Crystal Packing Motifs of Oligothiophenes End-Capped with N

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CRYSTAL GROWTH & DESIGN

Crystal Packing Motifs of Oligothiophenes End-Capped with N-Containing Aryls Wei Yue, HongKun Tian,* Ninghai Hu, Yanhou Geng,* and Fosong Wang State Key Laboratory of Polymer Physics and Chemistry, National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Graduate School of Chinese Academy of Sciences, Changchun 130022, P. R. China

2008 VOL. 8, NO. 7 2352–2358

ReceiVed NoVember 23, 2007; ReVised Manuscript ReceiVed March 20, 2008

ABSTRACT: Oligothiophenes (OThs) end-capped with 3-quinolyl or pyridyl with nitrogen atom at meta-, ortho- or para-position were synthesized. The single-crystal structures of the resulting molecules, i.e., o-PyTh4, m-PyTh4, p-PyTh4, QuTh2, and QuTh3, were successfully determined by single-crystal X-ray analysis. Pyridyl end-capped OThs, o-PyTh4, m-PyTh4, and p-PyTh4, adopt the different herringbone packing arrangement in crystals depending on the position of the nitrogen atom because of the presence of weak C-H · · · N hydrogen bonds. The p-PyTh4 molecules are linked each other along the long axis of the molecules to form the extended chains by C-H · · · N dimer synthon. For m-PyTh4, the C-H · · · N interactions two-dimensionally extend through C-H · · · N trimer synthon. The weak hydrogen-bonding network is much more complex in o-PyTh4 crystals because o-PyTh4 has two crystallographically independent molecules. Two-dimensional (2D) hydrogen-bonding networks arranging along the direction of diagonals in the ab plane are formed by the C-H · · · N trimer synthon. The crystal packing motifs of 3-quinolyl end-capped OThs are distinctly different from pyridyl end-capped ones. The QuTh2 molecules form a 2D face to face π-π slip stacking driven by the interaction of donor and acceptor segments between the neighboring molecules. For QuTh3, the weak C-H · · · N hydrogen bonds between the two molecules in the same layer and the CH/π weak interactions together force the molecules to form a sandwichherringbone crystal packing motif. These results provide a new protocol to control molecular packing arrangement of conjugated oligomers. Introduction The intermolecular packing arrangement is one of the critical factors governing the intermolecular electronic interaction and intermolecular charge transport properties of organic semiconductors.1 Therefore, understanding the nature of the intermolecular interactions and then controlling the molecular packing arrangement in the solid state are fundamental issues for obtaining the desired organic semiconducting materials. In principle, crystal packing motif of a given conjugated molecule is determined by a convolution of a large number of strong and weak interactions, typically including hydrogen bond, electrostatic forces, π-π interaction, and CH/π interaction. Each of these interactions affects the other intimately. A small change in the molecular structure, which may impart weak interactions or cause variation of electronic structure, can therefore result in the distinct crystal structures.2 Typical organic semiconductors, such as acenes and oligothiophenes (OThs), generally adopt herringbone packing arrangement in crystals because of the repulsion between π-orbitals and the CH/π interactions of neighboring molecules.3 However, this molecular packing arrangement meanwhile also cause reduction of intermolecular electronic interaction.1d,4 In the last several years, several strategies of molecular design have been reported by different groups to tune the packing arrangement of acenes. Anthony and co-workers reported that the introduction of the bulky alkynyl groups into acenes could tune the packing structure from a herringbone motif to a face-to-face π-π stacking motif.5 Sarma and Desiraju pointed out that halogen groups could promote π-stacking.6 Bao and co-workers also reported that tetracene with halogen atoms at 5,11-positions adopted a face-to-face π-π stacking crystal structure.7 The chalcogen-chalcogen interaction was also introduced by Kobayashi and co-workers to realize face-to-face π-π stacking arrangement of acenes.8 Moreover, * Corresponding author. E-mail: [email protected] (Y.G.); [email protected].

