Five new thioantimonates have been synthesized in the presence of organic amines under solvothermal conditions and their structures determined by single-crystal X-ray diffraction. All of the compounds are layered and contain antimony-sulphide anions of stoichiometry [Sb 4 S 7 ] 2À , but the structure of the anion formed is dependent on the amine used in synthesis. (H 3 N(CH 2 ) 4 NH 3 )[Sb 4 S 7 ] (1) contains [Sb 4 S 7 ] 2À double chains directed along [010]. Weak interchain Sb-S interactions between neighbouring chains cause the double chains to pack into layers in the ab plane. In the [001] direction, the layers of double chains alternate with doubly protonated diaminobutane molecules to which the chains are hydrogen bonded. Compounds of general formula (TH) 2 [Sb 4 S 7 ] (T ¼ CH 3 (CH 2 ) 2 NH 2 (2), (CH 3 ) 2 CHNH 2 (3), CH 3 (CH 2 ) 3 NH 2 (4) and CH 3 (CH 2 ) 4 NH 2 (5)) adopt a more complex structure in which [Sb 3 S 8 ] 7À units are linked by SbS 3 3À pyramids to form chains, which in turn are bridged by sulphur atoms to create sheets containing large heterorings. Pairs of such sheets form double layers of four atoms thickness that are stacked along [001]. Protonated amine molecules are located between anionic antimony-sulphide layers to which they are hydrogen bonded. Thermal analysis reveals that the decomposition temperature of materials containing [Sb 4 S 7 ] 2À anions is dependent both on the structure of the anion, the lowest decomposition temperature being that of the low-dimensional phase (1) and on the identity of the amine, the decomposition temperature decreasing with an increasing number of carbon atoms and decreasing density.