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Reaction of (Et 4 N)Cl with AS 2 S 3  and Na 2 S in acetonitrile at 110°C affords the polymeric thioarsenate(III) (Et 4 N) 2 As 6 S 10  in which the cyclic [As 3 S 6 ] 3-  and chainlike [As 3 S 7 ] 5-  trinuclear molecular building units are linked together through common sulphur atoms into infinite double chains. In contrast, reaction of the same starting materials at higher temperatures (180°C) in water leads to formation of a markedly denser phase (Et 4 N) 2 As 8 S 13 , whose thioarsenate(III)  1  ∞  [As 8 S 13  2- ] anions exhibit a higher condensation grade. These likewise double chains are composed of cyclic [AS 3 S 6 ] 3-  and dinuclear [As 2 S s ] 4-  units with shared ѱ-AsS 3  tetrahedra corners. Analogous treatment of (Et 4 N)Cl with As 2 Se 3  and Na 2 Se in acetonitrile (T =110°C) yields (Et 4 N)[SeAsSe 7 ].

Solventothermal Synthesis and Structure of the Polymerie Thioarsenates(III) (Et 4 N) 2 As 6 S 10 and (Et 4 N) 2 As 8 S 13