The first synthesis and crystallographic characterization of a main-group metal complex of the N2S2 ligand N,N'-ethylenebis(thiosalicylideneimine) (tsalen) is reported, with the isolation and characterization of the indium(III) compound [In(tsalen)(OAc)]. This compound has been crystallographically characterized and is shown to have a distorted trigonal bipyramidal geometry with a ligand that is unusually distorted from planarity. A byproduct of the synthesis, In(en)(2)(OAc)(2), has also been isolated and characterized.