Unique coordination in metal nitroprussides: The structure of Cu[Fe(CN)5NO]·2H2O and Cu[Fe(CN)5NO]

The structures of copper pentacyanonitrosylferrate dihydrate, Cu[Fe(CN)5NO]·2H2O, and anhydrous, Cu[Fe(CN)5NO], have been determined from their XRD powder patterns and refined using the Rietveld method. The dihydrate structure was solved by direct methods and the anhydrous one was elucidated by chem...

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Detalles Bibliográficos
Autores: GOMEZ, A., RODRIGUEZ HERNANDEZ, J., REGUERA, E.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2004
País:México
Institución:Instituto Politécnico Nacional
Repositorio:Repositorio Digital del IPN
OAI Identifier:oai:www.repositoriodigital.ipn.mx:123456789/11548
Acceso en línea:http://hdl.handle.net/123456789/1210
http://www.repositoriodigital.ipn.mx/handle/123456789/11548
Access Level:acceso abierto
Palabra clave:Copper nitroprussides
crystal structure
copper pentacyanonitrosylferrates
powder diffraction
Descripción
Sumario:The structures of copper pentacyanonitrosylferrate dihydrate, Cu[Fe(CN)5NO]·2H2O, and anhydrous, Cu[Fe(CN)5NO], have been determined from their XRD powder patterns and refined using the Rietveld method. The dihydrate structure was solved by direct methods and the anhydrous one was elucidated by chemical intuition. Cu[Fe(CN)5NO]·2H2O is orthorhombic, space group Amm2 (38) and Z = 2. In this structure the iron is coordinated to fiveCNand aNOligand, while the copper atom is coordinated, in a unique fashion, to four equatorial CN groups at N ends and two water molecules. Cu[Fe(CN)5NO] is tetragonal, space group I4 mm (107) and Z = 2. This structure is obtained from the dehydration of the orthorhombic one; reordering allows the Cu atom to coordinate not only to the four equatorial cyanides but also to the axial cyanide. The coordination of the iron atom remains as in the orthorhombic structure. Agreement factor obtained from the final refinement were as follows: Rwp = 5.10 and RB = 4.57 for the orthorhombic structure and Rwp = 6.52 and RB = 7.82 for the tetragonal one. These crystal structures are also supported by IR and M¨ossbauer spectroscopic data and thermogravimetry.