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Crystal structure of orthorhombic ferrous nitroprusside: Fe[Fe(CN)5NO].2H2O

Published online by Cambridge University Press:  01 March 2012

J. Rodríguez-Hernández
Affiliation:
Institute of Materials and Reagents, University of Havana, San Lazaro and L, 10400 Havana, Cuba
E. Reguera*
Affiliation:
Institute of Materials and Reagents, University of Havana, San Lazaro and L, 10400 Havana, Cuba
A. Gómez
Affiliation:
Department of Physics, University of Guelph, MacNaughton Building, Gordon Street, Guelph, Ontario, Canada
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]

Abstract

Ferrous nitroprusside can be obtained in three structural modifications: two different unstable phases, monoclinic trihydrate and cubic pentahydrate, and the stable one, an orthorhombic dihydrate. This contribution reports the crystal structure of the last one. Cell parameters are: a=13.9734 (2), b=7.4274 (1), and c=10.4697 (1) Å; with four formula units per cell (Z=4). The crystal structure was refined from the corresponding XRD powder pattern using the Rietveld method. Final agreement factors of the refinement process were Rwp=8.46, Rp=6.54, and S=1.38. The crystal structure is formed by a tridimensional assembling of the [Fe(CN)5NO] molecular block through iron atoms bounded at the N end of the CN ligands. The NO group remains unlinked at its O atom. The octahedral coordination of the assembling metal is completed with a coordinated water molecule which stabilizes a second water through a strong hydrogen bond interaction. The tridimensional structure appears as piled up rippled sheets leading to a system of interconnected small cavities which increase their available volume on the material dehydration. This complex loses its crystal water below 100 °C and then remains stable up to above 160 °C when the decomposition process begins with the loss of the NO ligand.

Type
Technical Articles
Copyright
Copyright © Cambridge University Press 2005

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References

Balmaseda, J., Reguera, E., Gómez, A., Roque, J., Vazquez, C., and Autie, M. (2003). “On the microporous nature of transition metal nitroprusside,” J. Phys. Chem. B JPCBFK 107, 1136011369.CrossRefGoogle Scholar
Benavente, A., de Moran, J. A., Piro, O. E., Castellano, E. E., and Aymonino, P. J. (1997). “Crystal and anion structure, TGA, DTA and infrared and Raman spectra of manganese (II) nitroprusside dihydrate, Mn[Fe(CN)5NO].2H2O,” J. Chem. Crystallog. 27, 343352.CrossRefGoogle Scholar
Berar, J. F. and Lelann, P. (1991). “ESDs and estimated probable-error obtained in rietveld refinements with local correlations,” J. Appl. Crystallogr. JACGAR 24, 1–5.CrossRefGoogle Scholar
Boxhoorn, G., Moolhuysen, J., Coolegem, J. G. F., and Van Santen, R.-A. (1985). “Cyanometalates: An underestimated class of molecular sieves,” J. Chem. Soc., Chem. Commun. JCCCAT 19, 13051307.CrossRefGoogle Scholar
Danon, J. “Mössbauer effect and chemical bonding in transition metal complexes,” in Applications of the Mössbauer effect in Chemistry and Solid State Physics (1966) (IAEA, Vienna,), pp. 89141.Google Scholar
Gomez, A., Reguera, E., and Cranswick, L. M. D. (2001). “The structure of two orthorhombic nitroprussides: Cd[Fe(CN)5NO].2H2O and Zn[Fe(CN)5NO].2H2O,” Polyhedron PLYHDE 20, 165170.CrossRefGoogle Scholar
Gu, Z. Z., Sato, O., Iyoda, T., Hashimoto, K., and Fujishima, A. (1996). “Molecular level design of a photoinduced magnetic spin coupling system: Nickel nitroprusside,” J. Phys. Chem. JPCHAX 100, 1828918291.CrossRefGoogle Scholar
Gu, Z. Z., Sato, O., Iyoda, T., Hashimoto, K., and Fujishima, A. (1997). “Spin switching effect in nickel nitroprusside: Design of a molecular spin device based on spin exchange interaction,” Chem. Mater. CMATEX 9, 10921097.CrossRefGoogle Scholar
Gutlich, P., Garcia, Y., and Woike, Th. (2001). “Photoswitchable coordination compounds,” Coord. Chem. Rev. CCHRAM 219, 839879.CrossRefGoogle Scholar
Haussühl, S., Schetter, G., and Woike, Th. (1995). “Nitroprussides: A new group of materials for holographic information storage on the bases of metastable electronic states,” Opt. Commun. OPCOB8 114, 219222.CrossRefGoogle Scholar
Imlau, M., Woike, T., Schieder, R., and Rupp, R. A. (1999). “Holographic scattering in centrosymmetric Na2[Fe(CN)5NO].2H2O in the red and near-infrared spectral range,” Phys. Rev. Lett. PRLTAO 82, 28602863.CrossRefGoogle Scholar
Mullica, D. F., Tippin, D. B., and Sappenfield, E. L. (1991). “The crystal structure analysis of iron nitroprusside, Fe[Fe(CN)5NO].3H2O,” J. Crystallogr. Spectrosc. Res. JCREDB 21, 8185.CrossRefGoogle Scholar
Mullica, D. F., Tippin, D. B., and Sappenfield, E. L. (1990). “The crystal structures of two nitroprussides: Mn[Fe(CN)5NO].3H2O and Cd[Fe(CN)5NO].3H2O,” Inorg. Chem. INOCAJ 174, 129135.Google Scholar
Reguera, E., Dago, A., Gómez, A., and Bertran, J. F. (1996). “Structural changes in insoloble metal nitroprussides on ageing,” Polyhedron PLYHDE 15, 31393145.CrossRefGoogle Scholar
Rodriguez-Carvajal, J., (1998). Program FULLPROF 98, Institute Leon Brillouin, Saclay, France.Google Scholar