Hydrogen-Bonded Analogues of Cavitands
Alexander Shivanyuk Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorThomas P. Spaniol Dr.
Institut für Anorganische Chemie und Analytische Chemie Fachbereich Chemie und Pharmazie Johannes Gutenberg-Universität Duesbergweg 10–14, 55099 Mainz (Germany)
Search for more papers by this authorKari Rissanen Prof. Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorErkki Kolehmainen Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorVolker Böhmer Dr.
Abteilung Lehramt Chemie Fachbereich Chemie und Pharmazie, Johannes Gutenberg-Universität Duesbergweg 10–14, 55099 Mainz (Germany)
Search for more papers by this authorAlexander Shivanyuk Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorThomas P. Spaniol Dr.
Institut für Anorganische Chemie und Analytische Chemie Fachbereich Chemie und Pharmazie Johannes Gutenberg-Universität Duesbergweg 10–14, 55099 Mainz (Germany)
Search for more papers by this authorKari Rissanen Prof. Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorErkki Kolehmainen Dr.
Department of Chemistry University of Jyväskylä P.O. Box 35, 40351, Jyväskylä (Finland) Fax: (+358) 14 2602-501
Search for more papers by this authorVolker Böhmer Dr.
Abteilung Lehramt Chemie Fachbereich Chemie und Pharmazie, Johannes Gutenberg-Universität Duesbergweg 10–14, 55099 Mainz (Germany)
Search for more papers by this authorWe are grateful to Mr. R. Kauppinen for his assistance with NMR measurements. This work was supported by the Finnish Academy.
Abstract
The shallow cavity of resorcarene is extended at the wide rim by a cyclic hydrogen-bonded array of four halide ions and four ammonium groups. Depending on the anion (chloride, bromide) these structures are capable of complexing certain alcohols by the formation of hydrogen bonds and inclusion into the π-basic cavity of the resorcarene (see picture).
References
- 1 M. M. Conn, J. Rebek, Jr., Chem. Rev. 1997, 97, 1647–1668.
- 2a
B. C. Hamman, K. D. Shimizu, J. Rebek, Jr., Angew. Chem. 1996, 108, 1425–1427; Angew. Chem. Int. Ed. Engl. 1996, 35, 1326–1329;
10.1002/ange.19961081214 Google Scholar
- 2b O. Mogck, E. F. Paulus, V. Böhmer, I. Thondorf, W. Vogt, Chem. Commun. 1996, 2533–2534.
- 3 D. M. Rudkevich, G. Hilmersson, J. Rebek, Jr., J. Am. Chem. Soc. 1998, 120, 12 216–12 225.
- 4 For a review on resorcarenes, see P. Timmerman, W. Verboom, D. N. Reinhoudt, Tetrahedron 1996, 52, 2663–2704.
- 5a Y. Matsushita, T. Matsui, Tetrahedron Lett. 1993, 34, 7433–7437;
- 5b W. Iwanek, J. Mattay, Liebigs Anal. 1995, 1463–1469;
- 5c M. T. El Gihani, H. Heaney, A. M. Z. Slawin, Tetrahedron Lett. 1995, 4905–4908;
- 5d R. Arnecke, V. Böhmer, E. F. Paulus, W. Vogt, J. Am. Chem. Soc. 1995, 117, 3286–3287.
- 6 K. Airola, V. Böhmer, E. F. Paulus, K. Rissanen, C. Schmidt, I. Thondorf, W. Vogt, Tetrahedron 1997, 10 709–10 724.
- 7 Crystallographic data measurements were carried out at 173.0(2) K on a Kappa-CCD diffractometer using MoKα radiation (graphite monochromator, λ=0.7107 Å). Direct methods (G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467) and full-matrix-block refinement versus F 2 ( G. M. Sheldrick, SHELXL-97, Programm for the Refinement of Crystal Structures, Universität Göttingen, Germany, 1997) were used to solve the structure. The disordered parts of the butyl chains and one water molecule with partial occupancy were treated isotropically. No absorption correction was applied. C52H80N4O8Cl4×2 MeCN×1.75 H2O; crystal dimensions 0.4×0.2×0.2 mm3, monoclinic, P21/a, a=22.4419(3), b=22.9653(5), c=24.8565(4) Å, β=113.457(9)o, Z=4, V=12263.7(4) Å3, ρcalcd=1.217 g cm−3, 2θmax=50.02o, μ=0.25 mm−1, 1485 parameters, R=0.1172 (for 14 640 reflections I>2σ(I)), wR(F 2)=0.3185 for all 21 494 reflections (Rint=0.044), S=1.057, min/max residual electron density=−0.52/0.79 e Å−3. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-142155. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: [email protected]).
- 8 For the extension of the resorcarene cavity by hydrogen-bonded pyridine bases, see
- 8a L. R. MacGillivray, J. L. Atwood, J. Am. Chem. Soc. 1997, 119, 6931–6932;
- 8b L. R. MacGillivray, J. L. Atwood, Chem. Commun. 1999, 181–182;
- 8c L. R. MacGillivray, H. A. Spinney, J. L. Reid, J. A. Ripmeester, Chem. Commun. 2000, 517–518.
- 9 For anion recognition, see F. Schmidtchen, M. Berger, Chem. Rev. 1997, 97, 1609–1646.
- 10 Compare with, for example, W. Xu, J. J. Vittal, R. J. Puddephat, J. Am. Chem. Soc. 1995, 117, 8362–8371.
- 11 The inverse ratio of 4:1 was observed for these signals with [Et3NH+Br−]:[1 c4+⋅4 Cl−]=1:1.
- 12 This result is also in accordance with the fact that no interaction occurs between the acetonitrile molecule and 1 c4+⋅4 Cl− in CDCl3.
- 13 D. J. Cram, S. Karbach, H.-E. Kim, C. B. Knobler, E. F. Maverick, J. L. Ericson, R. C. Helgeson, J. Am. Chem. Soc. 1988, 110, 2229–2237.
39:19<>1.0.co;2-w.cover.gif)
