research communications
H-6,11-epoxycyclopenta[a]anthracene-2,2-dicarboxylate
of dimethyl 5-(4-ethylphenyl)-4-[(4-ethylphenyl)ethynyl]-6,11-diphenyl-1,3,6,11-tetrahydro-2aSchool of Chemistry and Materials Engineering, Chaohu College, Chaohu Anhui, People's Republic of China
*Correspondence e-mail: mxzcd79@163.com
In the central fused ring system of the title compound, C51H42O5, all of the five-membered rings are in an The dihedral angle between the two benzene rings in the fused ring system is 74.66 (7)°. In the crystal, molecules are linked by C—H⋯π interactions, forming a layer parallel to the ab plane. Each molecule acts as a double donor as well as a double acceptor of the C—H⋯π interactions. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (61.4%) and C⋯H/H⋯C (25.3%) contacts.
Keywords: crystal structure; C—H⋯π interactions; Hirshfeld surface analysis; hexadehydro-Diels–Alder reaction.
CCDC reference: 2003756
1. Chemical context
The hexadehydro-Diels–Alder reaction, by which benzyne intermediates (Niu et al., 2013) as well as highly functionalized benzenoid products (Karmakar et al., 2013) are prepared, has played a very significant role in the field of organic synthesis. Zhang et al. (2015) observed that benzyne intermediates can be captured by five-membered such as furans, pyrroles and thiophenes. As part of our work on the application of the hexadehydro-Diels–Alder reaction (Meng et al., 2017), we report herein the synthesis and of the title compound.
2. Structural commentary
The molecular structure of the title compound is shown in Fig. 1. One ethyl group (C46–C47) is disordered over two sites around the C43—C46 bond axis with occupancies of 0.548 (9) and 0.452 (9). The fused ring system is not planar, and the five-membered rings (C4/C5/O5/C12/C13 and C5/C6/C11/C12/O5) adopt envelope conformations with atom O5 as the flap. The C4–C6/C11–C13 ring adopts a boat conformation. The C1–C3/C16/C17 ring adopts an with atom C1 as the flap and has puckering parameters Q2 = 0.3132 (18) Å and φ2 = 178.5 (3)°. The angle between the two benzene rings (C6–C11 and C3/C4/C13–C16) in the fused ring system is 74.66 (7)°. The sp-hybridized character of atoms C38 and C39 is confirmed by the C38—C39 [1.188 (2) Å] bond length, and the C15—C38—C39 [177.2 (2)°] and C38—C39—C40 [178.4 (2)°] bond angles. The C3/C4/C13–C16 benzene ring is inclined to the C30–C35 and C40–C45 benzene rings by 57.72 (7) and 35.48 (3)°, respectively, the latter two rings being inclined to each other by 77.78 (7)°.
3. Supramolecular features
In the crystal, the molecules are linked by weak C—H⋯π interactions (C20—H20⋯Cg4i and C26—H26⋯Cg7ii; symmetry codes as in Table 1), forming a layer parallel to the ab plane (Fig. 2); Cg4 and Cg7 are the centroids of the C3/C4/C13–C16 and C18—C23 rings, respectively.
In order to investigate the intermolecular interactions in a visual manner, a Hirshfeld surface analysis was performed using CrystalExplorer (Spackman & Jayatilaka, 2009; Turner et al., 2017). The bright-red spots on the Hirshfeld surface mapped over dnorm (Fig. 3a) show the presence of C—H⋯π interactions with neighbouring molecules. The absence of adjacent red and blue triangles on the shape-index map (Fig. 3b) suggests that there are no notable π–π interactions. The fingerprint plots (Fig. 4) are given for all contacts, and those delineated into C⋯C (0.8%), C⋯O/O⋯C (0.2%), H⋯O/O⋯H (12.2%), C⋯H/H⋯C (25.3%) and H⋯H (61.4%) contacts. The most important contributions to the crystal packing are H⋯H and C⋯H/H⋯C contacts.
4. Database survey
A search of the Cambridge Structural Database (CSD, version 5.40, last update August 2019; Groom et al., 2016) gave twelve hits for compounds having a 9,10-dihydro-9,10-epoxyanthracene fragment. In these structures, all five-membered rings are in an and the benzene rings in each fused ring system show a similar dihedral angle of ca 72°. A search for structures with a 3,6,7,8-tetrahydro-1H-indeno[4,5-c]furan fragment revealed two hits, and one of the compounds, dimethyl 5-phenyl-4-(phenylethynyl)-1,3,6,9-tetrahydro-2H-6,9-epoxycyclopenta[a]naphthalene-2,2-dicarboxylate (refcode IKOJUP; Zhang et al., 2015) is closely related to the title compound.
5. Synthesis and crystallization
Dimethyl 2,2-bis[5-(4-ethylphenyl)penta-2,4-diyn-1-yl]malonate (0.46 g) and 1,3-diphenylisobenzofuran (0.3 g) were added to toluene (2.0 ml), and the mixture was stirred at room temperature and then heated at 373 K for 10 h in air. The reaction mixture was cooled to room temperature, and the solvent was evaporated in vacuo. The residue was purified by on silica gel using n-hexane/ethyl acetate (20:1, v:v) as to afford the compound (0.46 g) as a white solid. Part of the purified product was redissolved in n-hexane/ethyl acetate and colourless crystals suitable for X-ray diffraction were formed after slow evaporation for several days.
