On an Unexpected 2D‐linked Rare Earth 1,2,4‐Triazolate Network: Synthesis,Crystal Structure,Spectroscopic and Thermal Properties of $_{\infty}^{2}\rm [Ho(Tz)_{3}(TzH)_{2}]TzH$

The network compound , (Tz^? = 1,2,4‐triazolate anion, C₂H₂N₃^?, TzH = 1,2,4‐1H‐triazole, C₂H₃N₃), was obtained as pink single crystals by the reaction of the holmium metal with a melt of the amine 1,2,4‐1H‐triazole. No additional solvent was used. The compound is an unexpected example of a 2D‐linked network structure as other lanthanides give 3D‐frameworks and MOFs with 1,2,4‐1H‐triazole instead. This illustrates that the series of lanthanides yields very different results in attempts to create MOF structures. In the triazolate ligands Tz^? function both as μ‐η¹:η² linkers as well as η¹ end on ligands. The latter coordination mode is also found for additional triazole molecules. C.N. is nine for holmium(III). The layers exhibit a system of intra and inter layer hydrogen bonding and to triazole molecules from the melt reaction intercalated in‐between the layers. The product was investigated by X‐ray single crystal analysis, Mid IR, Far IR and Raman spectroscopy, and with DTA/TG regarding its thermal behaviour.