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_1562682
_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), 2(N O3), (C3.33 H5.33 O0.5)'
_chemical_formula_sum            'C215.33 H189.33 N10 O30.5 Pt2'
_chemical_formula_weight         3975.29
_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             2021-03-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-03-14 deposited with the CCDC.	2021-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                93.016(2)
_cell_angle_beta                 101.669(2)
_cell_angle_gamma                106.888(2)
_cell_formula_units_Z            2
_cell_length_a                   18.6373(5)
_cell_length_b                   22.0540(5)
_cell_length_c                   27.1149(5)
_cell_measurement_reflns_used    19850
_cell_measurement_temperature    90.0
_cell_measurement_theta_max      71.1260
_cell_measurement_theta_min      2.5350
_cell_volume                     10369.9(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.42a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      90.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.900
_diffrn_measured_fraction_theta_max 0.867
_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      0.00  41.00   0.50   60.00    --    0.00  91.00 119.00   82
  2  \w    -13.00  19.00   0.50   60.00    --  -55.36  91.00 119.00   64
  3  \w    -31.00  -3.00   0.50   60.00    --    0.00  91.00 119.00   56
  4  \w    -22.00  27.00   0.50   60.00    --  -55.36  15.00  90.00   98
  5  \w    -50.00 -24.00   0.50   70.00    -- -102.00  91.00 119.00   52
  6  \w   -102.00 -58.00   0.50   70.00    -- -102.00  91.00 119.00   88
  7  \w    -99.00 -34.00   0.50   60.00    --  -55.36  91.00 119.00  130
  8  \w    -55.00 -19.00   0.50   70.00    -- -102.00  50.00 -30.00   72
  9  \w   -111.00 -14.00   0.50   60.00    --  -55.36 125.00 -90.00  194
 10  \w    -41.00  26.00   0.50   60.00    --   55.36 -15.00  60.00  134
 11  \w     19.00  45.00   0.50   70.00    --  110.71 -91.00   6.00   52
 12  \w     49.00 106.00   0.50   70.00    --  110.71 -91.00   6.00  114
 13  \w     17.00 108.00   0.50   70.00    --  110.71 -77.00  90.00  182
 14  \w     13.00 173.00   0.50   70.00    --  110.71   0.00 -60.00  320
 15  \w     85.00 110.00   0.50   60.00    --   55.36  91.00 119.00   50
 16  \w    152.00 178.00   0.50   70.00    --  110.71  91.00 119.00   52
 17  \w     84.00 149.00   0.50   70.00    --  110.71  91.00 119.00  130
 18  \w     15.00 106.00   0.50   70.00    --  110.71 -91.00-150.00  182
 19  \w     20.00 107.00   0.50   70.00    --  110.71-111.00 -60.00  174
 20  \w    -36.00  68.00   0.50   60.00    --   55.36 -91.00   6.00  208
 21  \w    -35.00  36.00   0.50   60.00    --    0.00 -91.00   6.00  142
 22  \w   -106.00 -81.00   0.50   60.00    --  -55.36 -91.00   6.00   50
 23  \w   -150.00-115.00   0.50   60.00    --  -55.36 -91.00   6.00   70
 24  \w   -142.00 -74.00   0.50   60.00    --  -55.36-125.00 120.00  136
 25  \w   -174.00 -80.00   0.50   70.00    -- -102.00 -91.00   6.00  188
 26  \w   -175.00 -55.00   0.50   70.00    -- -102.00 -77.00  60.00  240
;
_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      0.0818848000
_diffrn_orient_matrix_UB_12      0.0441279000
_diffrn_orient_matrix_UB_13      0.0243132000
_diffrn_orient_matrix_UB_21      -0.0004764000
_diffrn_orient_matrix_UB_22      -0.0346686000
_diffrn_orient_matrix_UB_23      0.0478525000
_diffrn_orient_matrix_UB_31      0.0341331000
_diffrn_orient_matrix_UB_32      -0.0475027000
_diffrn_orient_matrix_UB_33      -0.0230865000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0743
_diffrn_reflns_av_unetI/netI     0.0908
_diffrn_reflns_Laue_measured_fraction_full 0.900
_diffrn_reflns_Laue_measured_fraction_max 0.867
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            62197
_diffrn_reflns_point_group_measured_fraction_full 0.900
_diffrn_reflns_point_group_measured_fraction_max 0.867
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.300
_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    3.033
_exptl_absorpt_correction_T_max  0.886
_exptl_absorpt_correction_T_min  0.809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.42a (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    1.215
_exptl_crystal_description       block
_exptl_crystal_F_000             3903
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.065
