The synthesis and characterization of 4,7-dimethyl-4,7,10,11,15, 18-hexaazabicy-clo[8.5.5]octane (L) is described. The ligation properties of the macrobicyclic ligand towards alkaline metal cations are considered. The crystalline structures of the ligand L and of the first small azacage complexes with six-coordinate lithium geometry, [LiL] + [BPh 4 ] - and [LiL] + [ClO 4 ] - , are presented.