This website uses cookies to give you the best user experience. If you continue
without changing your settings we'll assume you are happy to receive all RSC cookies.
You can change your cookie settings by navigating to our Privacy and Cookies page and following the instructions. These instructions
are also obtainable from the privacy link at the bottom of any RSC page.
Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0812, Japan
E-mail: zunqi85@es.hokudai.ac.jp
; Fax: +81-11-706-9420
; Tel: +81-11-706-9419
b
Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan
E-mail: kkubo@es.hokudai.ac.jp
; Fax: +81-11-706-9420
; Tel: +81-11-706-9455
c
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan
E-mail: akuta@tagen.tohoku.ac.jp
; Fax: +81-22-217-5655
; Tel: +81-22-217-5653
Dalton Trans., 2013,42, 2930-2939
DOI:
10.1039/C2DT32542J
Received
24 Oct 2012,
Accepted
23 Nov 2012
First published online
27 Nov 2012
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.
Fetching data from CrossRef. This may take some time to load.