fused R-oligothiophenes with the relatively high C/H ratio can adopt the face-to-face π-π stacking arrangement in crystals due to the diminished CH/π interactions.9 In contrast, few approaches have been reported to modulate crystal structures of OThs. Almost all OThs reported to date adopt herringbone packing motifs in crystals, even when other aryl units, i.e., phenyl, biphenyl, naphthyl, and thionaphthyl, are incorporated.10 Effect of weak hydrogen bonds such as C-H · · · O and C-H · · · N interactions on crystal structures have been extensively investigated in crystal engineering area, and it was found that these weak interactions could play a significant role in packing arrangement of the molecules.2,11 Most importantly, the weak hydrogen bonds can have a influence on crystal structures even when the strong interactions, i.e., strong hydrogen bonds and π-π interactions, exist and act as the main driving forces of the molecular packing arrangement.12,13 The basic nitrogen atom and acidic C-H in electron-deficient heterocyclic aromatic units such as pyridine13 and pyrazine14 have been proved to be able to form C-H · · · N weak hydrogen bonds for tuning crystal structures of the nonconjugated small molecules. In addition, thiazole-containing oligomers tend to exhibit π-stacking motif, which is different from OThs.15 Following these clues, we designed and synthesized three pyridyl end-capped OThs and two 3-quinolyl end-capped OThs, i.e., o-PyTh4, m-PyTh4, p-PyTh4, QuTh2, and QuTh3 (Figure 1), for modulation of crystal packing motif of OThs. Their single crystals were grown from slow sublimation and the structures were successfully determined. Results and Discussion Crystal Structures of Pyridyl End-Capped OThs. The single crystals of three pyridyl end-capped OThs are all monoclinic and belong to space groups Cc with Z ) 8, P21/c with Z ) 2, and P21/c with Z ) 2 for o-PyTh4, m-PyTh4, and

10.1021/cg701148z CCC: $40.75  2008 American Chemical Society Published on Web 06/07/2008

Motifs of Oligothiophenes End-Capped with Aryls

Figure 1. Chemical structures of pyridyl and 3-quinolyl end-capped OThs.

p-PyTh4, respectively, and their detailed crystallographic data are summarized in Table 1. Depending on the position of N atom in pyridyl units relative to neighboring thiophene unit, the molecules adopt different conformations. As shown in Figure 2a-c, although quaterthiophene segments (Th4) in the pyridyl end-capped OThs are all quasi-planar, i.e., the inter-ring dihedral angle is 2σ(I)] wR2 [I > 2σ(I)] R1 (all data) wR2 (all data) final diff Fmax (e Å3)

o-PyTh4

m-PyTh4

p-PyTh4

QuTh2

QuTh3

C26H16N2S4 484.65 293 (2) monoclinic Cc 9.750 (2) 16.272 (3) 27.749 (6) 90.00 91.229 (3) 90.00 4401.5 (16) 8 1.463 0.450 1.47-26.02 12221 5805 5320 0.0196 1.030 0.0349 0.0884 0.0386 0.0918 0.230, -0.250

C26H16N2S4 484.65 293 (2) monoclinic P21/c 21.339 (8) 5.714 (2) 8.900 (3) 90.00 90.529 (5) 90.00 1085.2 (7) 2 1.483 0.456 2.86-26.05 5484 2120 1708 0.0202 1.051 0.0369 0.0973 0.0471 0.1041 0.299, -0.233

C26H16N2S4 484.65 293 (2) monoclinic P21/c 23.490 (3) 7.7172(10) 5.9857 (8) 90.00 94.968 (2) 90.00 1081.0 (2) 2 1.489 0.458 1.74-26.02 5742 2117 1729 0.0240 0.996 0.0350 0.0937 0.0436 0.1005 0.228, -0.233

C26H16N2S2 420.53 293(2) triclinic P1 6.1928(11) 8.2608(14) 9.9612(17) 85.299(2) 75.535(2) 76.100(2) 478.86(14) 1 1.458 0.295 2.11-25.04 2489 1668 1536 0.0068 1.081 0.0326 0.0872 0.0351 0.0902 0.175, -0.196

C30H18N2S3 502.64 293(2) monoclinic P21/c 21.688(4) 5.9423(10) 17.939(3) 90.00 97.188(3) 90.00 2293.8(7) 4 1.456 0.347 1.89-25.25 11514 4137 2681 0.0369 0.803 0.0489 0.1220 0.0852 0.1500 0.273, -0.221

respectively. To adapt these C-H · · · N trimer synthons, 2D hydrogen-bonded networks arranging along the direction of

diagonals in ab plane are formed (Figure 6). Meanwhile, from the above discussion on the packing diagram shown in Figure

Figure 2. ORTEP front views and side views of (a) o-PyTh4, (b) m-PyTh4, and (c) p-PyTh4.

