Polymorphism and Magnetism of (cis-Cyclohexane-1,4-diammonium)(Dicyclohexano[18]crown-6)2[Ni(dmit)2]2Salts

Supramolecular cationic structures of (CHDA2+)(DCH[18]crown-6)2were introduced into [Ni(dmit)2]−salts (where CHDA2+, DCH[18]crown-6, and dmit2−represent cis-cyclohexane-1,4-diammonium, meso-dicyclohexano[18]crown-6, and 2-thioxo-1,3-dithiole-4,5-dithiolate, respectively). The crystal polymorphs of (CHDA2+)(DCH[18]crown-6)2[Ni(dmit)2]2(crystals 1and 2) within the same crystallization batch were classified in the space groups P21/n(1) and P1̅ (2). The N−H+∼O hydrogen-bonding interactions between the axial- and equatorial-ammonium moieties of the CHDA2+cation and the oxygen atoms of DCH[18]crown-6 yielded a sandwich-type 1:2 adduct of the supramolecular cation in 1and 2. Although the overall cationic structures in 1and 2resembled one another, the [Ni(dmit)2]−anion arrangements were distinctively different from each other. The lateral [Ni(dmit)2]−dimer along the short axis of the anion was observed in 1, whereas two types of [Ni(dmit)2]−π-dimer existed independently in 2. The weak intermolecular interactions between the [Ni(dmit)2]−anions in 1was reflected by the temperature dependent magnetic susceptibility, which followed the Curie−Weiss model. For 2, two different magnetic exchange energies arising from the different strengths of the π-dimer units dominated the magnetic properties.