Guest-adaptive hydrogen-bonded dimerization of a C3-symmetric tribenzotriquinacene molecular bowl
Yang, Tian-Shu; Duan, Xiao-Fang; Yin, Fan; Cai, Li-Xuan; Zhou, Li-Peng; Hu, Shao-Jun; Guo, Xiao-Qing; Sun, Qing-Fu; CrystEngComm 27 (2025) 2025–2032; doi:10.1039/D5CE00038F

data_7250047
_publ_section_title
;
 Guest-adaptive hydrogen-bonded dimerization of a C3-symmetric
 tribenzotriquinacene molecular bowl
;
_journal_issue                   13
_journal_name_full               CrystEngComm
_journal_page_first              2025
_journal_page_last               2032
_journal_paper_doi               10.1039/D5CE00038F
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety
'2(C59 H57 N15 O3), 3.5(C6 H12), 3(C1 H1 Cl3), 2.1[CHCl3], 2.1[CHCl3]'
_chemical_formula_sum            'C146.2 H163.2 Cl21.6 N30 O6'
_chemical_formula_weight         3202.38
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc2mbpvj
_audit_creation_date             2025-02-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-12 deposited with the CCDC.	2025-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.8874(11)
_cell_length_b                   22.8874(11)
_cell_length_c                   57.200(5)
_cell_measurement_reflns_used    6314
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      66.3210
_cell_measurement_theta_min      2.4190
_cell_volume                     25949(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.962
_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    -53.00 -27.00   0.50    3.50    --  -97.00  54.00-179.00   52
  2  \w    -53.00 -24.00   0.50    3.50    --  -97.00  45.00 -90.00   58
  3  \w    -69.00 -27.00   0.50    3.50    --  -97.00  61.00 -60.00   84
  4  \w    -54.00 -29.00   0.50    3.50    --  -97.00  45.00 -60.00   50
  5  \w    -54.00 -27.00   0.50    3.50    --  -97.00  45.00 120.00   54
  6  \w    -98.00 -39.00   0.50    3.50    --  -97.00 117.00 154.00  118
  7  \w     66.00 114.00   0.50    0.88    --   46.22 141.00  50.00   96
  8  \w    112.00 163.00   0.50    3.50    --  107.47  54.00-179.00  102
  9  \w    -24.00  21.00   0.50    0.88    --   46.22 -19.00 -30.00   90
 10  \w   -118.00 -93.00   0.50    0.88    --  -46.22-141.00  -7.00   50
 11  \w    -28.00  11.00   0.50    0.88    --   46.22 -19.00  60.00   78
 12  \w     40.00  68.00   0.50    3.50    --  107.47-113.00-114.00   56
 13  \w     76.00 108.00   0.50    3.50    --  107.47-113.00-114.00   64
 14  \w     61.00  92.00   0.50    3.50    --  107.47 -95.00 -90.00   62
 15  \w     50.00  79.00   0.50    3.50    --  107.47 -81.00  48.00   58
 16  \w    106.00 133.00   0.50    3.50    --  107.47 -81.00  48.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0159408000
_diffrn_orient_matrix_UB_12      0.0280516000
_diffrn_orient_matrix_UB_13      0.0251292000
_diffrn_orient_matrix_UB_21      -0.0479422667
_diffrn_orient_matrix_UB_22      -0.0711899333
_diffrn_orient_matrix_UB_23      0.0096397667
_diffrn_orient_matrix_UB_31      0.0589909333
_diffrn_orient_matrix_UB_32      -0.0140533333
_diffrn_orient_matrix_UB_33      0.0010913667
_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  0.0465
_diffrn_reflns_av_unetI/netI     0.0467
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       67
_diffrn_reflns_limit_l_min       -63
_diffrn_reflns_number            29664
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        66.564
_diffrn_reflns_theta_max         66.564
_diffrn_reflns_theta_min         2.359
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56595
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       block
_exptl_crystal_F_000             9994
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.816
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.456
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     711
_refine_ls_number_reflns         9828
_refine_ls_number_restraints     390
_refine_ls_restrained_S_all      1.515
_refine_ls_R_factor_all          0.1723
_refine_ls_R_factor_gt           0.1446
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3752
_refine_ls_wR_factor_ref         0.4041
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5921
_reflns_number_total             9828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00038f2.cif
_cod_data_source_block           CYH
_cod_depositor_comments
'Adding full bibliography for 7250046--7250051.cif.'
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C146.20 H163.20 Cl21.60 N30 O6'
_cod_database_code               7250047
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H O N Cl'
_shelx_estimated_absorpt_t_max   0.716
_shelx_estimated_absorpt_t_min   0.653
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C45-C44 \\sim C44-C43 \\sim C48-C43 \\sim C48-C47 \\sim C47-C46 \\sim C46-C45
 with sigma of 0.02
 C43-C45 \\sim C44-C46 \\sim C45-C47 \\sim C46-C48 \\sim C47-C43 \\sim C48-C44
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C43A \\sim C44A
\\sim C45A \\sim C46A \\sim C47A \\sim C48A: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C40 \\sim C41 \\sim C42 \\sim C41A \\sim C42A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C50 \\sim C50A \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim Cl1A \\sim Cl2A \\sim Cl3A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C19 \\sim C20 \\sim C21 \\sim C20A \\sim C21A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C19, C20A, C21A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C19, C20, C21}
{C40, C41A, C42A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C40, C41, C42}
{C43A, C44A, C45A, C46A, C47A, C48A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C43, C44, C45, C46, C47, C48}
{C50A, Cl1A, Cl2A, Cl3A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C50, Cl1, Cl2, Cl3}
5. Others
 Sof(H19A)=Sof(H40A)=Sof(C43A)=Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44C)=
 Sof(H44D)=Sof(C45A)=Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=
 Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(C49A)=
 Sof(H49C)=Sof(H49D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C42A)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(1)
 Sof(H19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(H40)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=
 Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=FVAR(1)
 Sof(C50A)=Sof(H50A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=1-FVAR(2)
 Sof(C50)=Sof(H50)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(2)
 Fixed Sof: H1A(0.33333) H1B(0.33333) H1C(0.33333) H22A(0.33333) H22B(0.33333)
 H22C(0.33333)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C19(H19A), C40(H40), C40(H40A), C50(H50), C50A(H50A)
6.b Secondary CH2 refined with riding coordinates:
 C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,
 H47B), C48(H48A,H48B), C49(H49A,H49B), C43A(H43C,H43D), C44A(H44C,H44D),
 C45A(H45C,H45D), C46A(H46C,H46D), C47A(H47C,H47D), C48A(H48C,H48D), C49A(H49C,
 H49D)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C11(H11), C15(H15), C16(H16), C17(H17), N5(H5),
 C27(H27), C28(H28), C30(H30), C32(H32), C36(H36), C37(H37), C38(H38), N10(H10)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C25(H25A,H25B,H25C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F), C41A(H41D,H41E,H41F),
 C42A(H42D,H42E,H42F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1440 electrons were 
found in a volume of 6405\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
2.1[CHCl3], 2.1[CHCl3] per Asymmetric Unit 
which account for 1462 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              96623
_shelx_fab_checksum              48073
_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 2.338
_oxdiff_exptl_absorpt_empirical_full_min 0.336