Spectroscopic data: FT–IR (KBr): 3028, 2949, 1741, 1728, 1508, 1446, 1243, 1049, 619 cm−1; 1H NMR (C6D6, 300 MHz): δ 8.17–8.14 (d, J = 7.5Hz, 2H), 7.75–7.73 (d, J = 6.0 Hz, 1H), 7.60–7.56 (m, 3H), 7.35–7.31 (m, 2H), 7.24–7.16 (m, 5H), 7.00 (s, 2H), 6.91–6.76 (m, 7H), 4.29–4.23 (d, J = 17.1 Hz, 1H), 3.80–3.74 (d, J = 16.8Hz, 2H), 3.49–3.43 (d, J = 16.5Hz, 1H), 3.19 (s, 3H), 3.15 (s, 3H), 2.39–2.37 (m, 2H), 2.27–2.25 (m, 2H), 1.07–1.02 (t, J = 7.2Hz, 3H), 0.96–0.91 (t, J = 7.2Hz, 3H); 13C NMR (C6D6, 125 MHz): δ 171.9, 171.4, 151.6, 151.3, 149.6, 147.7, 144.6, 143.8, 143.1, 137.6, 135.9, 134.8, 134.7, 132.6, 131.9, 130.0, 129.8, 129.4, 128.9, 128.4, 127.7, 127.0, 126.4, 126.2, 122.9, 122.4, 121.3, 118.4, 97.3, 93.1, 91.1, 87.7, 60.8, 52.6, 52.5, 41.1, 39.7, 29.1, 29.1, 16.3, 15.6.
6. Refinement
Crystal data, data collection and structure . All H atoms were included in calculated positions (C—H = 0.93–0.97 Å) using a riding model, with Uiso(H) = 1.5 or 1.2Ueq(C). The ethyl group (C46–C47) was found to be disordered over two sites around the C43—C46 bond axis and the occupancies were refined to 0.548 (9) and 0.452 (9). For the two ethyl groups (C36–C37 and C46—C47), displacement restraints (DELU and SIMU) were applied. For the disordered atoms (C47 and C47A), ISOR restraint and EADP constraint were also applied.
details are summarized in Table 2
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Supporting information
CCDC reference: 2003756
https://doi.org/10.1107/S2056989020006404/is5535sup1.cif
contains datablocks general, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020006404/is5535Isup2.hkl
Data collection: APEX2 (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHLEXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C51H42O5 | F(000) = 1552 |
Mr = 734.84 | Dx = 1.198 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3654 (10) Å | Cell parameters from 9893 reflections |
b = 14.2430 (12) Å | θ = 2.2–27.3° |
c = 25.168 (2) Å | µ = 0.08 mm−1 |
β = 91.207 (1)° | T = 293 K |
V = 4073.2 (6) Å3 | Block, colourless |
Z = 4 | 0.23 × 0.22 × 0.20 mm |
Bruker APEXII CCD area detector diffractometer | 6819 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
phi and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −14→14 |
Tmin = 0.983, Tmax = 0.985 | k = −18→17 |
34227 measured reflections | l = −32→32 |
9159 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.056 | w = 1/[σ2(Fo2) + (0.0848P)2 + 1.1068P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.169 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.33 e Å−3 |
9159 reflections | Δρmin = −0.30 e Å−3 |
515 parameters | Extinction correction: SHELXL-2018/3, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
20 restraints | Extinction coefficient: 0.0288 (14) |
Primary atom site location: dual |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.67845 (14) | 0.32574 (12) | 0.38548 (7) | 0.0473 (4) | |
C2 | 0.59520 (14) | 0.34546 (12) | 0.33729 (7) | 0.0457 (4) | |
H2A | 0.553476 | 0.404303 | 0.341554 | 0.055* | |
H2B | 0.638223 | 0.347262 | 0.304421 | 0.055* | |
