Crystal structure and magnetic behavior of decamethylferrocenium bis(2-thioxo-1,3-dithiole-4,5-diselenolato)nickelate(III)

The synthesis, crystal structure and magnetic properties of the charge transfer salt [Fe(Cp∗)2][Ni(dsit)2], dsit = (2-thioxo-1,3-dithiole-4,5-diselenolato) are described. The crystal structure consists of layers composed by parallel chains, where side-by-side pairs of cations, alternate with face-to-face pairs of anions, ⋯D+D+A−A−D+D+A−A−⋯. The acceptors in the AA pairs are strongly dimerized through a Ni–Se bond. Short interdimer contacts (Se–Se and S–S) give rise to a porous 3D network, and the [Fe(Cp∗)2]+pairs are located in the cavities of the acceptors network. The [Fe(Cp∗)2]+ donors are relatively isolated leading to weak DA and DD interactions and the magnetic behavior of this compound can be basically described as the sum of two contributions: one from nearly independent donors, and the second from the acceptors network, with strong AA AFM coupling, both intradimer and between dimers in adjacent chains.