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_7250051
_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), 4(C8 H10), C H Cl3, 2(H2 O)'
_chemical_formula_sum            'C150.98 H158.98 Cl3 N30 O8'
_chemical_formula_weight         2628.42
_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   mixed
_audit_block_doi                 10.5517/ccdc.csd.cc2mbq3t
_audit_creation_date             2025-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-14 deposited with the CCDC.	2025-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                72.734(3)
_cell_angle_beta                 80.346(3)
_cell_angle_gamma                79.345(3)
_cell_formula_units_Z            1
_cell_length_a                   14.7305(5)
_cell_length_b                   15.2894(5)
_cell_length_c                   17.0209(5)
_cell_measurement_reflns_used    16155
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9040
_cell_measurement_theta_min      2.6920
_cell_volume                     3571.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.914
_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    -91.00 -65.00   0.50    0.74    --  -46.22 142.00 158.00   52
  2  \w    -78.00 -51.00   0.50    0.74    --  -46.22 129.00 -12.00   54
  3  \w   -102.00 -76.00   0.50    0.74    --  -46.22-142.00 102.00   52
  4  \w     43.00  95.00   0.50    0.74    --   46.22-129.00 -86.00  104
  5  \w     61.00  99.00   0.50    0.74    --   46.22-142.00 102.00   76
  6  \w     65.00 119.00   0.50    0.74    --   46.22 142.00 158.00  108
  7  \w   -144.00-119.00   0.50    2.97    --  -97.00-142.00 102.00   50
  8  \w   -124.00 -84.00   0.50    2.97    --  -97.00-129.00 -86.00   80
  9  \w   -113.00 -41.00   0.50    2.97    --  -97.00 129.00 -12.00  144
 10  \w   -124.00 -42.00   0.50    2.97    --  -97.00 142.00 158.00  164
 11  \w     94.00 119.00   0.50    2.97    --  107.47 142.00 158.00   50
 12  \w     60.00 114.00   0.50    2.97    --  107.47-142.00 102.00  108
 13  \w     86.00 112.00   0.50    2.97    --  107.47-129.00 -86.00   52
 14  \w     78.00 162.00   0.50    2.97    --  107.47 129.00 -12.00  168
 15  \w   -114.00 -23.00   0.50    0.74    --  -46.22 -77.00 -60.00  182
 16  \w    -28.00  28.00   0.50    0.74    --  -46.22  19.00-180.00  112
 17  \w    -29.00  29.00   0.50    0.74    --  -46.22  19.00 -90.00  116
 18  \w    -27.00  19.00   0.50    0.74    --   46.22 -19.00 -60.00   92
 19  \w    -24.00  18.00   0.50    0.74    --   46.22 -19.00  90.00   84
 20  \w    -25.00  23.00   0.50    0.74    --   46.22 -19.00 -30.00   96
 21  \w    -71.00 -32.00   0.50    2.97    --  -97.00  61.00  30.00   78
 22  \w   -162.00 -84.00   0.50    2.97    --  -97.00 -15.00 -30.00  156
 23  \w    -54.00 -29.00   0.50    2.97    --  -97.00  45.00 -60.00   50
 24  \w   -106.00 -27.00   0.50    2.97    --  -97.00 106.00 136.18  158
 25  \w    -51.00 -24.00   0.50    2.97    --  -97.00  45.00 -90.00   54
 26  \w   -158.00-132.00   0.50    2.97    --  -97.00 -61.00 150.00   52
 27  \w   -158.00-130.00   0.50    2.97    --  -97.00 -45.00 -30.00   56
 28  \w   -160.00 -81.00   0.50    2.97    --  -97.00 -15.00  90.00  158
 29  \w   -110.00 -79.00   0.50    2.97    --  -97.00 -61.00 150.00   62
 30  \w   -132.00-105.00   0.50    2.97    --  -97.00 -95.00-150.00   54
 31  \w   -169.00 -80.00   0.50    2.97    --  -97.00 -61.00 -60.00  178
 32  \w    -50.00 -25.00   0.50    2.97    --  -97.00  61.00-150.00   50
 33  \w   -122.00 -96.00   0.50    2.97    --  -97.00 -45.00 -30.00   52
 34  \w   -107.00 -66.00   0.50    2.97    --  -97.00 106.00  12.23   82
 35  \w   -112.00 -28.00   0.50    2.97    --  -97.00 125.00 150.00  168
 36  \w     35.00  66.00   0.50    2.97    --  107.47 -77.00  60.00   62
 37  \w     71.00 110.00   0.50    2.97    --  107.47-125.00 -60.00   78
 38  \w     95.00 174.00   0.50    2.97    --  107.47  45.00 150.00  158
 39  \w     95.00 175.00   0.50    2.97    --  107.47  45.00  30.00  160
 40  \w     58.00 111.00   0.50    2.97    --  107.47-125.00 120.00  106
 41  \w     67.00  93.00   0.50    2.97    --  107.47 -95.00 -60.00   52
 42  \w     41.00  66.00   0.50    2.97    --  107.47 -61.00  60.00   50