C3 | 0.51201 (13) | 0.26312 (10) | 0.33826 (6) | 0.0387 (3) | |
C4 | 0.40374 (13) | 0.24906 (10) | 0.31442 (6) | 0.0371 (3) | |
C5 | 0.32602 (13) | 0.30966 (11) | 0.27700 (6) | 0.0393 (3) | |
C6 | 0.33055 (15) | 0.25996 (12) | 0.22280 (6) | 0.0441 (4) | |
C7 | 0.38339 (19) | 0.27862 (14) | 0.17523 (7) | 0.0605 (5) | |
H7 | 0.425215 | 0.333947 | 0.170291 | 0.073* | |
C8 | 0.3725 (2) | 0.21236 (17) | 0.13465 (8) | 0.0737 (6) | |
H8 | 0.405699 | 0.224808 | 0.101928 | 0.088* | |
C9 | 0.3143 (2) | 0.12947 (16) | 0.14186 (8) | 0.0692 (6) | |
H9 | 0.309206 | 0.086263 | 0.114200 | 0.083* | |
C10 | 0.26254 (17) | 0.10908 (14) | 0.19004 (7) | 0.0550 (4) | |
H10 | 0.224551 | 0.052124 | 0.195377 | 0.066* | |
C11 | 0.26919 (14) | 0.17587 (12) | 0.22980 (6) | 0.0441 (4) | |
C12 | 0.22847 (13) | 0.17681 (11) | 0.28746 (6) | 0.0407 (3) | |
C13 | 0.34321 (13) | 0.16415 (11) | 0.32089 (6) | 0.0379 (3) | |
C14 | 0.39041 (14) | 0.08984 (10) | 0.34996 (6) | 0.0392 (3) | |
C15 | 0.50249 (14) | 0.10493 (11) | 0.37516 (6) | 0.0402 (3) | |
C16 | 0.55998 (13) | 0.18993 (11) | 0.36889 (6) | 0.0405 (3) | |
C17 | 0.68014 (15) | 0.21714 (12) | 0.38992 (7) | 0.0505 (4) | |
H17A | 0.741600 | 0.190258 | 0.368502 | 0.061* | |
H17B | 0.691648 | 0.197196 | 0.426511 | 0.061* | |
C18 | 0.33666 (13) | 0.41416 (11) | 0.28409 (6) | 0.0409 (3) | |
C19 | 0.3906 (2) | 0.47302 (14) | 0.24958 (9) | 0.0707 (6) | |
H19 | 0.419039 | 0.449371 | 0.217893 | 0.085* | |
C20 | 0.4037 (2) | 0.56778 (15) | 0.26106 (11) | 0.0796 (7) | |
H20 | 0.442902 | 0.606349 | 0.237434 | 0.096* | |
C21 | 0.3608 (2) | 0.60460 (14) | 0.30570 (9) | 0.0666 (5) | |
H21 | 0.370153 | 0.668137 | 0.313189 | 0.080* | |
C22 | 0.3027 (3) | 0.54696 (16) | 0.34017 (9) | 0.0839 (8) | |
H22 | 0.271439 | 0.571660 | 0.371031 | 0.101* | |
C23 | 0.2907 (2) | 0.45260 (14) | 0.32917 (8) | 0.0722 (6) | |
H23 | 0.250777 | 0.414320 | 0.352688 | 0.087* | |
C24 | 0.11663 (14) | 0.12878 (11) | 0.30320 (7) | 0.0449 (4) | |
C25 | 0.03121 (16) | 0.10294 (15) | 0.26622 (8) | 0.0594 (5) | |
H25 | 0.044218 | 0.112279 | 0.230250 | 0.071* | |
C26 | −0.07348 (18) | 0.06334 (17) | 0.28205 (10) | 0.0726 (6) | |
H26 | −0.129658 | 0.045456 | 0.256624 | 0.087* | |
C27 | −0.09501 (18) | 0.05029 (16) | 0.33468 (11) | 0.0732 (6) | |
H27 | −0.165477 | 0.023556 | 0.345167 | 0.088* | |
C28 | −0.01173 (18) | 0.07699 (16) | 0.37203 (9) | 0.0692 (6) | |
H28 | −0.026166 | 0.068634 | 0.407954 | 0.083* | |
C29 | 0.09345 (16) | 0.11620 (14) | 0.35656 (8) | 0.0553 (4) | |
H29 | 0.149089 | 0.134284 | 0.382182 | 0.066* | |
C30 | 0.32887 (14) | −0.00163 (11) | 0.35447 (6) | 0.0432 (4) | |
C31 | 0.29777 (19) | −0.03780 (13) | 0.40336 (8) | 0.0589 (5) | |
H31 | 0.322227 | −0.007798 | 0.434503 | 0.071* | |
C32 | 0.2301 (2) | −0.11886 (15) | 0.40585 (9) | 0.0715 (6) | |
H32 | 0.209412 | −0.142128 | 0.438890 | 0.086* | |
C33 | 0.19276 (19) | −0.16572 (14) | 0.36061 (10) | 0.0663 (5) | |
C34 | 0.22917 (18) | −0.13207 (14) | 0.31229 (9) | 0.0630 (5) | |
H34 | 0.208653 | −0.164396 | 0.281355 | 0.076* | |
C35 | 0.29538 (16) | −0.05141 (12) | 0.30907 (7) | 0.0511 (4) | |
H35 | 0.318123 | −0.029833 | 0.275960 | 0.061* | |
