Supramolecular cationic structures of (CHDA2+)(DCHcrown-6) 2 were introduced into [Ni(dmit)2]- salts (where CHDA2+, DCHcrown-6, and dmit2- represent cis-cyclohexane-1,4-diammonium, meso-dicyclohexanocrown-6, and 2-thioxo-1,3-dithiole-4,5-dithiolate, respectively). The crystal polymorphs of (CHDA2+)(DCHcrown-6)2[Ni(dmit)2] 2 (crystals 1 and 2) within the same crystallization batch were classified in the space groups P21/n (1) and P1̄ (2). The N-H+∼O hydrogen-bonding interactions between the axial-and equatorial-ammonium moieties of the CHDA2+ cation and the oxygen atoms of DCHcrown-6 yielded a sandwich-type 1:2 adduct of the supramolecular cation in 1 and 2. Although the overall cationic structures in 1 and 2 resembled 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 1 was 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.
ASJC Scopus subject areas
- 化学 (全般)