Crystal engineering via negatively charged O–H  · · ·  O^– and charge- assisted C–H^δ+  · · ·  O^δ– hydrogen bonds from the reaction of [Co(η⁵-C₅H₅)₂][OH] with polycarboxylic acids §

Abstract

The polycarboxylic acids C₆H₃(CO₂H)₃-1,3,5 (trimesic acid, H₃tma) and O  ²,O  ³-dibenzoyl-L-tartaric acid (L-H₂bta) reacted in water or thf with [Co(η⁵-C₅H₅)₂][OH] prepared in situ by oxidation of [Co(η⁵-C₅H₅)₂] to generate organic superanions self-assembled via negatively charged O–H  · · ·  O^– and neutral O–H  · · ·  O hydrogen bonds. The resulting organic host accommodates the cations via charge assisted C–H^δ+  · · ·  O^δ– hydrogen bonds between organometallic and organic components. Crystalline [Co(η⁵-C₅H₅)₂]⁺[(H₃tma)(H₂tma)]^–·2H₂O 1 was obtained as the major product from acid and base in a 1∶2 stoichiometric ratio. Compound 1 contains a complex hydrogen bonded honeycomb-type structure formed by superanions [(H₃tma)(H₂tma)]^– and water molecules. The mixed salt [Co(η⁵-C₅H₅)₂]⁺[Co(H₂O)₆]²⁺[tma]^3– 2 was obtained as a minor product from the same reaction. In crystalline 2 the water molecules of the aqua complex form hydrogen bonds with the three carboxylic groups of the organic anion resulting in a caged structure that encapsulates the [Co(η⁵-C₅H₅)₂]⁺ cation. When dibenzoyl-L-tartaric acid was used the chiral crystal [Co(η⁵-C₅H₅)₂]⁺[L-Hbta]^– 3 is obtained. The crystal contains chains of O–H  · · ·  O^– hydrogen bonded anions. These results are used to discuss a design strategy for the engineering of organometallic crystals with predesigned structures. Though on a limited data set, the structure of the elusive crystalline hydrate [Co(η⁵-C₅H₅)₂]⁺[OH]^–·4H₂O 4, which is liquid at ambient temperature, is discussed.

