Molecular motion in pyridazinium/crown ether supramolecular cation salts of a nickel dithiolene complex

• Published in: Dalton transactions : an international journal of inorganic chemistry 2013-02, Vol.42 (8), p.2930-2939
• Main Authors: Liu, Zun-qi, Kubo, Kazuya, Lin, Li, Hoshino, Norihisa, Noro, Shin-ichiro, Akutagawa, Tomoyuki, Nakamura, Takayoshi
• Format: Article
• Language: English
• Subjects: Anions; Antiferromagnetism; Cations; Cations - chemistry; Chain dynamics; Crown Ethers - chemistry; Dynamics; Flip-flops; Hydrogen Bonding; Macromolecular Substances - chemical synthesis; Macromolecular Substances - chemistry; Models, Molecular; Molecular motion; Molecular Structure; Nickel - chemistry; Nitrogen atoms; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Pyridazines - chemistry; Salts - chemistry; Sulfhydryl Compounds - chemistry
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt32542j

Supramolecular cations formed by monoprotonated pyridazinium cations and cis-anti-cis-dicyclohexano[18]-crown-6 (DCH[18]-crown-6) or dibenzo[18]-crown-6 (DB[18]-crown-6) were introduced into [Ni(dmit)2]− salts (where dmit2− = 2-thione-1,3-dithiole-4,5-dithiolate). X-ray crystal structure analysis of (pyridazinium+)(DCH[18]-crown-6)[Ni(dmit)2]− (1) revealed a chair-type conformation of the DCH[18]-crown-6 moiety. A V-shaped conformation of the DB[18]-crown-6 moiety was observed in (pyridazinium+)(DB[18]-crown-6)2[Ni(dmit)2]−(H2O)2 (2). Nitrogen atoms in the pyridazinium cations interacted with the oxygen atoms of the DCH[18]-crown-6 and DB[18]-crown-6 through N–H+O hydrogen bonds, forming 1:1 and 1:2 supramolecular structures, respectively. Sufficient space for molecular motions of the pyridazinium cations, namely flip-flop and in-plane rotations, exists in salt 1. Disorder in nitrogen atoms was observed by X-ray analysis, indicating dynamic motion of the pyridazinium cation, namely flip-flop motion and in-plane motion. A potential energy calculation further supported the possibility of dynamic motion of cations in the crystal. By contrast, the flip-flop motion of the pyridazinium group in salt 2 is restricted by the two nearest-neighbouring DB[18]-crown-6 molecules. Weak antiferromagnetic intermolecular interactions between the [Ni(dmit)2]− anions in the two-dimensional layers of salt 1 were observed, resulting in alternating antiferromagnetic Heisenberg chain-type magnetic susceptibility. Quasi-one-dimensional intermolecular interactions between the [Ni(dmit)2]− anions were observed in salt 2, whose magnetic behaviour followed the Bonner–Fisher model.