Four new phenylarseniato adducts and derivatives have been synthesized on allowing SnR2Cl2 (R = Ph, Bu) to react with Cy2NH2.NH2PhAsO3H.3/2H2O in specific ratios. The obtained new tin (IV) compounds were studied by infrared, infinite chain and discrete structures were suggested on the basis of spectroscopic data, the oxyanion behaving as a bridging bidentate or a tridentate ligand. When secondary interactions are involved supramolecular architectures were obtained.