References

1. Part 2, D. Braga, A. Angeloni, F. Grepioni and E. Tagliavini, Organometallics, 1997, 16, 5478.
2. D. Braga and F. Grepioni, Chem. Commun., 1996, 571; J. Hulliger, Angew. Chem., Int. Ed. Engl., 1994, 33, 143; C. L. Bowes and G. A. Ozin, Adv. Mater., 1986, 8, 13; G. A. Ozin, Acc. Chem. Res., 1997, 30, 17; M. J. Zaworotko, Nature (London), 1997, 386, 220; O. M. Yaghi, L. Guangming and H. Li, Nature (London), 1995, 378, 703; P. Ball, Nature (London), 1996, 381, 648.
3. A. Gavezzotti, Acc. Chem. Res., 1994, 27, 309; H. R. Karfunkel and R. J. Gdanitz, J. Comput. Chem., 1992, 13, 1171; R. J. Gdanitz, Chem. Phys. Lett., 1992, 190, 391; S. J. Maginn, Acta Crystallogr., Sect. A, 1996, 52, C79; Theoretical Aspects and Computational Modeling of the Molecular Solid State, ed. A. Gavezzotti, Wiley, Chichester, 1997.
4. O. Khan, Molecular Magnetism, VCH, New York, 1993; D. Gatteschi, Adv. Mater., 1994, 6, 635.
5. J. M. Williams, H. H. Wang, T. J. Emge, U. Geiser, M. A. Beno, P. C. W. Leung, K. Douglas Carson, R. J. Thorn, A. J. Schultz and M. Whangbo, Prog. Inorg. Chem., 1987, 35, 218; J. M. Williams, J. R. Ferraro, R. J. Thorn, K. D. Carlson, U. Geiser, H.-H. Wang, A. M. Kini and M.-H. Whangbo, Organic Superconductors, (including Fullerenes): Syntheses, Structure, Properties and Theory, Prentice Hall, Englewood Cliffs, NJ, 1992.
6. J. S. Miller and A. J. Epstein, Angew. Chem., Int. Ed. Engl., 1994, 33, 385; Chem. Eng. News, 1995, 73; 30.
7. S. R. Marder, Inorg. Mater., 1992, 115; N. J. Long, Angew. Chem., Int. Ed. Engl., 1995, 34, 21; T. J. Marks and M. A. Ratner, Angew. Chem., Int. Ed. Engl., 1995, 34, 155; D. R. Kanis, M. A. Ratner and T. J. Marks, Chem. Rev., 1994, 94, 195.
8. P. J. Fagan and M. D. Ward, The Crystal as a Supramolecular Entity. Perspectives in Supramolecular Chemistry, ed. G. R. Desiraju, Wiley, Chichester, 1996, vol. 2, p. 107.
9. D. Braga and F. Grepioni, Acc. Chem. Res., 1994, 27, 51; Coord. Chem. Rev., in the press.
10. G. R. Desiraju, Angew. Chem., Int. Ed. Engl., 1995, 34, 2311; A. D. Burrows, C.-W. Chan, M. M. Chowdry, J. E. McGrady and D. M. P. Mingos, Chem. Soc. Rev., 1995, 329.
11. D. Braga, A. L. Costa, F. Grepioni, L. Scaccianoce and E. Tagliavini, Organometallics, 1996, 15, 1084.
12. D. Braga and F. Grepioni, Acc. Chem. Res., 1997, 30, 81; Current Challenges on Large Supramolecular Assemblies, ed. G. Tsoucaris, Kluwer, Dordrecht, 1998, in the press; D. Braga, G. Cojazzi, F. Grepioni, N. Scully and S. M. Draper, Organometallics, 1998, 17, 296.
13. (a) G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467; (b) G. M. Sheldrick, SHELXL 92, Program for Crystal Structure Determination, University of Göttingen, 1993; (c) E. Keller, SCHAKAL 92, Graphical Representation of Molecular Models, University of Freiburg, 1993; (d) A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, C31.
14. (a) D. J. Duchamp and R. E. Marsh, Acta Crystallogr., Sect. B, 1969, 25, 5; (b) F. H. Herbstein and R. E. Marsh, Acta Crystallogr., Sect. B, 1977, 33, 2358.
15. See, for example, F. H. Herbstein and M. Kapon, Acta Crystallogr., Sect. B, 1978, 34, 1608; F. H. Herbstein, M. Kapon and G. M. Reisner, J. Inclusion Phenom., 1987, 5, 211; F. H. Herbstein, M. Kapon, I. Maor and G. M. Reisner, Acta Crystallogr., Sect. B, 1981, 37, 136.
16. See, for example, F. H. Herbstein and M. Kapon, Acta Crystallogr., Sect. B, 1979, 35, 1614; H. Oshio and H. Ichida, J. Phys. Chem., 1995, 99, 3294; O. M. Yaghi, L. Guangming and L. Hailian, Nature (London), 1995, 14, 378.
17. M. Meot-Ner (Mautner), J. Am. Chem. Soc., 1984, 106, 1257; M. Meot-Ner (Mautner) and L. W. Sieck, J. Am. Chem. Soc., 1986, 108, 7525.
18. D. Braga, F. Grepioni, K. Biradha, V. R. Pedireddi and G. R. Desiraju, J. Am. Chem. Soc., 1995, 117, 3156.
19. C. B. Aakeroy and M. Nieuwenhuyzen, J. Am. Chem. Soc., 1994, 116, 10 983; J. Mol. Struct., 1996, 374, 223.
20. M. W. Hosseini, R. Ruppert, P. Schaeffer, A. De Cian, N. Kyritsakas and J. Fisher, J. Chem. Soc., Chem. Commun., 1994, 2135; O. Félix, M. W. Hosseini, A. De Cian and J. Fisher, Tetrahedron Lett., 1997, 38, 1933 and refs. therein G. Brand, M. W. Hosseini, R. Ruppert, A. De Cian, J. Fisher and N. Kyritsakas, New J. Chem., 1995, 19, 9; O. Félix, M. W. Hosseini, A. De Cian and J. Fisher, Angew. Chem., Int. Ed. Engl., 1997, 36, 102.
21. V. A. Russell, C. C. Evans, W. Li and M. D. Ward, Science, 1997, 276, 575.