Sandwich-type hydrogen-bonded supramolecular dications (DAAz 2+)([18]crown-6) 2 and (DAAz 2+) (dicyclohexane[18]crown-6) 2 (DAAz 2+ = 4,4′- (phenylazophenyl)diammonium) were introduced into [Ni(dmit) 2] - anions via a diffusion method to form novel single crystals (DAAz 2+)([18]crown-6) 2[Ni(dmit) 2] 2 (1) and (DAAz 2+)(dicyclohexane[18]crown-6) 2[Ni(dmit) 2] 2 (2), respectively, which were characterized based on their crystal structures and magnetic susceptibilities. The molecular assembly structures and its physical properties were expanded in the use of a three component molecular network system. The two ammonium groups (-NH 3+) of the DAAz 2+ dication formed N-H +-O hydrogen-bonding interactions with the oxygen atoms of [18]crown-6 and dicyclohexane[18]crown-6. In the case of crystal 1, an alternating π-stacking interaction was observed for the [Ni(dmit) 2] - anions, whereas orthogonal linear π-S interactions were detected for crystal 2. Temperature-dependent magnetic susceptibilities of crystals 1 and 2 followed the alternate Heisenberg antiferromagnetic chain (J = -15.8 K) and linear Heisenberg antiferromagnetic chain (J = -13.7 K) models, respectively. © 2012 The Royal Society of Chemistry.