Motifs of Oligothiophenes End-Capped with Aryls

Crystal Growth & Design, Vol. 8, No. 7, 2008 2355

Figure 4. Hydrogen bonding spatial sketch map of (a) o-PyTh4, (b) m-PyTh4, and (c) p-PyTh4. (For clarity, partial aryl rings in the molecules were omitted.)

Figure 3. Packing diagrams of o-PyTh4 (a) along the a axis and (b) along the molecular long axis, (c) m-PyTh4, and (d) p-PyTh4 along the molecular long axis (the hydrogen atoms were omitted for clarity). Table 2. Hydrogen Bond Parameters in the Crystal Structure of o-PyTh4, m-PyTh4, p-PyTh4, and QuTh3 compd

C-H · · · N

C(25)-H · · · N(3) C(29)-H · · · N(2) m-PyTh4 C(12)-H · · · N(1) p-PyTh4 C(11)-H · · · N(1) QuTh3 C(26)-H · · · N(1) C(8)-H · · · N(2) o-PyTh4

H · · · N (Å) C · · · N (Å) C-H · · · N (deg) 2.68 2.71 2.68 2.80 2.60 2.756

3.465(3) 3.365(5) 3.537(3) 3.457(3) 3.462(5) 3.563(4)

142 128 153 128 155 146

3a-d, molecules in the same layer still adopt herringbone packing arrangement mediated by CH/π weak interactions and π-π interactions, identical to the case in the most of reported OThs.3b,c Therefore, C-H · · · N contacts mainly affects the interlayer packing arrangement of the molecules, but are also important factors determining intermolecular arrangement in the same layer. Crystal Structures of 3-Quinolyl End-Capped OThs. QuTh2 and QuTh3 crystallize in P1 and P21/c space groups with Z ) 1 and Z ) 4, respectively (see Table 1). As shown in Figure 7, the position of the N atom relative to the S atom in the adjacent thiophene unit is different for these two molecules. In QuTh2, the N and S atoms show a trans-conformation, whereas they adopt a cis-conformation in QuTh3 molecules. QuTh2 have only one conformer with a center of symmetry lying on the middle of the molecule. The two thiophene rings are strictly coplanar in this molecule, and a dihedral angle of 8.4° between the quinolyl unit and thiophene ring, larger than that of naphthyl end-capped bithiophene (3.7°),10c was found (Figure 7a). For QuTh3 (Figure 7b), only one conformer without a center of symmetry was observed. The terthiophene segment (Th3) is also quasi-planar with smaller dihedral angles between the 3-quinolyl unit and terthiophene segment (1.8 and 2.5°). The whole molecule exhibits a more planar structure than naphthyl and thionaphthyl end-capped terthiophenes.10c The crystal packing motifs of QuTh2 and QuTh3 are distinctly different from o-PyTh4, m-PyTh4, p-PyTh4, and naphthyl/thionaphthyl end-capped bithiophenes and terthiophenes.10c All these molecules exhibit the herringbone packing arrangement. Figure 8 shows the packing diagrams of QuTh2 and QuTh3. The QuTh2 molecules form a face-to-face π-π

