A 3D-Honeycomb Network with Unique Encapsulation of Dimers of 1D-Chains Kumar Biradha* and Goutam Mahata Department of Chemistry, Indian Institute of Technology, Kharagpur-721302, India Received February 23, 2004;
CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 1 49-51
Revised Manuscript Received April 5, 2004
ABSTRACT: Arylmonosulfonates upon treatment with 4,4′-bipyridine resulted in the formation of a 3D-honeycomb network containing continuous channels, which are occupied by the π stacking dimers of 1D-chains of 4,4′-bipyridine-H, and a bilayer architecture. Development of novel supramoleular synthons is an important aspect of crystal engineering as it generates new structures with novel architectures and topologies which in turn lead to new materials and properties.1 The synthon I formed between carboxylates and pyridine moieties was well exploited to engineer several crystalline architectures.2,3 However, the isostructural synthon II that can be formed between sulfonates and pyridine moieties has not been explored to that extent.4 To exploit II, we have carried out the reactions of sulfanilic acid (SA)/p-toluenesulfonic acid (TSA) with 4,4′-bipyridine (bipy). Recently, a series of organodisulfonates and guanidinium ions were shown to assemble into lamellar architectures (Scheme 1b).1f,5 In Scheme 1 a
a (a) Supramolecular synthons between (I) carboxylate and pyridinium; (II) sulfonate and pyridinium; layered architectures between (b) guanidinium and sulfonate ions; (c) H2O and sulfonate ion.
these structures, sulfonates and guanidinum ions form a 2D-layer that serves as a basic building block. Here, we observed two more interesting ways of sulfonates forming layered materials. In one of those cases, water assembles the sulfonate ions to form a honeycomb layer via O-H‚‚‚O hydrogen bonds (Scheme 1c), whereas in the other case, 4,4′-bipyridine assembles sulfonates via synthon II and C-H‚‚‚O hydrogen bonds. Crystals of the complex, (bipy-H)(SA)‚2(H2O), 1, were grown in water, only 1 equiv of SA reacted with bipy although 2 equiv of SA was used in the reaction.6 The single-crystal analysis of the structure reveals the forma* To whom correspondence should be addressed. Fax: +91-3222-282252; tel: +91-3222-283346; e-mail:
[email protected].
Figure 1. Illustration of the crystal structure 1: (a) layer formed between sulfonates and water molecule (C6H4-NH2 were not shown for the sake of clarity); (b) space filling drawing of the 3D-network exhibited in 1; bipy-H moieties were shown in cylinder mode (green color).
tion of a layer via O-H‚‚‚O hydrogen bonds (O‚‚‚O 2.727, 2.837, 2.814, 2.924 Å).7 The 2D-layer is highly corrugated, and H2O assumes the role of a spacer in assembling the sulfonates into a distorted honeycomb layer (Figure 1a). The C6H4-NH2 moieties hang above and below the layers. In principle, 1.5 equiv of water (three donors) is enough per sulfonate (three acceptors); however, one of the sulfonate O-atom forms bifurcated O-H‚‚‚O bonds (accepting two protons), as we have two water molecules (four donors)
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Figure 2. Dimers of 1D-chains exhibited in crystal structure of 1: (a) side view; (b) top view.
Figure 3. Illustration for crystal structure 2; a) hydrogen bond layer between bipy-H2 and sulfonates (p-CH3-C6H4 groups were not shown for the sake of clarity); (b) bilayer architecture, please note the interdegitation of tolyl groups.
per sulfonate in the crystal. These layers are linked together by the NH2 of SA and H2O via N-H‚‚‚O interactions (N‚‚‚O, N-H‚‚‚O; 3.006 Å; 153°; 3.065 Å, 170°) to form a 3D-honeycomb network (Figure 1b). Further, the protonated bipy does not form synthon II with sulfonates but interacts with itself to form a 1D-chain (N‚‚‚N, N-H‚‚‚N; 2.726 Å, 172°). Two of these 1D-chains assemble with each other via π-π interactions in centrosymmetric fashion and fit in the channels of the 3Dhoneycomb network (Figure 2).8 In the dimeric coloumn, bipy units stack on each other with a plane-plane distance of 3.6 Å. Protonated pyridine rings stack in an offset fashion, while the neutral pyridine rings perfectly stack on each other (center‚‚‚center 3.68 Å). The monomeric chains are polar in direction but oppose each other in the dimer. In contrast to the above reaction, 2 equiv of TSA was found to react with 1 equiv of bipy in water to form the crystals of (bipy-H2)(TSA)2, 2.9 The crystal structure analysis reveals the formation of bilayer architecture (Figure 3). Unlike the above structure, sulfonates are involved in the formation of synthon II with bipy-H2 (N‚‚‚O, N-H‚‚‚O; 2.995 Å, 124°; 2.812 Å, 147°; 3.108 Å, 122°; 2.820 Å, 149°; C‚‚‚O, C-H‚‚‚O 3.434 Å, 180°, 3.492 Å, 174°; 3.526 Å, 174°; 3.213 Å; 144°). Each bipy was surrounded by six sulfonates; four are engaged in synthon II formation and the other two are engaged in C-H‚‚‚O hydrogen bonds formation. It is worthy to note that the inversion center exists between the layers but not within the layer. The tolyl groups of adjacent layers interdegitate each other with the interlayer separation of 10 Å. On the other hand, C-H‚‚‚O and N-H‚‚‚O hydrogen bond layers pack on each other such that there are no π-π interactions between bipy units, and the interlayer separation is 3 Å. These results indicate that the matching of acid and base strengths of sulfonic acid and bipy are important in determining the
stoichiometry of complex and synthons formation. The bilayer structure observed here has striking similarities with those of the complexes between trimesic acid and N-alkylamines.10 Supporting Information Available: Crystallographic data (CIF) of compounds. This material is available free of charge via the Internet at http://pubs.acs.org.
