Coexistence of two donor packing motifs in the stable molecular metal α-‘pseudo-κ’-(BEDT-TTF)4(H3O)[Fe(C2O4)3]·C6H4Br2

The crystal and electronic structure of a new radical cation salt α-‘pseudo-κ’-(BEDT-TTF)4H3O[Fe(C2O4)3]·C6H4Br2 have been studied. The new triclinic crystals contain two conducting organic layers which are characterized by different BEDT-TTF packing motifs: a ‘pseudo-κ’-layer which is composed of charged dimers and neutral monomers of BEDT-TTF orthogonal to each other and an α-layer which consists of inclined, uniformly charged BEDT-TTF stacks. According to electronic band structure calculations, the ‘pseudo-κ’ layer has a large gap between the HOMO bands at the Fermi level and should be associated with an activated conductivity. In contrast, the α-layer is a strongly two-dimensional electronic system with uniform intermolecular interactions. The absence of any nesting in the Fermi surface of the α-layer suggests that this salt should be a stable metal down to low temperatures. Metallic properties have been observed in the crystals in the 300–0.4 K temperature range. Besides, well pronounced Shubnikov–de Haas oscillations of the magnetoresistance have been revealed at B > 8 T. The salt investigated is a new phase in the (BEDT-TTF)4AI[MIII(C2O4)3]G family of organic molecular conductors with paramagnetic anions and different guest solvent molecules G in the anion layer. Structural features of the new α-‘pseudo-κ’-crystals and other known phases of the family (β″, ‘pseudo-κ’ and α-β″) have been compared.