Hostname: page-component-cd9895bd7-mkpzs Total loading time: 0 Render date: 2024-12-26T09:25:41.109Z Has data issue: false hasContentIssue false
  • English
  • Français

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: [email protected]
Get access Rights & Permissions [Opens in a new window]

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

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Balmaseda, J., Reguera, E., Gomez, A., Roque, J., Vazquez, C., and Autie, M. (2003). “On the microporous nature of transition metal nitroprussides,” J. Phys. Chem. BJPCBFK10.1021/jp027678g 107, 11360–11369.Google Scholar
Culp, J. T., Matranga, C., Smith, M., Bittner, E. W., and Bockrath, B. (2006). “Hydrogen storage properties of metal nitroprussides M[Fe(CN)5NO], (M=Co, Ni),” J. Phys. Chem. BJPCBFK 110, 8325–8328.CrossRefGoogle ScholarPubMed
Ferreira, F. F., Granado, E., Carvalho, W. Jr., Kycia, S. W., Bruno, D., and Droppa, R. Jr. (2006). “X-ray powder diffraction beamline at D10B of LNLS: application to the Ba2FeReO6 double perovskite,” J. Synchrotron Radiat.JSYRES10.1107/S0909049505039208 13, 46–53.Google Scholar
Gómez, 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,” PolyhedronPLYHDE10.1016/S0277-5387(00)00564-7 20, 165–170.CrossRefGoogle Scholar
Gómez, A., Rodríguez-Hernández, J., and Reguera, E. (2004). “Unique coordination in metal nitroprussides: The structure of Cu[Fe(CN)5NO]·2H2O and Cu[Fe(CN)5NO],” Chem. Soc. Jpn. Bull.BCSJA8 34, 893–903.Google Scholar
Gómez, A., Rodríguez-Hernández, J., and Reguera, E. (2007). “Crystal structures of cubic nitroprussides: M[Fe(CN)5NO]·xH2O (M=Fe, Co, Ni). Obtaining structural information from the background,” Powder Diffr.PODIE2 22, in press.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.CMATEX10.1021/cm9606383 9, 1092–1097.CrossRefGoogle Scholar
Gütlich, P., Garcia, Y., and Woike, Th. (2001). “Photoswitchable coordination compounds,” Coord. Chem. Rev.CCHRAM 219–221, 839–879.Google Scholar
Mullica, D. F., Sappenfield, E. L., Tippin, D. B. and Leschnitzer, D. H. (1989). “Synthesis, spectroscopic studies and crystal structure analysis of zince nitrosylpentacyanoferrate trihydrate, Zn[Fe(CN)5NO]·3H2O,” Inorg. Chim. ActaICHAA310.1016/S0020-1693(00)80882-8 164, 99–103.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. Chim. ActaICHAA310.1016/S0020-1693(00)80287-X 174, 129–135.CrossRefGoogle Scholar
Reguera, E., Dago, A., Gómez, A., and Bertran, J. F. (1996). “Structural changes in insoluble metal nitroprussides on ageing,” PolyhedronPLYHDE10.1016/0277-5387(95)00582-X 15, 3139–3145.Google Scholar
Rodriguez-Carvajal, J. (2000). “The FULLPROF Program,” Institute Leon Brillouin, Saclay, France.Google Scholar