The Raman spectrum of Ge2Cl6 shows close analogies with that of the isoelectronic [Ga2Cl6](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 GeCl4 as one of the products. A sealed sample stored at room temperature gave colorless cuboidal crystals shown by X-ray crystallography to be Ge5Cl12. GeCl4. The Ge-Ge distance in the neopentyl-like Ge-5 skeleton is 2.420(6) Angstrom, and the Ge-Cl distance in the Ge5Cl12 moiety is 2.119(5) Angstrom whereas in the case of the GeCl4 molecule it is 2.082(7) Angstrom. The symmetric stretching frequency of the Ge-5 tetrahedron is assigned to the band at 224 cm(-1).