Structural, spectral and magnetic investigations of various types of compounds and their isomers isolated from the system copper(II)–C(CN)3––pyrazole
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 7,p. 1773-1778
- https://doi.org/10.1039/dt9910001773
Abstract
From the system CuII–C(CN)3 ––Hpz (Hpz = pyrazole) the following compounds were isolated: [Cu{C(CN)3}(Hpz)4][C(CN)3]1, [Cu{C(CN)3}2(Hpz)3]2, α-[Cu{C(CN)3}2(Hpz)2]3, β-[Cu{C(CN)3}2(Hpz)2]4 and [Cu{Hpz·C(CN)3}2]5. They were studied by the use of spectroscopic and cryomagnetic methods. The structures of 1 and 2 were refined to R values of 0.0369 and 0.0374 for 1346 and 2066 independent reflections respectively. Compound 1 crystallises in space group P21/c, with a= 9.568(4), b= 16.692(7), c= 14.957(9)Å, β= 94.05(4)° and Z= 4; 2 crystallises in space group P, with a= 7.607(4), b= 8.942(6), c= 16.027(10)Å, α= 95.95(6), β= 90.83(5), γ= 106.88(5)° and Z= 2. Both compounds show elongated pseudo-octahedral copper environments, with the Hpz molecules in the equatorial plane. In 1 one C(CN)3 group bridges the CuII atoms in axial positions while the second group is anionic. Compound 2 contains mono- as well as bi-dentate bridging C(CN)3 groups; the latter join the basic structure units into binuclear species. Weak ferromagnetic coupling operates between the copper(II) centres inside the dimers. Physical measurements show that compounds 3 and 4 display rhombic octahedral arrangements around CuII in which all C(CN)3 groups are bridging. The α and β compounds are distortion isomers. Compound 5, a coligand isomer with respect to 3 and 4, contains new anionic chelate ligands, HNC(pz)CH(CN)2 –, formed by nucleophilic addition. In all these three compounds polymeric chains are present in which and between which there is magnetic interaction.Keywords
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