The reactions of titanium(III) and (IV) chlorides with the crown thioether [9]aneS₃ were investigated. [TiCl_3- (MeCN)₃] gives a purple 1:1 adduct with a proposed octahedral structure involving tridentate fac-attachment of the ligand. With [TiCl₄(MeCN)₂] the identity of the yellow 1∶1 adduct obtained is discussed in terms of a six-coordinate species with bidentate ligand chelation. The title compound was isolated from the reactions of [9]aneS₃ with [TiCl₃(MeCN)₃] [SbCl₆] (by accident) and iron filings/SbCl₅ in MeCN solution and characterised crystallographically. The cation has two macrocyclic ligands coordinated facially to a six-coordinate Fe²⁺ ion; the anion comprises dimeric [(SbCl₄)₂] units linked together into a polymeric chain by weak halogen bridging.