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Nitrogen‐Rich Compounds Of The Lanthanoids: The 5,5′‐Azobis[1H‐tetrazol‐1‐ides] Of The Light Rare Earths (Ce, Pr, Nd, Sm, Eu, Gd)

G. Steinhauser, G. Giester, N. Leopold, C. Wagner, Mario Villa
Published 2009 · Chemistry

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On the occasion of Carl Auer von Welsbach's 150th birthday in 2008, we investigated the 5,5′-azobis[1H-tetrazol-1-ides] (C2N; (ZT)2−) of the light lanthanoids (Ln) cerium, praseodymium, neodymium, samarium, europium, and gadolinium. Their synthesis was performed by crystallization from aqueous solutions of disodium 5,5′-azobis[1H-tetrazol-1-ide] and the respective lanthanoid nitrate. All compounds are isotypic (triclinic space group P-1) and crystallize according to the general formula [Ln(H2O)7]2(ZT)3⋅10 H2O. The crystal structures of all compounds were determined. A distinct lanthanoid contraction could be established, clearly observable by the decrease in the bond lengths in the LnNO7 polyhedra from the Ce to the Gd compound. Further, and in contrast to the previously published 5,5′-azobis[1H-tetrazol-1-ides] of the heavy yttric earths, the light Ln cations in this study are coordinated not only by H2O molecules but also by one (ZT)2− anion. Further characterization was performed by vibrational (IR and Raman) spectroscopy and elemental analysis.
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