slip stacking along the b axis with a face-to-face distance of 3.57 Å (Figure 8a), whereas the QuTh3 molecules adopt a herringbone packing arrangement with a dimer structure as illustrated in Figure 8b. This packing structure is also named sandwich-herringbone, which is seldom observed in organic conjugated semiconductors.6,8a,17 The dimer molecules form a face-to-face π-π slip stacking with a face-to-face distance of 3.55 Å. The herringbone angle of QuTh3 is 46.0°, which is the minimal value among the four molecules following the herringbone crystal packing motifs in current report and also smaller than the that of naphthyl end-capped terthiophene (51.6 and 74.2°).10c The close intermolecular C · · · C′ contacts are within 3.607(4) Å, with the shortest one being 3.530(4) Å (C17 · · · C′11). The intermolecular shortest S · · · S′ and S · · · C distances are 4.027(3) and 3.771(3) Å, respectively. Moreover, the distance between molecular centers of transverse dimers is 5.42 Å, larger than that of naphthyl end-capped terthiophene.10c Weak C-H · · · N hydrogen-bonding interactions were also found in QuTh3 crystals. But different from those in the pyridyl end-capped OThs, in which the C-H · · · N interaction occurred between the molecules from different layers, the hydrogen bonds in QuTh3 crystals are formed between the adjacent molecules in the same layer. As shown in Figure 9a and Table 2, two C-H · · · N contacts with the H · · · N distance of 2.60 (H(26) · · · N(1), hydrogen bond angle: 155°) and 2.76 Å (H(8) · · · N(2), hydrogen bond angle: 146°) were observed. Although the distance of H(8) · · · N(2) is 2.76 Å, little larger than the 2.75 Å, we still list this C-H · · · N contact as the weak hydrogen bond considering it can stabilize the C(26)-H · · · N(1) weak interaction. The two neighboring molecules in the same layer are rivet by each other via four weak hydrogen bonds to form a dimer structure arranged perpendicularly to the (304) plane (Figure 10). In consequence, these weak interactions with the CH/π weak interactions and π-π interactions together induce the sandwichherringbone arrangement of QuTh3. For QuTh2, the formation of the 2D face-to-face π-π slip stacking may be attributed to a favorable donor-acceptor (D-A) interaction between the 3-quinolyl unit (acceptor) and the thiophene unit (donor) of the adjacent molecules (Figure 9b), similar to that of 5,5′-bis(4,4′dibutyl-2,2′-bithiazol-5-yl)-(3,4,3′,4′-bis(ethylenedioxy)-2,2′dithienyl) (BT2B).15 The different crystal packing motifs of QuTh2 and QuTh3 indicate that the molecular length, which might be able to affect the relative strength of different weak interactions, is also an important factor determining molecular arrangement in crystals. Conclusions The single-crystal structures of five conjugated oligomers, i.e., o-PyTh4, m-PyTh4, p-PyTh4, QuTh2, and QuTh3, have

2356 Crystal Growth & Design, Vol. 8, No. 7, 2008

Yue et al.

Figure 5. Hydrogen-bonded network of (a) p-PyTh4 and (b) m-PyTh4.

Figure 6. Hydrogen-bonded network of o-PyTh4.

Figure 8. Packing diagrams of (a) QuTh2 and (b) QuTh3 (hydrogen atoms were omitted for clarity).

Figure 9. Hydrogen bonding spatial sketch map of (a) QuTh3, and (b) the sketch map of interaction between the 3-quinolyl group (acceptor) and the thiophene group (donor) of the adjacent molecules (for clarity, partial aryl rings in the molecules were omitted). Figure 7. ORTEP front views and side views of (a) QuTh2 and (b) QuTh3.

been resolved. It was found that introduction of nitrogencontaining aryls into the terminals of OThs could introduce weak

C-H · · · N or D-A interactions, thereby affecting the crystal packing motifs. For pyridyl end-capped OThs o-PyTh4, mPyTh4, and p-PyTh4, the weak C-H · · · N hydrogen bonds occur between the interlayer molecules. Depending on the position of the nitrogen atoms, one- and two-dimensional

Motifs of Oligothiophenes End-Capped with Aryls

Figure 10. Hydrogen bonding network of QuTh3.

