Cyclic Monoterpenes Trapped in a Polyaromatic Capsule: Unusual Selectivity, Isomerization, and Volatility Suppression
Sumida, Ryuki; Tanaka, Yuya; Niki, Keita; Sei, Yoshihisa; Toyota, Shinji; Yoshizawa, Michito; Chemical Science  (2021) –; doi:10.1039/D1SC01987B

data_1562681
_publ_section_title
;
 Cyclic Monoterpenes Trapped in a Polyaromatic Capsule: Unusual
 Selectivity, Isomerization, and Volatility Suppression
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01987B
_journal_year                    2021
_chemical_formula_moiety         'C212 H184 N8 O24 Pt2, N O3, 1(C10 H18 O)'
_chemical_formula_sum            'C222 H202 N9 O28 Pt2'
_chemical_formula_weight         3834.10
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-01-25
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-01-26 deposited with the CCDC.	2021-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                93.167(3)
_cell_angle_beta                 101.052(3)
_cell_angle_gamma                107.422(3)
_cell_formula_units_Z            2
_cell_length_a                   18.7348(5)
_cell_length_b                   21.8196(9)
_cell_length_c                   27.4073(11)
_cell_measurement_reflns_used    12991
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      63.7620
_cell_measurement_theta_min      2.5060
_cell_volume                     10415.3(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.944
_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    -19.00  28.00   0.50   20.00    --  -41.93  37.00 -30.00   94
  2  \w    -39.00  29.00   0.50   20.00    --  -41.93  67.00  30.00  136
  3  \w     17.00 112.00   0.50   20.00    --   41.93  67.00  30.00  190
  4  \w     83.00 178.00   0.50   20.00    --  106.13  67.00  30.00  190
  5  \w     67.00 104.00   0.50   20.00    --  106.13 -94.00-150.00   74
  6  \w     43.00  81.00   0.50   20.00    --  106.13 -67.00-103.00   76
  7  \w     56.00 112.00   0.50   20.00    --  106.13-125.00   0.00  112
  8  \w     77.00 112.00   0.50   20.00    --  106.13-125.00  30.00   70
  9  \w     78.00 108.00   0.50   20.00    --  106.13-125.00 150.00   60
 10  \w     33.00  69.00   0.50   20.00    --  106.13 -61.00  60.00   72
 11  \w     32.00  73.00   0.50   20.00    --  106.13 -61.00  90.00   82
 12  \w     34.00  75.00   0.50   20.00    --  106.13-125.00 150.00   82
 13  \w     33.00  77.00   0.50   20.00    --  106.13-125.00  60.00   88
 14  \w     28.00  65.00   0.50   20.00    --   41.93 -67.00-103.00   74
 15  \w     19.00  95.00   0.50   20.00    --   41.93-125.00 -90.00  152
 16  \w     33.00  59.00   0.50   20.00    --  106.13 -94.00-150.00   52
 17  \w    -23.00  15.00   0.50   20.00    --   41.93 -67.00-103.00   76
 18  \w    -23.00  34.00   0.50   20.00    --  -41.93  19.00-180.00  114
 19  \w    -69.00 -30.00   0.50   20.00    -- -102.00  61.00-120.00   78
 20  \w    -79.00 -30.00   0.50   20.00    -- -102.00  67.00  30.00   98
 21  \w    -67.00 -31.00   0.50   20.00    -- -102.00  61.00  60.00   72
 22  \w    -62.00 -32.00   0.50   20.00    -- -102.00  61.00 150.00   60
 23  \w    -89.00 -30.00   0.50   20.00    -- -102.00 114.00 139.82  118
 24  \w    -95.00 -29.00   0.50   20.00    -- -102.00 125.00  30.00  132
 25  \w   -102.00 -28.00   0.50   20.00    -- -102.00 125.00 150.00  148
 26  \w   -108.00 -69.00   0.50   20.00    -- -102.00 110.00  71.17   78
 27  \w   -120.00 -94.00   0.50   20.00    -- -102.00 137.00 168.37   52
 28  \w   -107.00 -82.00   0.50   20.00    -- -102.00 103.00 178.42   50
 29  \w   -175.00 -61.00   0.50   20.00    -- -102.00 -15.00 120.00  228
 30  \w   -134.00 -94.00   0.50   20.00    -- -102.00 -94.00  30.00   80
 31  \w   -107.00 -27.00   0.50   20.00    --  -41.93 -67.00-103.00  160
 32  \w    -19.00  38.00   0.50   20.00    --   41.93 -37.00  90.00  114