C36 | 0.1087 (3) | −0.24775 (19) | 0.36355 (14) | 0.1012 (8) | |
H36A | 0.130152 | −0.294591 | 0.337497 | 0.121* | |
H36B | 0.115443 | −0.276292 | 0.398479 | 0.121* | |
C37 | −0.0154 (3) | −0.2178 (2) | 0.35341 (15) | 0.1107 (8) | |
H37A | −0.023092 | −0.192468 | 0.318176 | 0.166* | |
H37B | −0.036399 | −0.170793 | 0.378823 | 0.166* | |
H37C | −0.066614 | −0.271027 | 0.356715 | 0.166* | |
C38 | 0.55911 (15) | 0.03226 (11) | 0.40587 (6) | 0.0452 (4) | |
C39 | 0.60910 (16) | −0.02503 (12) | 0.43218 (7) | 0.0488 (4) | |
C40 | 0.66926 (16) | −0.09620 (12) | 0.46286 (6) | 0.0479 (4) | |
C41 | 0.60811 (19) | −0.15832 (14) | 0.49438 (7) | 0.0585 (5) | |
H41 | 0.526864 | −0.153142 | 0.496954 | 0.070* | |
C42 | 0.6680 (2) | −0.22811 (15) | 0.52203 (8) | 0.0707 (6) | |
H42 | 0.625907 | −0.269003 | 0.543290 | 0.085* | |
C43 | 0.7868 (2) | −0.23862 (16) | 0.51901 (8) | 0.0722 (6) | |
C44 | 0.8472 (2) | −0.17530 (19) | 0.48899 (10) | 0.0843 (7) | |
H44 | 0.928670 | −0.179979 | 0.487244 | 0.101* | |
C45 | 0.7898 (2) | −0.10488 (17) | 0.46135 (9) | 0.0740 (6) | |
H45 | 0.833043 | −0.062660 | 0.441415 | 0.089* | |
C46 | 0.8509 (4) | −0.3181 (2) | 0.54713 (12) | 0.1143 (10) | |
H46A | 0.934866 | −0.306750 | 0.545226 | 0.137* | 0.548 (9) |
H46B | 0.830517 | −0.316916 | 0.584359 | 0.137* | 0.548 (9) |
H46C | 0.800764 | −0.344924 | 0.573909 | 0.137* | 0.452 (9) |
H46D | 0.921346 | −0.294122 | 0.564826 | 0.137* | 0.452 (9) |
C47 | 0.8270 (10) | −0.4094 (5) | 0.5268 (3) | 0.1202 (12) | 0.548 (9) |
H47A | 0.746809 | −0.425897 | 0.533709 | 0.180* | 0.548 (9) |
H47B | 0.878766 | −0.453993 | 0.543778 | 0.180* | 0.548 (9) |
H47C | 0.839107 | −0.410076 | 0.489164 | 0.180* | 0.548 (9) |
C48 | 0.62644 (18) | 0.37218 (14) | 0.43477 (8) | 0.0582 (5) | |
C49 | 0.6058 (4) | 0.3681 (3) | 0.52714 (10) | 0.1300 (14) | |
H49A | 0.525800 | 0.388312 | 0.522056 | 0.195* | |
H49B | 0.654441 | 0.421213 | 0.535929 | 0.195* | |
H49C | 0.610197 | 0.323156 | 0.555545 | 0.195* | |
C50 | 0.80048 (16) | 0.36611 (15) | 0.37898 (8) | 0.0586 (5) | |
C51 | 0.96438 (18) | 0.3759 (2) | 0.32348 (11) | 0.0918 (8) | |
H51A | 0.979822 | 0.369125 | 0.286322 | 0.138* | |
H51B | 1.018019 | 0.337334 | 0.343772 | 0.138* | |
H51C | 0.974645 | 0.440409 | 0.333676 | 0.138* | |
O1 | 0.5728 (2) | 0.44286 (14) | 0.43391 (7) | 0.1123 (7) | |
O2 | 0.64680 (18) | 0.32502 (13) | 0.47847 (6) | 0.0914 (6) | |
O3 | 0.8505 (2) | 0.4118 (2) | 0.41081 (10) | 0.1535 (12) | |
O4 | 0.84501 (12) | 0.34724 (14) | 0.33351 (6) | 0.0822 (5) | |
O5 | 0.21155 (9) | 0.27792 (7) | 0.29414 (4) | 0.0413 (3) | |
C47A | 0.8856 (12) | −0.3967 (6) | 0.5060 (4) | 0.1202 (12) | 0.452 (9) |
H47D | 0.816351 | −0.417779 | 0.487026 | 0.180* | 0.452 (9) |
H47E | 0.921157 | −0.448603 | 0.524583 | 0.180* | 0.452 (9) |
H47F | 0.940502 | −0.371375 | 0.481252 | 0.180* | 0.452 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0418 (9) | 0.0482 (9) | 0.0518 (9) | −0.0037 (7) | −0.0007 (7) | 0.0007 (7) |
C2 | 0.0389 (8) | 0.0445 (9) | 0.0536 (9) | −0.0025 (7) | −0.0009 (7) | 0.0047 (7) |
C3 | 0.0372 (8) | 0.0374 (8) | 0.0416 (8) | 0.0023 (6) | 0.0049 (6) | 0.0001 (6) |