hydrogen bonding networks connected by C-H · · · N dimer and trimer synthons can be formed. The different crystal packing motifs were found in crystals of QuTh2 and QuTh3. For QuTh2, the D-A interaction between quinolyl and thiophene units becomes the dominating factor to determine the crystal packing motif, and the 2D face-to-face π-π slip stacking was observed. For the longer molecule, QuTh3, the weak C-H · · · N hydrogen bonds between the dimer molecules and the CH/π weak interactions may be together force the molecules to form a sandwich-herringbone crystal structure. Experimental Section Materials. All chemical reagents and solvents were used as received from commercial sources without further purification except diethyl ether (Et2O) and N,N-dimethyl formamide (DMF) that had been distilled over sodium/benzophenone and CaH2, respectively. The compounds 5,5′′′-bis(pyrid-2-yl)-2,2′:5′,2′′:5′′,2′′′-quaterthiophene (o-PyTh4),18a 5,5′′′-bis(pyrid-4-yl)-2,2′:5′,2′′:5′′,2′′′-quarter-thiophene (p-PyTh4),18b 5,5′-bis(quinol-3-yl)-2,2′-bithiophene (QuTh2),19 5,5′-bis(tributylstannyl)- 2,2′-bithiophene,20 and 5,5′′-bis(tributylstannyl)-2,2′:5′,2′′-terthiophene21 were prepared according to the literature. 3-Thien-2-yl-pyridine: 2-Thienylmagnesium bromide in anhydrous Et2O (50 mL, prepared from 6.52 g (40.0 mmol) 2-bromothiophene) was added dropwise to a stirred suspension of 3-bromopyridine (4.10 g, 50.6 mmol) and Pd(dppf)Cl2 (60.0 mg, 0.07 mmol) in anhydrous Et2O (60 mL) at -20 °C. The mixture was stirred overnight at room temperature and then poured into a saturated aqueous ammonium chloride solution (160 mL). The aqueous layer was extracted with Et2O (3 × 100 mL). The combined organic layers were washed with brine (3 × 100 mL) and subsequently dried with anhydrous MgSO4. After removal of the solvent, the residue was purified by column chromatography over Al2O3 with petroleum ether /dichloromethane (1:3) as eluent to give 3-thien-2-yl-pyridine as a yellow liquid (3.78 g, 92.6%). 1 H NMR (CDCl3, 300 MHz): δ (ppm) 8.92 (d, J ) 1.92 Hz, 1H), 8.55 (dd, J ) 4.80 Hz, 1.47 Hz, 1H), 7.88-7.92 (m, 1H), 7.38-7.40 (m, 2H), 7.33 (dd, J ) 4.32 Hz, 4.17 Hz,1H), 7.15 (dd, J ) 4.83 Hz, 3.87 Hz,1H). 3-(5-Bromothien-2-yl)-pyridine: 3-Thien-2-yl-pyridine (4.62 g, 28.7 mmol) in acetic acid (170 mL) was refluxed and then bromine (6.86 g, 43.0 mmol) in acetic acid (30 mL) was added dropwise. After the addition the mixture was refluxed for further 3 h. The mixture was cooled to room temperature and then poured into water (300 mL) and neutralized with ammonia solution (25%) to pH 7-8. The mixture was extracted with dichloromethane (4 × 150 mL). The combined organic extracts were washed with brine (3 × 150 mL) and subsequently dried with anhydrous MgSO4. After removal of the solvent, the residue was recrystallized from petroleum ether to afford 3-(5-bromothien-2yl)pyridine as a light yellow solid (5.77 g, 83.9%). 1H NMR (CDCl3, 300 MHz): δ 8.80 (d, J ) 2.37 Hz, 1H), 8.54 (dd, J ) 4.80 Hz, 1.41 Hz, 1H), 7.76-7.80 (m, 1H), 7.29-7.33 (m, 1H), 7.11 (d, J ) 3.9 Hz, 1H), 7.08 (d, J ) 3.7 Hz, 1H). General Synthesis Procedure for m-PyTh4 and QuTh3. Into a Schlenk tube with bromo-substituted compounds (2.2 equiv.), corresponding bis(trin-butylstannyl)-substituted OThs (1 equiv.), and Pd(PPh3)4 (0.3 mol% to bromo-substituted compounds) was added anhydrous DMF. The mixture was stirred under argon at 90 °C for 1 day. After the reaction mixture had cooled to room temperature, the

