Tetrahomo corona[4]arene-based spirophanes: synthesis, structure, and properties.
Guo, Shen-Yi; Zhang, Zhuo-Ang; Tong, Shuo; Guo, Qing-Hui; Hua, Ruimao; Wang, Mei-Xiang; Chemical science 14 (2023) 8393–8400; doi:10.1039/d3sc02417b

data_1569497
_publ_section_title
;
 Tetrahomo corona[4]arene-based spirophanes: synthesis, structure, and
 properties.
;
_journal_issue                   31
_journal_name_full               'Chemical science'
_journal_page_first              8393
_journal_page_last               8400
_journal_paper_doi               10.1039/d3sc02417b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C64 H44 F8 N8 O10 S2, 2.5(C2 H3 N), C H4 O'
_chemical_formula_sum            'C70 H55.5 F8 N10.5 O11 S2'
_chemical_formula_weight         1435.87
_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             2022-11-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-08 deposited with the CCDC.	2023-07-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.7038(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.22933(19)
_cell_length_b                   23.1073(6)
_cell_length_c                   13.31714(19)
_cell_measurement_reflns_used    19068
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      74.5340
_cell_measurement_theta_min      3.2740
_cell_volume                     3455.26(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.962
_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     35.00 106.00   0.50    0.06    --  106.93 -99.00-150.00  142
  2  \w     30.00 106.00   0.50    0.05    --   47.89-145.00   8.00  152
  3  \w     36.00 126.00   0.50    0.06    --  106.93-145.00   8.00  180
  4  \w     19.00  95.00   0.50    0.05    --   47.89-126.00 176.00  152
  5  \w     35.00  72.00   0.50    0.06    --  106.93-126.00 176.00   74
  6  \w     36.00  96.00   0.50    0.06    --  106.93 -99.00-180.00  120
  7  \w     39.00  91.00   0.50    0.06    --  106.93 -77.00-150.00  104
  8  \w     38.00  65.00   0.50    0.06    --  106.93 -57.00-150.00   54
  9  \w    -25.00  28.00   0.50    0.05    --   47.89 -19.00 -90.00  106
 10  \w     42.00  67.00   0.50    0.06    --  106.93 -57.00  30.00   50
 11  \w     96.00 122.00   0.50    0.06    --  106.93  38.00  60.00   52
 12  \w    138.00 178.00   0.50    0.06    --  106.93  38.00  60.00   80
 13  \w   -106.00 -23.00   0.50    0.05    --  -47.89 145.00  60.00  166
 14  \w   -124.00 -85.00   0.50    0.06    -- -104.00 142.00 137.60   78
 15  \w   -121.00 -35.00   0.50    0.06    -- -104.00 145.00  60.00  172
 16  \w    -57.00 -32.00   0.50    0.06    -- -104.00  57.00 120.00   50
 17  \w    -22.00  26.00   0.50    0.05    --  -47.89  19.00  90.00   96
 18  \w    -64.00 -33.00   0.50    0.06    -- -104.00  57.00   0.00   62
 19  \w    -63.00 -33.00   0.50    0.06    -- -104.00  57.00 -60.00   60
 20  \w    -61.00 -33.00   0.50    0.06    -- -104.00  57.00 -90.00   56
 21  \w   -174.00 -96.00   0.50    0.06    -- -104.00 -19.00   0.00  156
 22  \w   -119.00 -80.00   0.50    0.05    --  -47.89-125.00-120.00   78
 23  \w   -120.00 -60.50   0.50    0.05    --  -47.89-145.00   8.00  119
 24  \w   -120.00 -74.00   0.50    0.05    --  -47.89-125.00  60.00   92
 25  \w   -174.00 -90.00   0.50    0.06    -- -104.00 -61.00  90.76  168
 26  \w   -120.00 -73.50   0.50    0.05    --  -47.89-126.00 176.00   93
 27  \w   -105.00 -74.00   0.50    0.06    -- -104.00-126.00 176.00   62
 28  \w   -169.00 -72.00   0.50    0.06    -- -104.00-145.00   8.00  194
;
_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      0.0639393000
_diffrn_orient_matrix_UB_12      0.0546692000
_diffrn_orient_matrix_UB_13      -0.0377469000
_diffrn_orient_matrix_UB_21      -0.1000994000
_diffrn_orient_matrix_UB_22      0.0379499000
_diffrn_orient_matrix_UB_23      0.0429968000
_diffrn_orient_matrix_UB_31      0.0686727000
_diffrn_orient_matrix_UB_32      0.0043817000
