Abstract
Two new complexes [Ni(tacn)2][Ni(CN)4]·2H2O (1) and Ni(tacn)Ni(CN)4·H2O (2) (tacn = 1,4,7-triazacyclononane) have been synthesized from water and characterized by chemical analysis and infrared spectroscopy. Single-crystal X-ray structure analysis of 1 revealed an ionic structure built up of [Ni(tacn)2]2+ and [Ni(CN)4]2− complex ions without coordinated water. While cationic Ni(II) atom is octahedrally coordinated by two tridentate tacn ligands with Ni–N bonds from 2.101(3)–2.118(3) Å, the anionic Ni(II) atom is square planar with Ni–C bonds from 1.866(4) to 1.880(3) Å. An extended hydrogen bonding system connects complex cations, complex anions and water yielding hydrogen-bonded layers. Magnetic study of 1 revealed a decrease of the effective magnetic moment from 2.90 (300 K) to 2.43 μB at 1.8 K due to zero-field splitting. Fitting of the susceptibility data yielded g = 2.05, D/hc = 3.82 cm–1 and E/hc = 0.23 cm–1. IR spectral data indicate the presence of bridging cyano ligands in the structure of 2.
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