Thallium(I)- and organothallium(III)-substituted mono-, bis- and tris-tetrazoles: synthesis and supramolecular structures

Six thallium(I) tetrazolates have been synthesized by either the addition of an alcoholic solution of the appropriate tetrazole to an ethanolic solution of thallium ethoxide, or from the sodium salt of the tetrazole with Tl2SO4. Seven diphenylthallium-substituted mono- and bis-tetrazoles have been synthesized by a condensation route involving the appropriate tetrazole and diphenylthallium hydroxide. 1-Diphenylthallyl-5-phenyltetrazole has also been prepared by a cycloaddition reaction between diphenylthallium azide and benzonitrile. The structures of [Tl(18-crown-6)+]2[C2N102−], Ph2TlN4CPh·MeOH, 1,4-(Ph2TlN4C)2C4H8·2MeOH and 1,2-(Ph2TlN4C)2C6H4·Ph2TlCl·2MeOH·2H2O have been determined. The last three compounds generate supramolecular structures which incorporate six-membered Tl2N4 rings. The last two contain the first examples of tetrazoles which utilise all four available ring nitrogens for co-ordination.