W0357

Ab-Initio Powder Structure Determination of Two New Cadmium and Zinc N,N’-Ethylene Diammonium Methylenephosphonates, Naima Bestaoui and Abraham Clearfield, Chemistry Dept., Texas A&M Univ. ,College Station, Texas 77843-3255.

Metal phosphonates are of considerable interest because of their potential application in catalysis1, ion exchange2, intercalation3 and many other fields4. These compounds present generally a layered structure. The metal atoms and the bridging oxygen atoms from the phosphonate groups form the layers. The organic moiety occupies the interlayer spacing.

One general ligand that has been used in our group is α,ω-alkyldiphosphonic acid. The resulting metal phosphonates form layered structures in which the layers are cross-linked by the alkyl groups5. By inserting imine groups in the alkyl chains, it Imports ion exchange and complexing ability to the compounds6.

Divalent metals often form crystalline phosphonates. It was of interest to prepare cross-linked layers containing the amino-functionality. Determination of such structures would provide a mechanism for understanding the ion exchange and complexion reactions via structural data.

In this communication, we present the crystal structures of cadmium and zinc ethylenediamine phosphonates as determined from X-ray powder data. These two compounds have layered structures, which are maintained by hydrogen bonding. The structures were determined and refined by using the two programs EXPO and GSAS.

References
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2Wang, J. D.; Clearfield, A.; Peng, G. –Z Mater. Chem. Phys. 1993, 35, 208.
3Alberti, G.; Costantino, U. In Comprehensive Supramolecular Chemistry; Lehn, J.M., Ed.; Pergamon-Elsevier Science Ltd: London, 1996, p 1.
4(a) Stein, E.; Clearfield, A.; Subramanian, M.A. Solid State Ionics 1996, 83, 113.(b) Cao, G.; Hong, H.; Mallouk, T.E. Acc. Chem. Res.1992, 25, 420 (c) Vermeulen, L.A.; Thompson, M.E. Nature 1992, 358, 656.
5(a) Clearfield, A. ,Wang, Z.J. Chem. Soc. Dalton Trans. 2002, 2937; (b) Yang, C.Y. Ph.D. Dissertation, Texas A&M Univ., Dec 1986.(c) Clearfield, A. Chem. Mater., 1998, 10, 2801.(d) Poojary, D.M.; Zhang, B.; Clearfield, A., J. Am. Chem. Soc. 1997, 119, 12550. (e) Arnold, D.I., Ouyang, X.; Clearfield, A.; Chem. Mater. 2002, 14, 2020.
6Ortiz-Avila, C. Y.; Bhardwaj, C.; Clearfield, A. Inorg. Chem. 1994, 33, 2499.