The co-condensation, by annealing from À 196 8C to room temperature, of the high-temperature species AlCl and 3-hexyne (EtCCEt) with an excess of toluene leads to the formation of the compound (AlCl´EtCCEt) 4 . Characterisation by X-ray analysis revealed the presence of two isomers in the same crystal: a dimeric 1,4-dialumina-2,5-cyclohexadiene and a 1,4,7,10-tetralumina-2,5,8,11-cyclododecatetraene. Both isomers exhibit aluminium ± olefin p-bonding, with the Al 4 entities present in a tetrahedral arrangement. The bonding in both isomers is discussed on the basis of ab initio calculations performed for model compounds.