C4 | 0.0368 (8) | 0.0365 (8) | 0.0381 (7) | 0.0044 (6) | 0.0038 (6) | 0.0024 (6) |
C5 | 0.0347 (7) | 0.0407 (8) | 0.0425 (8) | 0.0043 (6) | 0.0033 (6) | 0.0042 (6) |
C6 | 0.0447 (9) | 0.0460 (9) | 0.0415 (8) | 0.0102 (7) | 0.0002 (6) | 0.0053 (6) |
C7 | 0.0756 (13) | 0.0577 (11) | 0.0487 (10) | 0.0101 (9) | 0.0119 (9) | 0.0099 (8) |
C8 | 0.1065 (18) | 0.0739 (14) | 0.0413 (10) | 0.0202 (13) | 0.0150 (10) | 0.0041 (9) |
C9 | 0.0949 (16) | 0.0671 (13) | 0.0454 (10) | 0.0213 (12) | −0.0034 (10) | −0.0093 (9) |
C10 | 0.0620 (11) | 0.0530 (10) | 0.0496 (9) | 0.0114 (8) | −0.0087 (8) | −0.0058 (8) |
C11 | 0.0428 (8) | 0.0469 (9) | 0.0422 (8) | 0.0085 (7) | −0.0044 (6) | 0.0011 (7) |
C12 | 0.0398 (8) | 0.0382 (8) | 0.0439 (8) | 0.0029 (6) | −0.0011 (6) | −0.0008 (6) |
C13 | 0.0377 (8) | 0.0390 (8) | 0.0372 (7) | 0.0009 (6) | 0.0025 (6) | −0.0013 (6) |
C14 | 0.0425 (8) | 0.0374 (8) | 0.0378 (7) | 0.0016 (6) | 0.0020 (6) | −0.0007 (6) |
C15 | 0.0441 (8) | 0.0383 (8) | 0.0381 (7) | 0.0046 (6) | −0.0002 (6) | −0.0002 (6) |
C16 | 0.0384 (8) | 0.0412 (8) | 0.0419 (8) | 0.0046 (6) | −0.0001 (6) | −0.0013 (6) |
C17 | 0.0441 (9) | 0.0487 (10) | 0.0583 (10) | 0.0032 (7) | −0.0075 (7) | 0.0010 (8) |
C18 | 0.0360 (8) | 0.0404 (8) | 0.0464 (8) | 0.0050 (6) | −0.0014 (6) | 0.0046 (6) |
C19 | 0.0839 (15) | 0.0505 (11) | 0.0792 (14) | −0.0058 (10) | 0.0384 (12) | 0.0003 (10) |
C20 | 0.0913 (17) | 0.0488 (11) | 0.1003 (17) | −0.0142 (11) | 0.0370 (14) | 0.0061 (11) |
C21 | 0.0686 (13) | 0.0428 (10) | 0.0881 (15) | −0.0037 (9) | −0.0069 (11) | −0.0027 (10) |
C22 | 0.136 (2) | 0.0538 (12) | 0.0624 (13) | −0.0023 (13) | 0.0167 (13) | −0.0098 (10) |
C23 | 0.1158 (19) | 0.0472 (11) | 0.0544 (11) | −0.0035 (11) | 0.0213 (11) | 0.0020 (8) |
C24 | 0.0375 (8) | 0.0409 (8) | 0.0562 (9) | 0.0011 (6) | −0.0006 (7) | −0.0015 (7) |
C25 | 0.0463 (10) | 0.0669 (12) | 0.0648 (11) | −0.0043 (9) | −0.0063 (8) | −0.0006 (9) |
C26 | 0.0451 (11) | 0.0768 (14) | 0.0952 (17) | −0.0115 (10) | −0.0112 (10) | −0.0073 (12) |
C27 | 0.0465 (11) | 0.0692 (14) | 0.1044 (18) | −0.0115 (9) | 0.0113 (11) | 0.0022 (12) |
C28 | 0.0558 (12) | 0.0788 (14) | 0.0735 (13) | −0.0082 (10) | 0.0144 (10) | 0.0057 (11) |
C29 | 0.0460 (9) | 0.0616 (11) | 0.0584 (10) | −0.0047 (8) | 0.0046 (8) | −0.0039 (8) |
C30 | 0.0457 (9) | 0.0370 (8) | 0.0469 (8) | 0.0007 (6) | −0.0015 (7) | 0.0020 (6) |
C31 | 0.0739 (13) | 0.0520 (10) | 0.0507 (10) | −0.0127 (9) | 0.0008 (9) | 0.0039 (8) |
C32 | 0.0831 (15) | 0.0606 (12) | 0.0711 (13) | −0.0150 (11) | 0.0081 (11) | 0.0159 (10) |
C33 | 0.0607 (12) | 0.0447 (10) | 0.0935 (15) | −0.0082 (9) | 0.0002 (11) | 0.0004 (10) |
C34 | 0.0645 (12) | 0.0487 (10) | 0.0754 (13) | −0.0041 (9) | −0.0082 (10) | −0.0122 (9) |
C35 | 0.0562 (10) | 0.0447 (9) | 0.0525 (9) | 0.0020 (8) | −0.0017 (8) | −0.0033 (7) |
C36 | 0.0879 (13) | 0.0697 (14) | 0.147 (2) | −0.0314 (12) | 0.0153 (15) | −0.0122 (14) |
C37 | 0.0869 (14) | 0.0927 (16) | 0.153 (2) | −0.0297 (13) | 0.0180 (16) | −0.0223 (15) |
C38 | 0.0502 (9) | 0.0410 (9) | 0.0442 (8) | 0.0037 (7) | −0.0025 (7) | −0.0001 (7) |
