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Crystal structures of three anhydrous nitroprussides: M[Fe(CN)5NO] (M=Mn, Zn, Cd)

Published online by Cambridge University Press:  01 March 2012

J. Rodríguez-Hernández,
E. Reguera,
M. Mir and
Y. P. Mascarenhas
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.
M. Mir
Affiliation:
Instituto de Fisica de Sao Carlos, Universidade Sao Paulo, Sao Carlos, SP, Brazil
Y. P. Mascarenhas
Affiliation:
Instituto de Fisica de Sao Carlos, Universidade Sao Paulo, Sao Carlos, SP, Brazil
*
a)Author to whom correspondence should be addressed. Electronic mail: ereguera@yahoo.com
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Abstract

The crystal structures of Mn, Zn, and Cd nitroprussides in their anhydrous state, M[Fe(CN)5NO] (M=Mn, Zn, Cd), were refined from XRD powder patterns using the Rietveld method. These compounds have a porous framework useful for adsorption and storage of small molecules. Water crystallization can be removed by heating below 100 °C without disrupting the 3D network by introducing certain structural modification mainly around the M site (Mn, Zn, Cd). For M=Mn and Cd, the compounds were found to be orthorhombic with space group Pnma [Mn:a=13.7844(1), b=7.3750(2), c=10.9470(2) Å, V=1112.8(1) Å3, Z=4; Cd:a=13.9566(3), b=7.5040(4), c=11.0230(2) Å, V=1154.4(1) Å3, Z=4]. Anhydrous zinc nitroprusside crystallizes in rhombohedral with space group R3 [a=b=19.2525(1), c=17.7107(2) Å, γ=120.0°, V=5685.1(1) Å3, Z=18]. When exposed to humid air, these anhydrous compounds become hydrated. The XRD powder patterns were recorded under vacuum on samples dehydrated in situ. The structural information from XRD was complemented with thermo-gravimetric, infrared, and Mössbauer data.

Keywords

nitroprussideporous materialRietveldcrystal structurePrussian blue analogues

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Type
Technical Articles
Information
Powder Diffraction , Volume 22 , Issue 1 , March 2007, pp. 40 - 46
Copyright
Copyright © Cambridge University Press 2007

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