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_1569503
_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_absolute_configuration ad
_chemical_formula_moiety
'C6 H4 S4, C42 H30 F4 N8 O6 S2, 0.75(C2 H4 Cl2)'
_chemical_formula_sum            'C49.5 H37 Cl1.5 F4 N8 O6 S6'
_chemical_formula_weight         1161.40
_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             2023-04-21
_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                 94.936(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6988(4)
_cell_length_b                   17.9646(7)
_cell_length_c                   27.0532(16)
_cell_measurement_reflns_used    37838
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.7300
_cell_measurement_theta_min      3.0820
_cell_volume                     5180.3(4)
_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_temperature      172.99(10)
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1474
_diffrn_reflns_av_unetI/netI     0.0648
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            97629
_diffrn_reflns_point_group_measured_fraction_full 0.943
_diffrn_reflns_point_group_measured_fraction_max 0.896
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.906
_diffrn_reflns_theta_min         2.460
_exptl_absorpt_coefficient_mu    3.772
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55743
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.78a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       plate
_exptl_crystal_F_000             2382
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.005
_refine_diff_density_max         0.964
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.139
_refine_ls_abs_structure_details
;
 Flack x determined using 5338 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.105(13)
_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     1346
_refine_ls_number_reflns         19867
_refine_ls_number_restraints     429
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.1504
_refine_ls_R_factor_gt           0.1297
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0500P)^2^+50.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2950
_refine_ls_wR_factor_ref         0.3081
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    0.891
_reflns_Friedel_fraction_max     0.828
_reflns_number_gt                15956
_reflns_number_total             19867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02417b2.cif
_cod_data_source_block           23a-ttf-dce-hex_auto_auto_tw
_cod_depositor_comments
'Adding full bibliography for 1569486--1569506.cif.'
_cod_original_formula_sum        'C49.50 H37 Cl1.50 F4 N8 O6 S6'
_cod_database_code               1569503
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.397
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.803(3)
 0.197(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 C3F-C9
 1.45 with sigma of 0.02
 C8-Cl6
 1.65 with sigma of 0.02
 C3-C8
 1.55 with sigma of 0.02
 C15-C21
 1.5 with sigma of 0.02
 C21-Cl2
 1.7 with sigma of 0.02
 C15-Cl19
 1.7 with sigma of 0.02
4. Rigid bond restraints
 C1, C46, C3C, C2Z, C2T, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17, C14, C41, C40, C70, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C34, C2R, C12, C2H, C27, C1K, C45, O23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3F, C3B, C1B, C3K, C44, C3L
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3, C9, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl2, Cl19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C38, S1, N1, N11, N9, C6, N6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3, Cl1, C8, Cl6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C39, C37, C2J, C2X, C22, C16, F7, F12, F, F6, O1, O3
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C2L, C42, S4, C28, S5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1V, C36, C1Y, C1A, C31, C1G, F1, O10, F4, F9, F8, O23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O10, C2U, C14, C17, C57, C70, C40, C41, C1Q
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C15, Cl19, C21, Cl2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3M, C30, C1I, C2N, C2C, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C3C, C2Z, C2T, C19, C1, C46
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C70 \\sim C57 \\sim C17 \\sim C14 \\sim C41 \\sim C40: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C9 \\sim O3 \\sim C16: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C39 \\sim C37 \\sim C2J \\sim C2X \\sim C22 \\sim C16 \\sim F7 \\sim F12 \\sim
F \\sim F6 \\sim O1 \\sim O3: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C1V \\sim C36 \\sim C1Y \\sim C1A \\sim C31 \\sim C1G \\sim F1 \\sim O10 \\sim
F4 \\sim F9 \\sim F8 \\sim O23: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C3C \\sim C2Z \\sim C2T \\sim C19 \\sim C1 \\sim C46: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C45) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2U) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3M) \\sim Ueq, Uanis(C3D) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1Q) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
6. Others
 Fixed Sof: Cl6(0.5) C8(0.5) H8A(0.5) H8B(0.5) Cl1(0.5) C3(0.5) H3A(0.5)
 H3B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C13(H13A,H13B), C18(H18A,H18B), C1Q(H1QA,H1QB), C1R(H1RA,H1RB),
 C29(H29A,H29B), C2A(H2AA,H2AB), C2K(H2KA,H2KB), C2M(H2MA,H2MB), C2U(H2UA,H2UB),
  C33(H33A,H33B), C3D(H3DA,H3DB), C3E(H3EA,H3EB), C3H(H3HA,H3HB), C45(H45A,
 H45B), C9(H9A,H9B), C8(H8A,H8B), C3(H3A,H3B), C21(H21A,H21B), C15(H15A,H15B)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C40(H40), C17(H17), C43(H43), C1F(H1F), C1K(H1K), C1N(H1N), C1W(H1W),
 C1X(H1X), C25(H25), C27(H27), C2C(H2C), C2E(H2E), C2F(H2F), C2H(H2H), C2L(H2L),
  C2N(H2N), C2O(H2O), C2P(H2P), C2Q(H2Q), C2W(H2W), C2Y(H2Y), C30(H30),
 C34(H34), C1B(H1B), C3K(H3K), C44(H44), C3L(H3L), C3M(H3M), C42(H42), C70(H70),
  C57(H57), C1(H1), C2Z(H2Z), C3C(H3C), C46(H46)
7.c Fitted hexagon refined as free rotating group:
 C3B(C1B,C3K,C44,C3L,C3F), C1(C19,C2T,C2Z,C3C,C46)
;
_shelx_res_checksum              30940
_olex2_submission_special_instructions 'No special instructions were received'