C39 | 0.0579 (10) | 0.0417 (9) | 0.0465 (9) | 0.0031 (7) | −0.0051 (7) | 0.0012 (7) |
C40 | 0.0600 (11) | 0.0440 (9) | 0.0395 (8) | 0.0065 (7) | −0.0037 (7) | 0.0037 (7) |
C41 | 0.0670 (12) | 0.0549 (11) | 0.0538 (10) | 0.0038 (9) | 0.0074 (9) | 0.0054 (8) |
C42 | 0.0971 (17) | 0.0601 (12) | 0.0553 (11) | 0.0041 (11) | 0.0121 (11) | 0.0185 (9) |
C43 | 0.0997 (18) | 0.0679 (13) | 0.0488 (10) | 0.0251 (12) | −0.0048 (11) | 0.0144 (9) |
C44 | 0.0658 (14) | 0.1027 (19) | 0.0844 (16) | 0.0242 (13) | −0.0013 (12) | 0.0346 (14) |
C45 | 0.0635 (13) | 0.0812 (15) | 0.0772 (14) | 0.0060 (11) | 0.0020 (10) | 0.0357 (12) |
C46 | 0.166 (3) | 0.0848 (15) | 0.0915 (18) | 0.0494 (19) | −0.0128 (17) | 0.0307 (13) |
C47 | 0.172 (3) | 0.0868 (17) | 0.101 (2) | 0.048 (2) | −0.006 (2) | 0.0243 (18) |
C48 | 0.0632 (12) | 0.0553 (11) | 0.0563 (11) | −0.0093 (9) | 0.0046 (9) | −0.0017 (9) |
C49 | 0.212 (4) | 0.123 (3) | 0.0559 (14) | −0.015 (3) | 0.0250 (19) | −0.0133 (16) |
C50 | 0.0432 (10) | 0.0687 (12) | 0.0635 (11) | −0.0078 (8) | −0.0047 (8) | 0.0000 (9) |
C51 | 0.0402 (11) | 0.131 (2) | 0.1043 (19) | 0.0036 (12) | 0.0124 (11) | 0.0305 (17) |
O1 | 0.170 (2) | 0.0872 (13) | 0.0810 (12) | 0.0496 (13) | 0.0309 (12) | −0.0040 (10) |
O2 | 0.1366 (16) | 0.0861 (12) | 0.0514 (8) | 0.0106 (11) | 0.0029 (9) | 0.0001 (8) |
O3 | 0.0914 (14) | 0.236 (3) | 0.1336 (18) | −0.0870 (18) | 0.0265 (13) | −0.0883 (19) |
O4 | 0.0428 (7) | 0.1282 (14) | 0.0761 (10) | −0.0100 (8) | 0.0102 (7) | −0.0020 (9) |
O5 | 0.0343 (5) | 0.0400 (6) | 0.0496 (6) | 0.0032 (4) | 0.0037 (4) | 0.0001 (5) |
C47A | 0.172 (3) | 0.0868 (17) | 0.101 (2) | 0.048 (2) | −0.006 (2) | 0.0243 (18) |
C1—C2 | 1.548 (2) | C28—C29 | 1.383 (3) |
C1—C17 | 1.551 (2) | C29—H29 | 0.9300 |
C1—C48 | 1.535 (3) | C30—C31 | 1.387 (2) |
C1—C50 | 1.513 (2) | C30—C35 | 1.391 (2) |
C2—H2A | 0.9700 | C31—H31 | 0.9300 |
C2—H2B | 0.9700 | C31—C32 | 1.389 (3) |
C2—C3 | 1.507 (2) | C32—H32 | 0.9300 |
C3—C4 | 1.372 (2) | C32—C33 | 1.379 (3) |
C3—C16 | 1.400 (2) | C33—C34 | 1.379 (3) |
C4—C5 | 1.542 (2) | C33—C36 | 1.512 (3) |
C4—C13 | 1.403 (2) | C34—H34 | 0.9300 |
C5—C6 | 1.539 (2) | C34—C35 | 1.377 (3) |
C5—C18 | 1.504 (2) | C35—H35 | 0.9300 |
C5—O5 | 1.4514 (18) | C36—H36A | 0.9700 |
C6—C7 | 1.377 (2) | C36—H36B | 0.9700 |
C6—C11 | 1.399 (2) | C36—C37 | 1.491 (4) |
C7—H7 | 0.9300 | C37—H37A | 0.9600 |
C7—C8 | 1.394 (3) | C37—H37B | 0.9600 |
C8—H8 | 0.9300 | C37—H37C | 0.9600 |
C8—C9 | 1.368 (3) | C38—C39 | 1.188 (2) |
C9—H9 | 0.9300 | C39—C40 | 1.438 (2) |
C9—C10 | 1.389 (3) | C40—C41 | 1.385 (3) |
C10—H10 | 0.9300 | C40—C45 | 1.377 (3) |
C10—C11 | 1.382 (2) | C41—H41 | 0.9300 |
C11—C12 | 1.532 (2) | C41—C42 | 1.384 (3) |
C12—C13 | 1.548 (2) | C42—H42 | 0.9300 |
C12—C24 | 1.504 (2) | C42—C43 | 1.363 (3) |
C12—O5 | 1.4631 (18) | C43—C44 | 1.370 (3) |
C13—C14 | 1.388 (2) | C43—C46 | 1.514 (3) |
C14—C15 | 1.427 (2) | C44—H44 | 0.9300 |
C14—C30 | 1.484 (2) | C44—C45 | 1.377 (3) |
C15—C16 | 1.386 (2) | C45—H45 | 0.9300 |
C15—C38 | 1.436 (2) | C46—H46A | 0.9700 |
C16—C17 | 1.505 (2) | C46—H46B | 0.9700 |
C17—H17A | 0.9700 | C46—H46C | 0.9700 |
C17—H17B | 0.9700 | C46—H46D | 0.9700 |
