Abstract

(BEDO-TTF)₄[Fe(CN)₅NO] was synthesized by electrocrystallization using the nitroprussides M₂[Fe(CN)₅NO]·2H₂O (M = K, Rb) as supporting electrolytes and TCE (1,1,2-trichloroethane) and DCE (1,2-dichloroethane) as solvents. The crystal structure of this new salt (a = 4.0251(3), b = 15.266(2), c = 19.259(2) Å, α = 97.02(1), β = 93.23(1), γ = 96.04(1)°, V = 1165.1(2) Å³, Z = 3/4, space group P) is characterized by the presence of β″-type radical cation layers and anion layers containing disordered nitroprusside anions. The stoichiometry was confirmed by a micro-Raman spectroscopic study and the band structure and Fermi surface of this new salt were studied by means of the extended Hückel tight binding method. (BEDO-TTF)₄[Fe(CN)₅NO] is a two dimensional metal stable down to liquid helium temperatures.