Two bimetallic layered materials with "Cu4Fe3" defective cubane units: syntheses, structures and magnetic properties of {[Cu(I)(I)(tn)]2[Fe(I)(I)(CN)6]}3.[Na3Fe(I)(I)( I)(CN) 6]12H2O (1) and {[Cu(I)(I)(tn)]2[Fe(I)(I)(CN)6]}.KCl5H2O(2)

• Published in: Synthetic metals 2005-09, Vol.153 (1-3), p.477-480
• Main Authors: Thetiot, F, Triki, S, Pala, J S, Gomez-Garcia, C J
• Format: Article
• Language: English
• ISSN: 0379-6779
• DOI: 10.1016/j.synthmet.2005.07.293

Reactions of the [FeIII(CN)6]3-anion with the [CuII(tn)]2+ion (tn=1,3-diaminopropane) afford the compounds {[CuII(tn)]2[FeII(CN)6]}3.[Na3FeIII(CN) 6]DDT12H2O (1) and {[Cun(tn)]2[FeII(CN)6]}.KClDDT5H2O (2). Despite the differences concerning their asymmetric units, both structures present strong similar features: in both structures, the Cu(II) ion presents a square-base pyramidal CuN5 environment and each [FeII(CN)6]4-anion is linked to six Cu(II) ions through its six N atoms leading to infinite [CuII(tn)]2[FeII(CN)6] layers which can be viewed as 2-D layered arrangement generated by the defective cubane units Cu4Fe3 involving Fe-CN-Cu bridges. The most important differences between the two structures concern essentially the inter-layer arrangement which is occupied, in compound 1, by isolated paramagnetic [Fe(CN)6]3-anions and water molecules, while in compound 2, this interlayer space is occupied by K+, Cl-ions and water molecules. Magnetic data indicate for 1 weak antiferromagnetic interactions and presence of magnetically isolated [FeIII(CN)6]3-anion and for 2 weak ferromagnetic interactions between the Cu(II) ions.