The dimeric form of aluminium tribromide (Al2Br6) predominates in the solid state, in solutions in noncoordinating solvents (e.g. CS2), in the melt, and in the gas phase.
Theory suggests that the diatomic aluminium monobromide condenses to a dimer and then a tetrahedral cluster Al4Br4, akin to the analogous boron compound.
It is prepared by the reaction of HBr with Al: Alternatively, the direct bromination occurs also: Al2Br6 dissociates readily to give the strong Lewis acid, AlBr3.
Regarding the tendency of Al2Br6 to dimerize, it is common for heavier main group halides to exist as aggregates larger than implied by their empirical formulae.
Lighter main group halides such as boron tribromide do not show this tendency, in part due to the smaller size of the central atom.