Selbststapelnde Systeme, IV 2,3,7,8-Tetramethoxythianthreniumsalze/Selfstacking Systems, Part IV 2.3.7.8-Tetramethoxythianthrenium Salts

Abstract

Abstract By addition of solutions of nitrosyl hexachloroantimonate(V) in acetonitrile or of diiodine in n-hexane to a solution of 2.3.7.8-tetramethoxythianthrene (“Vn2S2”, 1) in toluene the oxidation products [Vn2S2][SbCl6] • CH3CN (2) and [Vn2S2]I3 (3), resp., are formed. Crystal structure determinations show both compounds to contain the [Vn2S2]+ ion. In contrast to the folded parent compound Vn2S2 its monocation [Vn2S2] T is planar, the short CS and CO distances (172-173 pm and 134-135 pm resp.) indicate an extended mesomeric system. Both compounds crystallize with segregated stacks of cations and anions. In 2 the coplanarly and equidistantly stacked [Vn2S2]+ ions have an A,B-sequence (distance between the planes of the ions 353 pm, intermolecular S···S distance 366 pm). In 3 the [Vn2S2]+ ions form dimers by SS contacts (S···S distance 316 pm); these dimers are arranged in a stair-like manner (distances between atoms of adjacent dimers 350-380 pm). The conductivities of 2 and 3 are 9.4 • 10-9 and 5.3 • 10-6 Sem-1 , resp.