 33  \w   -101.00 -32.00   0.50   20.00    -- -102.00  77.00 -60.00  138
 34  \w   -108.00 -78.00   0.50   20.00    -- -102.00 -30.00-180.00   60
 35  \w   -133.00 -95.00   0.50   20.00    -- -102.00 -30.00-120.00   76
 36  \w   -136.00-110.00   0.50   20.00    -- -102.00 -30.00-180.00   52
 37  \w   -142.00-117.00   0.50   20.00    -- -102.00 -67.00-103.00   50
 38  \w   -166.00 -80.00   0.50   20.00    -- -102.00 -45.00 -60.00  172
 39  \w   -175.00-149.00   0.50   20.00    -- -102.00 -94.00  30.00   52
 40  \w   -166.00 -86.00   0.50   20.00    -- -102.00 -30.00 -30.00  160
 41  \w   -168.00 -93.00   0.50   20.00    -- -102.00-125.00-180.00  150
 42  \w   -174.00-149.00   0.50   20.00    -- -102.00 -30.00-120.00   50
 43  \w   -121.00 -84.00   0.50   20.00    -- -102.00 138.00 -54.08   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0111287000
_diffrn_orient_matrix_UB_12      -0.0520674000
_diffrn_orient_matrix_UB_13      0.0360802000
_diffrn_orient_matrix_UB_21      -0.0853597000
_diffrn_orient_matrix_UB_22      -0.0281012000
_diffrn_orient_matrix_UB_23      -0.0262155000
_diffrn_orient_matrix_UB_31      0.0197501000
_diffrn_orient_matrix_UB_32      -0.0453395000
_diffrn_orient_matrix_UB_33      -0.0365941000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1525
_diffrn_reflns_av_unetI/netI     0.1376
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            139099
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.285
_diffrn_reflns_theta_min         2.533
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.014
_exptl_absorpt_correction_T_max  0.486
_exptl_absorpt_correction_T_min  0.255
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       block
_exptl_crystal_F_000             3954
_exptl_crystal_size_max          0.76
_exptl_crystal_size_mid          0.44
_exptl_crystal_size_min          0.24
_refine_diff_density_max         2.020
_refine_diff_density_min         -2.507
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.967
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2450
_refine_ls_number_reflns         43094
_refine_ls_number_restraints     3484
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.1741
_refine_ls_R_factor_gt           0.0917
_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^)+(0.1619P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2324
_refine_ls_wR_factor_ref         0.2877
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19098
_reflns_number_total             43094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01987b2.cif
_cod_data_source_block           RS214menthone
_cod_database_code               1562681
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.532
_shelx_estimated_absorpt_t_min   0.208
_diffrn_oxdiff_digest_frames
;
0170456761e4592c62b32ec24227269b340002580e4
;
_diffrn_oxdiff_digest_hkl
;
0105e99a65b9cd7e730b3d6650d822ba4dde41
;
_reflns_odcompleteness_completeness 99.74
_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 C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C1G-C2G
 1.5 with sigma of 0.001
 C6G-C7G
 1.5 with sigma of 0.001
 O107-C27
 1.5 with sigma of 0.02
 C24-C27
 2.5 with sigma of 0.04
 C27-C105
 3.05 with sigma of 0.04
 O1G-C1G \\sim O1H-C1H
 with sigma of 0.02
 O1G-C6G \\sim O1H-C6H
 with sigma of 0.04
 O1G-C2G \\sim O1H-C2H
 with sigma of 0.04
 C1G-C2G \\sim C2G-C3G \\sim C3G-C4G \\sim C4G-C5G \\sim C5G-C6G \\sim C6G-C1G
 with sigma of 0.01
 C5G-C4G \\sim C5H-C4H
 with sigma of 0.02
 C6G-C7G \\sim C7G-C8G \\sim C7G-C9G
 with sigma of 0.01
 C5G-C6G \\sim C5H-C6H
 with sigma of 0.02
 C1G-C6G \\sim C1H-C6H
 with sigma of 0.02
 C1G-C2G \\sim C1H-C2H
 with sigma of 0.02
 C4G-C3G \\sim C4H-C3H
 with sigma of 0.02
 C6G-C7G \\sim C6H-C7H
 with sigma of 0.02
