Crystal structures of hydrates of simple inorganic salts. III. Water‐rich aluminium halide hydrates: AlCl3·15H2O,AlBr3·15H2O,AlI3·15H2O,AlI3·17H2O and AlBr3·9H2O

Water‐rich aluminium halide hydrate structures are not known in the literature. The highest known water content per Al atom is nine for the perchlorate and fluoride. The nonahydrate of aluminium bromide, stable pentadecahydrates of aluminium chloride, bromide and iodide, and a metastable heptadecahydrate of the iodide have now been crystallized from low‐temperature solutions. The structures of these hydrates were determined and are discussed in terms of the development of cation hydration spheres. The pentadecahydrate of the chloride and bromide are isostructural. In AlI₃·15H₂O, half of the Al³⁺ cations are surrounded by two complete hydration spheres, with six H₂O in the primary and 12 in the secondary. For the heptadecahydrate of aluminium iodide, this hydration was found for every Al³⁺.