C18—C19 | 1.362 (2) | C46—C47 | 1.422 (8) |
C18—C23 | 1.373 (3) | C46—C47A | 1.581 (10) |
C19—H19 | 0.9300 | C47—H47A | 0.9600 |
C19—C20 | 1.388 (3) | C47—H47B | 0.9600 |
C20—H20 | 0.9300 | C47—H47C | 0.9600 |
C20—C21 | 1.341 (3) | C48—O1 | 1.177 (3) |
C21—H21 | 0.9300 | C48—O2 | 1.305 (2) |
C21—C22 | 1.373 (3) | C49—H49A | 0.9600 |
C22—H22 | 0.9300 | C49—H49B | 0.9600 |
C22—C23 | 1.378 (3) | C49—H49C | 0.9600 |
C23—H23 | 0.9300 | C49—O2 | 1.455 (3) |
C24—C25 | 1.381 (2) | C50—O3 | 1.170 (3) |
C24—C29 | 1.386 (2) | C50—O4 | 1.290 (2) |
C25—H25 | 0.9300 | C51—H51A | 0.9600 |
C25—C26 | 1.383 (3) | C51—H51B | 0.9600 |
C26—H26 | 0.9300 | C51—H51C | 0.9600 |
C26—C27 | 1.365 (3) | C51—O4 | 1.444 (3) |
C27—H27 | 0.9300 | C47A—H47D | 0.9600 |
C27—C28 | 1.374 (3) | C47A—H47E | 0.9600 |
C28—H28 | 0.9300 | C47A—H47F | 0.9600 |
C2—C1—C17 | 104.11 (14) | C24—C29—H29 | 119.7 |
C48—C1—C2 | 108.39 (15) | C28—C29—C24 | 120.55 (18) |
C48—C1—C17 | 112.08 (15) | C28—C29—H29 | 119.7 |
C50—C1—C2 | 113.12 (14) | C31—C30—C14 | 121.56 (15) |
C50—C1—C17 | 112.13 (15) | C31—C30—C35 | 117.97 (16) |
C50—C1—C48 | 107.04 (15) | C35—C30—C14 | 120.40 (15) |
C1—C2—H2A | 111.2 | C30—C31—H31 | 120.0 |
C1—C2—H2B | 111.2 | C30—C31—C32 | 120.02 (18) |
H2A—C2—H2B | 109.1 | C32—C31—H31 | 120.0 |
C3—C2—C1 | 102.67 (13) | C31—C32—H32 | 119.1 |
C3—C2—H2A | 111.2 | C33—C32—C31 | 121.7 (2) |
C3—C2—H2B | 111.2 | C33—C32—H32 | 119.1 |
C4—C3—C2 | 131.57 (14) | C32—C33—C36 | 121.1 (2) |
C4—C3—C16 | 117.85 (14) | C34—C33—C32 | 117.85 (18) |
C16—C3—C2 | 110.57 (14) | C34—C33—C36 | 120.9 (2) |
C3—C4—C5 | 133.03 (14) | C33—C34—H34 | 119.4 |
C3—C4—C13 | 120.84 (14) | C35—C34—C33 | 121.10 (19) |
C13—C4—C5 | 106.11 (13) | C35—C34—H34 | 119.4 |
C6—C5—C4 | 104.75 (12) | C30—C35—H35 | 119.4 |
C18—C5—C4 | 115.97 (13) | C34—C35—C30 | 121.17 (18) |
C18—C5—C6 | 123.82 (13) | C34—C35—H35 | 119.4 |
O5—C5—C4 | 98.61 (11) | C33—C36—H36A | 109.3 |
O5—C5—C6 | 99.63 (12) | C33—C36—H36B | 109.3 |
O5—C5—C18 | 110.08 (12) | H36A—C36—H36B | 108.0 |
C7—C6—C5 | 134.88 (17) | C37—C36—C33 | 111.5 (2) |
C7—C6—C11 | 120.18 (16) | C37—C36—H36A | 109.3 |
C11—C6—C5 | 104.84 (13) | C37—C36—H36B | 109.3 |
C6—C7—H7 | 120.9 | C36—C37—H37A | 109.5 |
C6—C7—C8 | 118.2 (2) | C36—C37—H37B | 109.5 |
C8—C7—H7 | 120.9 | C36—C37—H37C | 109.5 |
C7—C8—H8 | 119.2 | H37A—C37—H37B | 109.5 |
C9—C8—C7 | 121.52 (19) | H37A—C37—H37C | 109.5 |
C9—C8—H8 | 119.2 | H37B—C37—H37C | 109.5 |
C8—C9—H9 | 119.6 | C39—C38—C15 | 177.18 (19) |
C8—C9—C10 | 120.74 (19) | C38—C39—C40 | 178.44 (18) |
C10—C9—H9 | 119.6 | C41—C40—C39 | 121.27 (17) |
C9—C10—H10 | 121.0 | C45—C40—C39 | 120.69 (17) |
C11—C10—C9 | 118.07 (19) | C45—C40—C41 | 118.03 (17) |
C11—C10—H10 | 121.0 | C40—C41—H41 | 120.0 |
C6—C11—C12 | 105.85 (13) | C42—C41—C40 | 119.97 (19) |
C10—C11—C6 | 121.20 (16) | C42—C41—H41 | 120.0 |
C10—C11—C12 | 132.75 (16) | C41—C42—H42 | 119.1 |
C11—C12—C13 | 104.24 (12) | C43—C42—C41 | 121.9 (2) |
C24—C12—C11 | 121.28 (14) | C43—C42—H42 | 119.1 |
C24—C12—C13 | 120.73 (13) | C42—C43—C44 | 117.85 (19) |
O5—C12—C11 | 99.24 (12) | C42—C43—C46 | 121.6 (2) |
