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Crystal structures of cubic nitroprussides: M[Fe(CN)5NO]·xH2O(M=Fe, Co, Ni). Obtaining structural information from the background

Published online by Cambridge University Press:  01 March 2012

A. Gómez,
J. Rodríguez-Hernández and
E. Reguera
A. Gómez
Affiliation:
Department of Physics, University of Guelph, Guelph, Ontario NIG 2W1, Canada
J. Rodríguez-Hernández
Affiliation:
Institute of Materials Science and Technology, 10400 Havana University, Havana, Cuba
E. Reguera*
Affiliation:
Institute of Materials Science and Technology, 10400 Havana University, Havana, Cuba and Center of Applied Science and Technology of IPN, CICATA-Unidad Legaria, Mexico, D. F.
*
a)Author to whom correspondence should be addressed. Electronic mail: ereguera@yahoo.com
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Abstract

A new structural model is proposed for cubic nitroprussides and the crystal structure for the complex salts of Fe(2+), Co(2+), and Ni(2+) refined in that model. In cubic nitroprussides the building unit, [Fe(CN)5NO]2−, and the assembling metal (M=Fe2+,Co2+,Ni2+), have ¾ occupancy with three formula units per cell (Z=3). This leads to certain structural disorder and to different local environments for the outer metal. The crystallographic results are supported by the Mössbauer and infrared data. The XRD powder patterns, index in a cubic cell (Fm3m space group), show a sinuous background because of diffuse scattering from positional disorder of the metal centers. Because of this, the crystal structures were refined allowing the metal centers to move from the (0,0,0) and (0,0,1/2) positions (away from positional symmetry restrictions). The refinement under these conditions leads to excellent agreement factors (Rwp, Rp, S), good pattern background fitting, and produced a refined structural model consistent with the crystal chemistry of nitroprussides. The studied materials are obtained as hydrates. On heating, the crystal water evolves, and below 100°C an anhydrous phase is obtained, preserving the framework of the original hydrates. The loss of the crystal water leads to cell contraction that represents around 2% of cell volume reduction. On cooling down from room temperature to 77 and 12 K, a slight expansion for the -M-N≡C-Fe-C≡N-M- chain length is observed, suggesting that at low temperature and reduction in the metals charge delocalization on the CN bridges takes place. For M=Fe and Co the crystal structure was also refined for the anhydrous phase at 12, 77, and 300 K.

Keywords

nitroprussideporous materialRietveld refinementcrystal structurePrussian blue analogues

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Type
Technical Articles
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Powder Diffraction , Volume 22 , Issue 1 , March 2007, pp. 27 - 34
Copyright
Copyright © Cambridge University Press 2007

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