 43  \w     36.00 101.00   0.50    2.97    --  107.47 -95.00 -90.00  130
 44  \w     35.00  65.00   0.50    2.97    --  107.47 -61.00  90.00   60
 45  \w     37.00 100.00   0.50    2.97    --  107.47 -77.00 -60.00  126
 46  \w     73.00  98.00   0.50    2.97    --  107.47 -77.00  60.00   50
 47  \w     35.00  61.00   0.50    2.97    --  107.47 -61.00 150.00   52
;
_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      0.0684942000
_diffrn_orient_matrix_UB_12      0.0597735000
_diffrn_orient_matrix_UB_13      -0.0617668000
_diffrn_orient_matrix_UB_21      0.0370243000
_diffrn_orient_matrix_UB_22      0.0173740000
_diffrn_orient_matrix_UB_23      0.0726804000
_diffrn_orient_matrix_UB_31      0.0736786000
_diffrn_orient_matrix_UB_32      -0.0865611000
_diffrn_orient_matrix_UB_33      0.0041985000
_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  0.0724
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            47371
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.556
_diffrn_reflns_theta_min         2.738
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.121
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87605
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
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    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1390
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.151
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.588
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.112
_refine_ls_extinction_coef       0.0035(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1252
_refine_ls_number_reflns         14050
_refine_ls_number_restraints     1065
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1191
_refine_ls_R_factor_gt           0.0850
_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^)+(0.1828P)^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         0.2611
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9017
_reflns_number_total             14050
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00038f2.cif
_cod_data_source_block           m-xylene
_cod_depositor_comments
'Adding full bibliography for 7250046--7250051.cif.'
_cod_database_code               7250051
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Cl'
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.815
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C83-C82 \\sim C84-C81
 with sigma of 0.02
 Cl3-C85 \\sim Cl2-C85 \\sim Cl1-C85
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl1-Cl3 \\sim Cl3-Cl2
 with sigma of 0.02
 C75-C70 \\sim C74-C68
 with sigma of 0.02
 C74-C69 \\sim C74-C73
 with sigma of 0.02
 C75-C69 \\sim C75-C71
 with sigma of 0.02
 Cl1B-Cl2B \\sim Cl1B-Cl3B \\sim Cl2B-Cl3B
 with sigma of 0.02
3. Restrained planarity
 C68, C69, C70, C71, C72, C73, C74, C75
 with sigma of 0.01
 C68A, C69A, C70A, C71A, C72A, C73A, C74A, C75A
 with sigma of 0.01
 C68B, C69B, C70B, C71B, C72B, C73B, C74B, C75B
 with sigma of 0.01
 C60, C61, C62, C63, C64, C65, C66, C67
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C85A \\sim Cl1A \\sim Cl2A \\sim Cl3A \\sim C85 \\sim C85 \\sim Cl1 \\sim Cl1
\\sim Cl2 \\sim Cl2 \\sim Cl3 \\sim Cl3 \\sim C85B \\sim Cl1B \\sim Cl2B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim
C68A \\sim C69A \\sim C70A \\sim C71A \\sim C72A \\sim C73A \\sim C74A \\sim
C75A \\sim C68B \\sim C69B \\sim C70B \\sim C71B \\sim C72B \\sim C73B \\sim
C74B \\sim C75B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
N5 \\sim N6 \\sim N6 \\sim N7 \\sim N7 \\sim N8 \\sim N8 \\sim N9 \\sim N9
\\sim N10 \\sim N10 \\sim N11 \\sim N11 \\sim N12 \\sim N12 \\sim N13 \\sim N13
\\sim N14 \\sim N14 \\sim N15 \\sim N15 \\sim O1 \\sim O1 \\sim O2 \\sim O2
\\sim O3 \\sim O3 \\sim C23 \\sim C24 \\sim C24 \\sim C25 \\sim C25 \\sim C23A
\\sim C23A \\sim C24A \\sim C25A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 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
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C85B) \\sim Ueq, Uanis(Cl3B) \\sim Ueq, Uanis(Cl2B) \\sim Ueq,