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.985
_refine_diff_density_min         -1.501
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.915
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2400
_refine_ls_number_reflns         40243
_refine_ls_number_restraints     3418
_refine_ls_restrained_S_all      0.917
_refine_ls_R_factor_all          0.1037
_refine_ls_R_factor_gt           0.0779
_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          0.2310
_refine_ls_wR_factor_ref         0.2538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23575
_reflns_number_total             40243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01987b2.cif
_cod_data_source_block           RS214camphor
_cod_database_code               1562682
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C200N1632Pt2
_chemical_oxdiff_usercomment     camphor
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.816
_reflns_odcompleteness_completeness 90.32
_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
 C2G-C3G
 1.5 with sigma of 0.001
 O06J-C106
 1.5 with sigma of 0.001
 C3G-C7G
 2.452 with sigma of 0.001
 C9G-C7G
 2.452 with sigma of 0.001
 C6G-C8G
 2.413 with sigma of 0.001
 C112-O116
 2.2 with sigma of 0.001
 C106-C111
 3.5 with sigma of 0.001
 C2G-C3G \\sim C3G-C4G \\sim C3G-C1G \\sim C2G-C8G \\sim C8G-C9G \\sim C9G-C10G
\\sim C1G-C3G \\sim C3G-
 C6G \\sim C6G-C9G \\sim C5G-C6G \\sim C6G-C7G
 with sigma of 0.01
 N1C-O1C \\sim N1C-O2C \\sim N1C-O3C
 with sigma of 0.01
 O1C-O2C \\sim O2C-O3C \\sim O3C-O1C
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.003 and
sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: O1G(0.5) C2G(0.33333) C3G(0.33333) C9G(0.33333) H9G(0.33333)
 C6G(0.33333) C1G(0.33333) H1GA(0.33333) H1GB(0.33333) H1GC(0.33333)
 C4G(0.33333) H4GA(0.33333) H4GB(0.33333) C5G(0.33333) H5GA(0.33333)
 H5GB(0.33333) H5GC(0.33333) C10G(0.33333) H10M(0.33333) H10N(0.33333)
 C7G(0.33333) H7GA(0.33333) H7GB(0.33333) H7GC(0.33333) C8G(0.33333)
 H8GA(0.33333) H8GB(0.33333)
5.a Ternary CH refined with riding coordinates:
 C9G(H9G)
5.b Secondary CH2 refined with riding coordinates:
 C99(H99A,H99B), C030(H03A,H03B), C048(H04A,H04B), C04A(H04C,H04D), C04Q(H04P,
 H04Q), C05L(H05L,H05M), C05S(H05T,H05U), C05T(H05V,H05W), C05V(H05X,H05Y),
 C05Z(H0AA,H), C061(H06A,H06B), C062(H06C,H06D), C064(H06H,H06I), C069(H06J,
 H06K), C06C(H06P,H06Q), C06G(H06T,H06U), C06I(H06W,H06X), C06Q(H06,HC),
 C06R(H1AA,HD), C06X(H4AA,HI), C06Z(H5AA,HJ), C078(H07D,H07E), C4G(H4GA,H4GB),
 C10G(H10M,H10N), C8G(H8GA,H8GB), C110(H11D,H11E), C112(H11F,H11G)
5.c Me refined with riding coordinates:
 C5G(H5GA,H5GB,H5GC)
5.d Aromatic/amide H refined with riding coordinates:
 C97(H97), C86(H86), C82(H82), C81(H81), C80(H80), C98(H98), C01K(H01K),
 C01M(H01M), C01O(H01O), C01P(H01P), C01X(H01X), C01Y(H01Y), C01Z(H01Z),
 C021(H021), C027(H027), C02I(H02I), C02J(H02J), C02L(H02L), C02N(H02N),
 C02P(H02P), C02S(H02S), C02W(H02W), C02Z(H02Z), C031(H031), C032(H032),
 C033(H033), C035(H035), C036(H036), C038(H038), C039(H039), C03A(H03C),
 C03B(H03D), C03C(H03E), C03D(H03F), C03H(H03H), C03K(H03K), C03M(H03M),
 C03N(H03N), C03P(H03P), C03Q(H03Q), C03R(H03R), C03U(H03U), C03W(H03W),
 C03X(H03X), C03Y(H03Y), C03Z(H03Z), C040(H040), C042(H042), C043(H043),
 C044(H044), C045(H045), C046(H046), C04C(H04E), C04D(H04F), C04E(H04G),
 C04F(H04H), C04H(H04I), C04J(H04J), C04K(H04K), C04L(H04L), C04M(H04M),
 C04N(H04N), C04O(H04O), C04R(H04R), C04S(H04S), C04T(H04T), C04U(H04U),
 C04V(H04V), C04X(H04X), C04Y(H04Y), C04Z(H04Z), C050(H050), C053(H053),
 C054(H054), C055(H055), C056(H056), C058(H058), C059(H059), C05B(H05D),
 C05C(H05E), C05D(H05F), C05F(H05G), C05H(H05H), C05I(H05I), C05J(H05J),
 C05K(H05K), C05M(H05N), C05N(H05O), C05O(H05P), C05P(H05Q), C05Q(H05R),
 C05R(H05S), C05W(H05Z), C05Y(H05), C067(H067), C06B(H06O), C06D(H06R),
 C06E(H06S), C06H(H06V), C06K(H06Y)
5.e Idealised Me refined as rotating group:
 C05A(H05A,H05B,H05C), C063(H06E,H06F,H06G), C06A(H06L,H06M,H06N), C06L(H06Z,
 HA,HB), C06U(H2AA,HE,HF), C06W(H3AA,HG,HH), C100(H10A,H10B,H10C), C075(H07A,
 H07B,H07C), C102(H10D,H10E,H10F), C1G(H1GA,H1GB,H1GC), C7G(H7GA,H7GB,H7GC),
 C103(H10G,H10H,H10I), C106(H10J,H10K,H10L), C111(H11A,H11B,H11C)
;
_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 1.969
_oxdiff_exptl_absorpt_empirical_full_min 0.474