_diffrn_orient_matrix_UB_33      0.1005052000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            34533
_diffrn_reflns_point_group_measured_fraction_full 0.847
_diffrn_reflns_point_group_measured_fraction_max 0.793
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.493
_diffrn_reflns_theta_min         3.319
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.471
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43938
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       plate
_exptl_crystal_F_000             1482
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.371
_refine_diff_density_min         -0.620
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Flack x determined using 3670 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.504(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     861
_refine_ls_number_reflns         11655
_refine_ls_number_restraints     174
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.1012
_refine_ls_R_factor_gt           0.0962
_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^)+(0.1992P)^2^+2.4544P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2736
_refine_ls_wR_factor_ref         0.2803
_reflns_Friedel_coverage         0.607
_reflns_Friedel_fraction_full    0.688
_reflns_Friedel_fraction_max     0.615
_reflns_number_gt                10514
_reflns_number_total             11655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02417b2.cif
_cod_data_source_block           gsy1400b_auto
_cod_depositor_comments
'Adding full bibliography for 1569486--1569506.cif.'
_cod_original_cell_volume        3455.26(11)
_cod_original_formula_sum        'C70 H55.50 F8 N10.50 O11 S2'
_cod_database_code               1569497
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S'
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.472
_reflns_odcompleteness_completeness 99.92
_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, All O(H) groups
2. Rigid bond restraints
 C50, O48, C49, N51, N53, C47, N54, N52, S85, C86
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C40, O39, C36, N35, N34, C33, N38, N37, S32, C31
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C13, C12, O14
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C50) \\sim Ueq, Uanis(O48) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(N51)
\\sim Ueq, Uanis(N53) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(N54) \\sim Ueq,
Uanis(N52) \\sim Ueq, Uanis(S85) \\sim Ueq, Uanis(C86) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C40) \\sim Ueq, Uanis(O39) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(N35)
\\sim Ueq, Uanis(N34) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(N38) \\sim Ueq,
Uanis(N37) \\sim Ueq, Uanis(S32) \\sim Ueq, Uanis(C31) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C13) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: N3(0.5) C5(0.5) H5A(0.5) H5B(0.5) H5C(0.5) C28(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C40(H40A,H40B), C50(H50A,H50B), C60(H60A,H60B), C86(H86A,
 H86B), C20(H20A,H20B), C63(H63A,H63B), C57(H57A,H57B), C31(H31A,H31B),
 C70(H70A,H70B), C6(H6A,H6B), C13(H13A,H13B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C22(H22), C23(H23), C24(H24), C25(H25), C46(H46), C30(H30), C43(H43),
 C8(H8), C9(H9), C10(H10), C11(H11), C80(H80), C77(H77), C78(H78), C79(H79),
 C71(H71), C72(H72), C73(H73), C74(H74)
5.c Fitted hexagon refined as free rotating group:
 C21(C22,C23,C24,C25,C26), C68(C76,C75,C65,C66,C67), C12(C7,C8,C9,C10,C11),
 C87(C88,C18,C17,C16,C15), C80(C56,C55,C77,C78,C79), C61(C71,C72,C73,C74,C62)
5.d Idealised Me refined as rotating group:
 C95(H95A,H95B,H95C), C98(H98A,H98B,H98C), C5(H5A,H5B,H5C), C14(H14A,H14B,H14C)
5.e Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_shelx_res_checksum              4850
_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 2.091
_oxdiff_exptl_absorpt_empirical_full_min 0.550