References (1) Desiraju, G. R. Crystal Engineering, The Design of Organic Solids; Elsevier: Amsterdam, 1989; (b) Lehn, J. M. Supramolecular Chemistry: Concepts and Perspectives; VCH: Weinheim, Germany, 1995; (c) Philp, D.; Stoddart, J. F. Angew. Chem., Int. Ed. Engl. 1996, 35, 1154; (d) Steed, J.; Atwood, J. L.; Supramolecular Chemistry; John Wiley & Sons: New York, 2000; (e) Desiraju, G. R. in Stimulating Concepts in Chemistry; F. Vo¨gtle, F., Stoddart, J. F., Shibasaki, M., Eds.; Wiley-VCH: Weinheim, Germany, 2000; p 293; (f) Holman, K. T.; Pivovar, A. M.; Swift, J. A.; Ward, M. D. Acc. Chem. Res. 2001, 34, 107; (g) Aakero¨y, C. B.; Beatty, A. M.; Helfrich, B. A. Angew. Chem., Int. Ed. 2001, 40, 3240; (h) Aakero¨y, C. B. Acta Crystallogr. 1997, B53, 569; (i) Biradha, K. CrystEngComm 2003, 5, 274. (2) Sharma, C. V. K.; Zaworotko, M. J.; Chem. Commun. 1996, 2655; (b) Bhogala, B. R.; Vishweshwar, P.; Nangia, A. Cryst. Growth Des. 2002, 2, 325; (c) Bhogala, B. R.; Nangia, A. Cryst. Growth Des. 2003, 3, 547. (3) Recently synthon I was shown to be important in the crystal engineering of the composition of pharmaceutical phases; Walsh, R. D. B.; Bradner, M. W.; Fleischman, S.; Morales, L. A.; Moulton, B.; Hornedo, N. R.; Zaworotko, M. J. Chem. Commun. 2003, 186. (4) Barbour, L. J.; Atwood, J. L. Chem. Commun. 2001, 2020. (5) Holman, K. T.; Martin, S. M.; Parker, D. P.; Ward, M. D. J. Am. Chem. Soc. 2001, 123, 4421; (b) recent review on supramolecular chemistry of sulfonate: Coˆte´, A. O., Shimzu, G. K. H. Coord. Chem. Rev. 2003, 245, 49.
Communications (6) Usage of 1:1 equiv of molecular components also resulted in a similar type of crystals. The reaction was tried in other solvents (MeOH and CH3CN) to avoid water, but resulted in powdered material. (7) The single-crystal data was collected on a Bruker-Nonius Mach3 CAD4 X-ray diffractometer that uses graphite monochromated Mo KR radiation (λ ) 0.71073 Å) by ω-scan method. The structure was solved by direct methods and refined by least-squares methods on F2 using SHELX-97. Non-hydrogen atoms were refined anisotropically, and hydrogen atoms were fixed at calculated positions and refined using a riding model. Crystal data 1: C16H19N3O5S, M ) 361.37, monoclinic, space group ) P2(1)/n; a ) 9.753(2); b ) 10.353(2); c ) 17.208(3) Å, β ) 99.79(3)°; U ) 1712.2(6), Z ) 4, Dc ) 1.402 g cm-3, R1 ) 0.0623, wR2 ) 0.1490. Calc: C 52.60; H 5.205; N 11.50; exp. C 51.19; H 4.85; N 11.70.
Crystal Growth & Design, Vol. 5, No. 1, 2005 51 (8) One-dimensional coordination polymer of bipy was shown to be encapsulated by a hydrogen bond network of anion of SA and H2O: Wang, Y.; Feng, L.; Li, Y.; Hu, C.; Wang, E.; Hu, N.; Jia, H. Inorg. Chem. 2002, 41, 6351. (9) Crystal data 2: C24H24N2O6S2, M ) 500.57, orthorhombic, space group ) Pbca; a ) 9.521(2); b ) 19.944(4); c ) 26.149(5) Å, U ) 4965.4(17), Z ) 8, Dc ) 1.339 g cm-3, R1 ) 0.0687, wR2 ) 0.1715. Calc: C 57.548; H 4.779; N 5.575; exp. C 56.90; H 4.46; N 5.27. (10) Biradha, K.; Dennis, D.; Poirier, K. M.; Sharma, C. V. K.; Zaworotko, M. J. Transactions of the American Crystallographic Association; Rogers, R. D., Zaworotko, M. J., Eds.; American Crystallographic Association: Pittsburgh, PA, 1998; Vol. 33, p 85; (b) Biradha, K.; Dennis, D.; MacKinnon, V. A.; Sharma, C. V. K.; Zaworotko, M. J. J. Am. Chem. Soc. 1998, 120, 11894.
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