The Raman spectrum of Ge(2)Cl(6) shows close analogies with that of the isoelectronic [Ga(2)Cl(6)](2)(-). A band at 262 cm(-)(1) is assigned as principally a Ge-Ge stretching mode. The compound is very moisture-sensitive and decomposes readily in vacuo to give GeCl(4) as one of the products. A sealed sample stored at room temperature gave colorless cuboidal crystals shown by X-ray crystallography to be Ge(5)Cl(12).GeCl(4). The Ge-Ge distance in the neopentyl-like Ge(5) skeleton is 2.420(6) Å, and the Ge-Cl distance in the Ge(5)Cl(12) moiety is 2.119(5) Å whereas in the case of the GeCl(4) molecule it is 2.082(7) Å. The symmetric stretching frequency of the Ge(5) tetrahedron is assigned to the band at 224 cm(-)(1).