Treatment of 1,1,4,4-tetramethyl-2,3-diazabutadiene with the alane adduct [AlH 3 (NMe 2 Et)] yielded the hydrazine derivative (AlH 2 ) 2 -(AlH) 2 (N 2 iPr 2 ) 3 (1) by the hydroalumination of both C À N double bonds. Compound 1 has a complicated cage structure formed by three hydrazido groups and four aluminium atoms. As a particularly interesting structural motif it contains a NÀN group side-on-coordinated to one aluminium atom through its lone pairs of electrons. Sublimation of 1 gave a heterocubane-type compound (HAlNiPr) 4 (2) by the complete cleavage of all NÀN bonds, one face of which is bridged by weakly coordinated diisopropyldiazene with a NÀN double bond. Repeated sublimation gave the pure, unsupported heterocubane molecule 3. Heating of the rough product of the reaction of alane and diazabutadiene to 90 8C in a closed vessel yielded another product Al(AlH 2 ) 3 (N 2 iPr 2 ) 3 (4), which contains a cyclic chelating ligand formed by three hydrazido groups and three aluminium atoms. This heterocycle coordinates a fourth aluminum atom in the molecular center by close contacts to all six nitrogen atoms. A strongly flattened, distorted octahedral coordination sphere results for the inner metal atom.