Crystal and molecular structure of organic semiconductor (ET)(8)[Hg4Cl12]center dot 2C(6)H(6)

A new organic semiconductor, (ET)(8)[Hg4Cl12]. 2C(6)H(6), obtained in the ET(+)-HgCl-(-)(3)- PhF system has been studied by X-ray structural analysis. Radical cations of bis(ethylenedithio)tetrathiafulvalene (ET) in the organic layer of the structure are packed in stacks of alpha-type. The average angle between the planes of ET cations from adjacent stacks is 50.1 degrees. The anionic layer is formed by four-charge centrosymmetric [Hg4Cl12](4-) complexes and benzene solvate molecules. A comparative crystal-chemical study of the salts obtained by the reaction in the ET(+)-HgX(3)(-)-PhY system (where X = Cl, Br, and I; Y = F, Cl, and Br) made it possible to reveal a substantial effect of the sizes of the X and Y atoms in the composition of the salts and on the structural characteristics of the layers, which are responsible for the various conductivities of these salts.