O5—C12—C13 | 99.41 (11) | C44—C43—C46 | 120.6 (3) |
O5—C12—C24 | 107.67 (12) | C43—C44—H44 | 119.3 |
C4—C13—C12 | 104.25 (12) | C43—C44—C45 | 121.4 (2) |
C14—C13—C4 | 122.24 (14) | C45—C44—H44 | 119.3 |
C14—C13—C12 | 133.42 (14) | C40—C45—H45 | 119.6 |
C13—C14—C15 | 116.80 (14) | C44—C45—C40 | 120.8 (2) |
C13—C14—C30 | 122.15 (14) | C44—C45—H45 | 119.6 |
C15—C14—C30 | 121.05 (14) | C43—C46—H46A | 108.4 |
C14—C15—C38 | 121.08 (14) | C43—C46—H46B | 108.4 |
C16—C15—C14 | 119.95 (14) | C43—C46—H46C | 109.6 |
C16—C15—C38 | 118.94 (14) | C43—C46—H46D | 109.6 |
C3—C16—C17 | 109.98 (14) | C43—C46—C47A | 110.3 (3) |
C15—C16—C3 | 122.27 (14) | H46A—C46—H46B | 107.5 |
C15—C16—C17 | 127.68 (14) | H46C—C46—H46D | 108.1 |
C1—C17—H17A | 111.2 | C47—C46—C43 | 115.4 (4) |
C1—C17—H17B | 111.2 | C47—C46—H46A | 108.4 |
C16—C17—C1 | 102.81 (13) | C47—C46—H46B | 108.4 |
C16—C17—H17A | 111.2 | C47A—C46—H46C | 109.6 |
C16—C17—H17B | 111.2 | C47A—C46—H46D | 109.6 |
H17A—C17—H17B | 109.1 | C46—C47—H47A | 109.5 |
C19—C18—C5 | 124.73 (15) | C46—C47—H47B | 109.5 |
C19—C18—C23 | 117.76 (17) | C46—C47—H47C | 109.5 |
C23—C18—C5 | 117.51 (15) | H47A—C47—H47B | 109.5 |
C18—C19—H19 | 119.5 | H47A—C47—H47C | 109.5 |
C18—C19—C20 | 120.91 (19) | H47B—C47—H47C | 109.5 |
C20—C19—H19 | 119.5 | O1—C48—C1 | 124.19 (19) |
C19—C20—H20 | 119.5 | O1—C48—O2 | 122.6 (2) |
C21—C20—C19 | 121.0 (2) | O2—C48—C1 | 113.25 (18) |
C21—C20—H20 | 119.5 | H49A—C49—H49B | 109.5 |
C20—C21—H21 | 120.5 | H49A—C49—H49C | 109.5 |
C20—C21—C22 | 118.92 (19) | H49B—C49—H49C | 109.5 |
C22—C21—H21 | 120.5 | O2—C49—H49A | 109.5 |
C21—C22—H22 | 119.9 | O2—C49—H49B | 109.5 |
C21—C22—C23 | 120.2 (2) | O2—C49—H49C | 109.5 |
C23—C22—H22 | 119.9 | O3—C50—C1 | 124.8 (2) |
C18—C23—C22 | 121.1 (2) | O3—C50—O4 | 122.0 (2) |
C18—C23—H23 | 119.4 | O4—C50—C1 | 113.23 (16) |
C22—C23—H23 | 119.4 | H51A—C51—H51B | 109.5 |
C25—C24—C12 | 122.00 (16) | H51A—C51—H51C | 109.5 |
C25—C24—C29 | 118.26 (16) | H51B—C51—H51C | 109.5 |
C29—C24—C12 | 119.55 (15) | O4—C51—H51A | 109.5 |
C24—C25—H25 | 119.6 | O4—C51—H51B | 109.5 |
C24—C25—C26 | 120.8 (2) | O4—C51—H51C | 109.5 |
C26—C25—H25 | 119.6 | C48—O2—C49 | 116.0 (2) |
C25—C26—H26 | 119.7 | C50—O4—C51 | 118.93 (19) |
C27—C26—C25 | 120.5 (2) | C5—O5—C12 | 98.72 (10) |
C27—C26—H26 | 119.7 | C46—C47A—H47D | 109.5 |
C26—C27—H27 | 120.3 | C46—C47A—H47E | 109.5 |
C26—C27—C28 | 119.43 (19) | C46—C47A—H47F | 109.5 |
C28—C27—H27 | 120.3 | H47D—C47A—H47E | 109.5 |
C27—C28—H28 | 119.8 | H47D—C47A—H47F | 109.5 |
C27—C28—C29 | 120.4 (2) | H47E—C47A—H47F | 109.5 |
C29—C28—H28 | 119.8 |
Cg4 and Cg7 are the centroids of the C3/C4/C13–C16 and C18–C23 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20···Cg4i | 0.93 | 2.61 | 3.516 (3) | 165 |
C26—H26···Cg7ii | 0.93 | 2.82 | 3.713 (3) | 162 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2. |
Funding information
We acknowledge financial support from the Key Natural Science Foundation of Anhui Higher Education Institution (KJ2017A446), the Excellent Young Talents Support Program of Anhui Higher Education Institutions (gxyq2018075).
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