -58.00 -26.00   0.50    2.00    --  -99.00 125.00-120.00   64
 36  \w    -59.00 -33.00   0.50    2.00    --  -99.00 143.00  16.09   52
 37  \w    -58.00 -32.00   0.50    2.00    --  -99.00 138.00 165.54   52
 38  \w    -56.00 -29.00   0.50    2.00    --  -99.00  61.00 -30.00   54
 39  \w   -143.00 -90.00   0.50    2.00    --  -99.00 -73.00-173.74  106
 40  \w   -151.00 -94.00   0.50    2.00    --  -99.00 -53.00  12.80  114
 41  \w   -167.00-132.00   0.50    2.00    --  -99.00 -53.00  25.79   70
 42  \w   -160.00-124.00   0.50    2.00    --  -99.00 -77.00-120.00   72
 43  \w   -121.00 -94.00   0.50    2.00    --  -99.00 -53.00  25.79   54
 44  \w   -153.00 -85.00   0.50    2.00    --  -99.00 -52.00  43.12  136
 45  \w   -118.00 -78.00   0.50    2.00    --  -99.00 138.00 165.54   80
 46  \w   -126.00-100.00   0.50    2.00    --  -99.00 144.00-171.50   52
 47  \w   -125.00-100.00   0.50    2.00    --  -99.00 143.00  16.09   50
 48  \w    -51.00 -26.00   0.50    2.00    --  -99.00  77.00-180.00   50
 49  \w   -112.00 -86.00   0.50    2.00    --  -99.00 125.00-120.00   52
 50  \w     33.00 111.00   0.50    2.00    --  103.25-125.00   0.00  156
 51  \w     82.00 109.00   0.50    2.00    --  103.25 -77.00 -30.00   54
 52  \w     33.00  76.00   0.50    2.00    --  103.25 -77.00 -30.00   86
 53  \w     78.00 111.00   0.50    2.00    --  103.25-125.00 120.00   66
 54  \w     83.00 108.00   0.50    2.00    --  103.25-110.00 179.00   50
 55  \w     31.00  69.00   0.50    2.00    --  103.25 -61.00-180.00   76
 56  \w     40.00 109.00   0.50    2.00    --  103.25-125.00-180.00  138
 57  \w     61.00 106.00   0.50    2.00    --  103.25 -94.00 -30.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0247797000
_diffrn_orient_matrix_UB_12      -0.0646384000
_diffrn_orient_matrix_UB_13      0.0472127000
_diffrn_orient_matrix_UB_21      -0.0426026000
_diffrn_orient_matrix_UB_22      -0.0692274000
_diffrn_orient_matrix_UB_23      -0.0387692000
_diffrn_orient_matrix_UB_31      0.0644536000
_diffrn_orient_matrix_UB_32      -0.0208053000
_diffrn_orient_matrix_UB_33      -0.0177735000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            128124
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.437
_diffrn_reflns_theta_min         2.328
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.554
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
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    1.030
_exptl_crystal_description       plate
_exptl_crystal_F_000             2548
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.539
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 11569 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.23(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1665
_refine_ls_number_reflns         30735
_refine_ls_number_restraints     488
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0636
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1327P)^2^+1.3196P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1867
_refine_ls_wR_factor_ref         0.1945
_reflns_Friedel_coverage         0.889
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.940
_reflns_number_gt                27346
_reflns_number_total             30735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc04728k2.cif
_cod_data_source_block           tx2347c_sq
_cod_original_cell_volume        7722.22(10)
_cod_database_code               1565346
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_usercomment     'C  H  O  N  Zn'
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C98-C100 = C97-C103 = C110-C105 = C113-C106 = C150-C145 = C147-C146 = C44-C40
 = C47-C41 = C50-C49 = C54-C53 = C7-C4 = C3-C10 = C17-C16 = C20-C15
 1.51 with sigma of 0.01
 C101-C100 = C102-C101 = C103-C102 = C111-C110 = C112-C111 = C113-C112 = C150-
 C149 = C149-C148 = C148-C147 = C138-C137 = C139-C138 = C140-C139 = C51-C50 =
 C52-C51 = C53-C52 = C45-C44 = C46-C45 = C47-C46 = C8-C7 = C9-C8 = C9-C10 = C18-
 C17 = C19-C18 = C20-C19
 1.53 with sigma of 0.01
 C44A-C40 = C44-C40 = C47A-C41 = C47-C41
 1.51 with sigma of 0.01
 C45-C44 = C45A-C44A = C46-C45 = C46A-C45A = C47A-C46A = C47-C46 = C47A-C41 =
 C47-C41
 1.53 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C100 \\sim C101 \\sim C102 \\sim C103 \\sim C110 \\sim C111 \\sim C112 \\sim
C113 \\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C137 \\sim C138 \\sim
C139 \\sim C140 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C50 \\sim C51
\\sim C52 \\sim C53 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C17 \\sim C18
\\sim C19 \\sim C20: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C44 \\sim C45 \\sim C46 \\sim C46A \\sim C45A \\sim C44A \\sim C47 \\sim C47A:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C100) \\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq,
Uanis(C103) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq,
Uanis(C112) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C150) \\sim Ueq,
Uanis(C149) \\sim Ueq, Uanis(C148) \\sim Ueq, Uanis(C147) \\sim Ueq,
Uanis(C137) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C139) \\sim Ueq,
Uanis(C140) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\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(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C46A)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C45A) \\sim Ueq,
Uanis(C44A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C45A)=
 Sof(H45C)=Sof(H45D)=Sof(C44A)=Sof(H44C)=Sof(H44D)=1-FVAR(1)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(C47)=Sof(H47A)=Sof(H47B)=FVAR(1)
 Fixed Y: O24(0.17424)
5.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C29(H29A,H29B), C44(H44A,H44B),
  C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C50(H50A,H50B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C66(H66A,H66B), C85(H85A,H85B),
 C100(H10C,H10D), C101(H10E,H10F), C102(H10G,H10H), C103(H10I,H10J), C110(H11A,
 H11B), C111(H11C,H11D), C112(H11E,H11F), C113(H11G,H11H), C122(H12D,H12E),
 C137(H13D,H13E), C138(H13F,H13G), C139(H13H,H13I), C140(H14B,H14C), C147(H14D,
 H14E), C150(H15A,H15B), C47A(H47C,H47D), C46A(H46C,H46D), C45A(H45C,H45D),
 C44A(H44C,H44D)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C14(H14), C23(H23), C26(H26), C31(H31), C34(H34), C39(H39), C55(H55),
 C59(H59), C62(H62), C68(H68), C71(H71), C78(H78), C81(H81), C87(H87), C90(H90),
  C99(H99), C107(H107), C115(H115), C118(H118), C124(H124), C127(H127),
 C132(H132), C144(H144), C148(H148), C149(H149)
5.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C73(H73A,H73B,H73C), C74(H74A,
 H74B,H74C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C92(H92A,H92B,H92C),
 C93(H93A,H93B,H93C), C120(H12A,H12B,H12C), C129(H12F,H12G,H12H), C130(H13A,
 H13B,H13C), C155(H15C,H15D,H15E), C76(H76A,H76B,H76C), C154(H15F,H15G,H15H)
5.d Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O7(H7), O8(H8), O13(H13), O14(H14A), O19(H19), O20(H20)
;
_shelx_res_checksum              38770
_shelx_hkl_checksum              61809
_shelx_fab_checksum              9918
_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 1.611
_oxdiff_exptl_absorpt_empirical_full_min 0.507