 C2G-C3G \\sim C2H-C3H
 with sigma of 0.02
 C9G-C7G \\sim C9H-C7H
 with sigma of 0.02
 C7G-C8G \\sim C7H-C8H
 with sigma of 0.02
 C5G-C1G \\sim C5H-C1H
 with sigma of 0.04
 C5G-C3G \\sim C5H-C3H
 with sigma of 0.04
 C5G-C7G \\sim C5H-C7H
 with sigma of 0.04
 C1G-C3G \\sim C1H-C3H
 with sigma of 0.04
 C1G-C7G \\sim C1H-C7H
 with sigma of 0.04
 C4G-C6G \\sim C4H-C6H
 with sigma of 0.04
 C4G-C2G \\sim C4H-C2H
 with sigma of 0.04
 C6G-C2G \\sim C6H-C2H
 with sigma of 0.04
 C6G-C9G \\sim C6H-C9H
 with sigma of 0.04
 C6G-C8G \\sim C6H-C8H
 with sigma of 0.04
 C9G-C8G \\sim C9H-C8H
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C27: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.002
Uanis(C27) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(O1H)=Sof(C1H)=Sof(C2H)=Sof(H2HA)=Sof(H2HB)=Sof(C3H)=Sof(H3H)=Sof(C4H)=
 Sof(H4HA)=Sof(H4HB)=Sof(C5H)=Sof(H5HA)=Sof(H5HB)=Sof(C6H)=Sof(H6H)=Sof(C7H)=
 Sof(H7H)=Sof(C8H)=Sof(H8HA)=Sof(H8HB)=Sof(H8HC)=Sof(C9H)=Sof(H9HA)=Sof(H9HB)=
 Sof(H9HC)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=1-FVAR(1)
 Sof(O1G)=Sof(C5G)=Sof(H5GA)=Sof(H5GB)=Sof(C1G)=Sof(C4G)=Sof(H4GA)=Sof(H4GB)=
 Sof(C6G)=Sof(H6G)=Sof(C2G)=Sof(H2GA)=Sof(H2GB)=Sof(C3G)=Sof(H3G)=Sof(C9G)=
 Sof(H9GA)=Sof(H9GB)=Sof(H9GC)=Sof(C7G)=Sof(H7G)=Sof(C8G)=Sof(H8GA)=Sof(H8GB)=
 Sof(H8GC)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C6G(H6G), C3G(H3G), C7G(H7G), C3H(H3H), C6H(H6H), C7H(H7H)
5.b Secondary CH2 refined with riding coordinates:
 C01X(H01A,H01B), C03B(H03A,H03B), C03F(H03E,H03F), C03N(H03J,H03K), C04Z(H04B,
 H04F), C051(H05A,H05B), C057(H05C,H05D), C05G(H05I,H05J), C05T(H05R,H05S),
 C05V(H05T,H05V), C05X(H05X,H05Y), C061(H06A,H06B), C062(H06C,H06D), C066(H06E,
 H06F), C06A(H06G,H06H), C06E(H06P,H06Q), C06G(H06R,H06S), C06H(H06T,H06U),
 C06I(H06V,H06W), C06V(H1AA,HB), C079(H07G,H07H), C24(H24A,H24B), C105(H10A,
 H10B), C5G(H5GA,H5GB), C4G(H4GA,H4GB), C2G(H2GA,H2GB), C102(H10C,H10D),
 C2H(H2HA,H2HB), C4H(H4HA,H4HB), C5H(H5HA,H5HB)
5.c Me refined with riding coordinates:
 C05I(H05L,H05M,H05N), C06C(H06J,H06K,H06L), C06D(H06M,H06N,H06O), C06T(H0AA,H,
 HA), C071(H07A,H07B,H07C), C072(H07D,H07E,H07F), C07G(H07I,H07J,H07K),
 C108(H10E,H10F,H10G), C104(H10H,H10I,H10J), C103(H10K,H10L,H10M), C9G(H9GA,
 H9GB,H9GC), C8G(H8GA,H8GB,H8GC), C109(H10N,H10O,H10P), C8H(H8HA,H8HB,H8HC),
 C9H(H9HA,H9HB,H9HC), C21(H21A,H21B,H21C), C45(H45A,H45B,H45C), C27(H27A,H27B,
 H27C)
5.d Aromatic/amide H refined with riding coordinates:
 C80(H80), C97(H97), C86(H86), C100(H100), C82(H82), C85(H85), C81(H81),
 C88(H88), C93(H93), C95(H95), C96(H96), C01P(H01P), C01W(H01W), C020(H020),
 C022(H022), C024(H024), C029(H029), C02E(H02E), C02H(H02H), C02K(H02K),
 C02P(H02P), C02Q(H02Q), C02T(H02T), C02Z(H02Z), C030(H030), C031(H031),
 C033(H033), C035(H035), C036(H036), C037(H037), C038(H038), C039(H039),
 C03C(H03C), C03D(H03D), C03G(H03G), C03H(H03H), C03I(H03I), C03L(H03L),
 C03M(H03M), C03P(H03P), C03Q(H03Q), C03R(H03R), C03S(H03S), C03T(H03T),
 C03U(H03U), C03V(H03V), C03X(H03X), C03Z(H03Z), C041(H041), C042(H042),
 C044(H044), C046(H046), C048(H048), C049(H049), C04A(H04A), C04C(H04C),
 C04D(H04D), C04E(H04E), C04G(H04G), C04H(H04H), C04J(H04J), C04L(H04L),
 C04M(H04M), C04O(H04O), C04Q(H04Q), C04R(H04R), C04S(H04S), C04T(H04T),
 C04V(H04V), C04W(H04W), C04X(H04X), C04Y(H04Y), C052(H052), C053(H053),
 C054(H054), C055(H055), C056(H056), C058(H058), C059(H059), C05A(H05E),
 C05C(H05F), C05D(H05G), C05E(H05H), C05H(H05K), C05J(H05O), C05K(H05P),
 C05O(H05Q), C05U(H05U), C05W(H05W), C05Y(H05Z), C05Z(H05), C060(H060),
 C067(H067), C06B(H06I), C06L(H06X), C06M(H06Y), C06O(H06Z), C06P(H06),
 C06X(H2AA), C06Y(H3AA)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.709
_oxdiff_exptl_absorpt_empirical_full_min 0.608