Crystal structures and magnetic properties of (4,4′-phenylazophenyl)diammonium(crown ethers)[Ni(dmit)2]2 crystals

Abstract

Sandwich-type hydrogen-bonded supramolecular dications (DAAz²⁺)([18]crown-6)₂ and (DAAz²⁺)(dicyclohexane[18]crown-6)₂ (DAAz²⁺ = 4,4′-(phenylazophenyl)diammonium) were introduced into [Ni(dmit)₂]⁻ anions via a diffusion method to form novel single crystals (DAAz²⁺)([18]crown-6)₂[Ni(dmit)₂]₂ (1) and (DAAz²⁺)(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 (–NH₃⁺) of the DAAz²⁺ 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.