Crystal Growth & Design, Vol. 8, No. 7, 2008 2357 precipitate was collected by filtration and washed successively with water and acetone. The precipitate was then extracted with anhydrous toluene in Soxhlet extractor. The product was further purified by vacuum sublimation twice before characterization. 5,5′′′-Bis(pyrid-3-yl)-2,2′:5′,2′′:5′′,2′′′-quaterthiophene(m-PyTh4). Into a mixture of 3-(5-bromothien-2-yl)pyridine (6.00 g, 25.0 mmol), 5,5′-bis(tributylstannyl)-2,2′-bithiophene (8.46 g, 11.4 mmol), and Pd(PPh3)4 (0.39 g, 0.34 mmol) was added anhydrous DMF (160 mL). Red-yellow (2.68 g, 48.6%) crystals were obtained. M.p.: 304 °C (from DSC measurement). Anal. Calcd for C26H16N2S4: C, 64.43; H, 3.33; N, 5.78. Found: C, 64.52; H, 3.42; N, 5.73. 5,5”-Bis(quinol-3-yl)-2,2′:5′,2′′:5′′-terthiophene (QuTh3). Into a mixture of 3-bromoquinoline (3.64 g, 17.5 mmol), 5,5′′-bis(tributylstannyl)-2,2′:5′,2′′-terthiophene (6.58 g, 7.96 mmol), and Pd(PPh3)4 (0.27 g, 0.23 mmol) was added anhydrous DMF (120 mL). Orange (1.76 g, 44.0%) crystals were obtained. M.p.: 285 °C (from DSC measurement). Anal. Calcd for C30H18N2S3: C, 71.68; H, 3.61; N, 5.57. Found: C, 71.83; H, 3.62; N, 5.03. Crystallography. Data collection was carried out at 293 K with graphite-monochromated Mo KR radiation (λ ) 0.71073 Å) on a Bruker Smart APEX diffractometer with a charge-coupled device (CCD) detector and graphite monochromator. Lorentz and polarization corrections were applied to the data sets. The intensity data were collected in ω scan mode, and absorption corrections were performed using the SADABS program.21 The crystal structure was solved using the SHELXTL program and refined using full matrix least-squares.22 The hydrogen atom positions were calculated theoretically and included in the final cycles of refinement in a riding model along with attached carbon atoms. CCDC reference numbers 627860-627862 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Acknowledgment. This work is supported by the 973 Project (2002CB613404) of the Chinese Ministry of Science and Technology, NSFC (20423003 and 20521415), and the Science Fund for Creative Research Groups of NSFC (20621401). Supporting Information Available: X-ray crystallographic files (CIF); calculated distances of close intermolecular contacts, interlayer packing diagrams of p-PyTh4 and P6T, film UV-vis absorption spectra, TGA profiles, and DSC scans of the OThs end-capped with 3-quinolyl or pyridyl (PDF). This material is available free of charge via the Internet at http://pubs.acs.org.

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2358 Crystal Growth & Design, Vol. 8, No. 7, 2008 (11) (a) Desiraju, G. R.; Steiner, T. The Weak Hydrogen Bond in Structural Chemistry and Biology; Oxford Science Publications; Oxford, U.K., 1999; (b) Steiner, T. Angew. Chem., Int. Ed. 2002, 41, 48. (12) (a) Barclay, T. M.; Cordes, A. W.; MacKinnom, C. D.; Oakley, R. T.; Reed, R. W. Chem. Mater. 1997, 9, 981. (b) Koren, A. B.; Curtis, M. D.; Kampf, J. W. Chem. Mater. 2000, 12, 1519. (c) Zhang, H.; Zhang, Z.; Ye, K.; Zhang, J.; Wang, Y. AdV. Mater. 2006, 18, 2369. (13) (a) Sarkar, M.; Biradha, K. Cryst. Growth Des. 2006, 6, 202. (b) Lai, C.-S.; Mohr, F.; Tiekink, E. R. T. CrysEngComm. 2006, 8, 909. (14) Thalladi, V. R.; Gehrke, A.; Boese, R. New J. Chem. 2000, 24, 463. (15) Curtis, M. D.; Cao, J.; Kampf, J. W. J. Am. Chem. Soc. 2004, 126, 4318. (16) Horowitz, G.; Bachet, B.; Yassar, A.; Lang, P.; Demanze, F.; Fave, J.; Garnier, F. Chem. Mater. 1995, 7, 1337. (17) Kono, T.; Kumaki, D.; Nishida, J.; Sakanoue, T.; Kakita, M.; Tada, H.; Tokito, S.; Yamashita, Y. Chem. Mater. 2007, 19, 1218.

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