Uanis(Cl1B) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(Cl3)
\\sim Ueq, Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Same fragment restrains
{C40, C41A, C42A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C40, C41, C42}
{C68A, C69A, C70A, C71A, C72A, C73A, C74A, C75A} sigma for 1-2: 0.01, 1-3: 0.01
{C68B, C69B, C70B, C71B, C72B, C73B, C74B, C75B} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C68, C69, C70, C71, C72, C73, C74, C75}
{N5, C23A, C24A, C25A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{N5, C23, C24, C25}
{C85A, Cl1A, Cl3A, Cl2A} sigma for 1-2: 0.02, 1-3: 0.02
{C85B, Cl1B, Cl2B} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C85, Cl1, Cl2, Cl3}
6. Others
 1*[Sof(C68)+Sof(C69)+Sof(H69)+Sof(C70)+Sof(C71)+Sof(H71)+Sof(C72)+Sof(H72)+
 Sof(C73)+Sof(H73)+Sof(C74)+Sof(H74A)+Sof(H74B)+Sof(H74C)+Sof(C75)+Sof(H75A)+
 Sof(H75B)+Sof(H75C)]+1*[Sof(C68A)+Sof(C69A)+Sof(H69A)+Sof(C70A)+Sof(C71A)+
 Sof(H71A)+Sof(C72A)+Sof(H72A)+Sof(C73A)+Sof(H73A)+Sof(C74A)+Sof(H74D)+
 Sof(H74E)+Sof(H74F)+Sof(C75A)+Sof(H75D)+Sof(H75E)+Sof(H75F)]+1*[Sof(C68B)+
 Sof(C69B)+Sof(H69B)+Sof(C70B)+Sof(C71B)+Sof(H71B)+Sof(C72B)+Sof(H72B)+
 Sof(C73B)+Sof(H73B)+Sof(C74B)+Sof(H74G)+Sof(H74H)+Sof(H74I)+Sof(C75B)+
 Sof(H75G)+Sof(H75H)+Sof(H75I)]=1 with esd of 0
 1*[Sof(C85)+Sof(H85)+Sof(Cl1)+Sof(Cl2)+Sof(Cl3)]+1*[Sof(C85A)+Sof(H85A)+
 Sof(Cl1A)+Sof(Cl3A)+Sof(Cl2A)]+1*[Sof(C85B)+Sof(H85B)+Sof(Cl1B)+Sof(Cl2B)+
 Sof(Cl3B)]=0.5 with esd of 0
 Sof(C68)=Sof(C69)=Sof(H69)=Sof(C70)=Sof(C71)=Sof(H71)=Sof(C72)=Sof(H72)=
 Sof(C73)=Sof(H73)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=
 Sof(H75B)=Sof(H75C)=FVAR(1)
 Sof(H5B)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=
 Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(H5A)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
 Sof(H40A)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42A)=Sof(H42D)=
 Sof(H42E)=Sof(H42F)=1-FVAR(3)
 Sof(H40)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=FVAR(3)
 Sof(C85)=Sof(H85)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(4)
 Sof(C68A)=Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=
 Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=
 Sof(C75A)=Sof(H75D)=Sof(H75E)=Sof(H75F)=FVAR(5)
 Sof(C68B)=Sof(C69B)=Sof(H69B)=Sof(C70B)=Sof(C71B)=Sof(H71B)=Sof(C72B)=
 Sof(H72B)=Sof(C73B)=Sof(H73B)=Sof(C74B)=Sof(H74G)=Sof(H74H)=Sof(H74I)=
 Sof(C75B)=Sof(H75G)=Sof(H75H)=Sof(H75I)=FVAR(6)
 Sof(C85A)=Sof(H85A)=Sof(Cl1A)=Sof(Cl3A)=Sof(Cl2A)=FVAR(7)
 Sof(C85B)=Sof(H85B)=Sof(Cl1B)=Sof(Cl2B)=Sof(Cl3B)=FVAR(8)
 Fixed Sof: C60(0.5) C61(0.5) H61(0.5) C62(0.5) C63(0.5) H63(0.5) C64(0.5)
 H64(0.5) C65(0.5) H65(0.5) C66(0.5) H66A(0.5) H66B(0.5) H66C(0.5) C67(0.5)
 H67A(0.5) H67B(0.5) H67C(0.5) C76(0.5) H76(0.5) C78(0.5) H78(0.5) C79(0.5)
 H79(0.5) C80(0.5) H80(0.5) C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C82(0.5)
 H82A(0.5) H82B(0.5) H82C(0.5) C83(0.5) C84(0.5)
7.a Free rotating group:
 O4(H4A,H4B)
7.b Ternary CH refined with riding coordinates:
 C40(H40A), C40(H40), C57(H57), C23(H23), C85B(H85B), C85A(H85A), C85(H85),
 C23A(H23A)
7.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C15(H15), C19(H19), C20(H20), C21(H21),
 C27(H27), C28(H28), C30(H30), C32(H32), C36(H36), C37(H37), C38(H38), C44(H44),
  C46(H46), C47(H47), C49(H49), C53(H53), C54(H54), C55(H55), N5(H5A), N5(H5B),
 N10(H10A), N15(H15A), C69(H69), C71(H71), C72(H72), C73(H73), C69A(H69A),
 C71A(H71A), C72A(H72A), C73A(H73A), C69B(H69B), C71B(H71B), C72B(H72B),
 C73B(H73B), C61(H61), C63(H63), C64(H64), C65(H65), C76(H76), C78(H78),
 C79(H79), C80(H80)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C),
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C74(H74A,H74B,H74C), C75(H75A,H75B,
 H75C), C74A(H74D,H74E,H74F), C75A(H75D,H75E,H75F), C74B(H74G,H74H,H74I),
 C75B(H75G,H75H,H75I), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C81(H81A,H81B,
 H81C), C82(H82A,H82B,H82C), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F),
 C41A(H41D,H41E,H41F), C42A(H42D,H42E,H42F)
;
_shelx_res_checksum              320
_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 3.441
_oxdiff_exptl_absorpt_empirical_full_min 0.493