A series of complexes of formula (C 6H 5) 3SnX·L (X = Cl, NCS) for a range of ligands L, where L = o-HOC 6H 4CHNC 6H 4R; o-HOC 6H 3(OMe)CHNC 6- H 5 or 2-HOC 10H 6CHNC 6H 4R (R = CH 3, OCH 3) have been synthesised by the reactions of triphenyltin chloride or isothiocyanate with N-aryl-salicylideneimines and N-aryl-2-hydroxynaphthylideneimines. Infrared, PMR, conductivity and Mössbauer data are presented. The crystal structure of one complex, isothiocyanatotriphenyl (1-[(4′-methylphenylimino)- methyl]-2-naphthol)tin(IV), is reported. The crystals are monoclinic, space group P2 1/ c, a = 12.409(1), b = 15.229(3), c = 17.242(2) Å, β = 99.828(9) o, V = 3210.5 Å 3, Z = 4, D calc = 1.385 Mg m −3, μ = 0.89 mm −1, F(000) = 1336, T = 295 K, final R = 4.0% for 2898 unique observed reflections. The complex has a five coordinate distorted trigonal bipyramidal structure, with the phenyl groups taking up the equatorial positions around the tin atom. The ligand, which exists in the form of a zwitterion in the complex, binds to the tin via the phenolic oxygen atom. The other complexes are believed to have similar structures to this.