The structures of two 1 : 2 adducts between tin(IV) halides and AsPh3 have been determined. SnCl4(AsPh3)(2) adopts a six-coordinate geometry at tin in which the two organoarsine donors are mutually trans. In contrast, SnBr4(AsPh3)(2) is five-coordinate at tin and only one arsine is directly bonded to the metal, in an axial site of the trigonal bipyramid. The second AsPh3 group has a close contact with the axially bound bromine [As...Br: 3.567(3) Angstrom], which is a unique structural variation that depicts an intermediate in a halogen-transfer reaction between Group 14 and Group 15 elements. AACVD using SnCl4(AsPh3)(2) generates a film containing SnO2 and a second crystalline material which is possibly SnCl2, but which contains no arsenic.