Novel pyrazolate coordination modes and unusual Tl ⋯ Tl or Tl-π-(phenyl) interactions in the crystal structures of [{Tl3(Ph2pz)3}n], [{Tl4(Ph2pz)4}n], [{Tl4(Ph2pz)3(OH)}2] and [{Tl4(MePhpz)3(OH)}n] (Ph2pz = 3,5-diphenylpyrazolate; MePhpz = 3-methyl-5-phenylpyrazolate)

Glen B Deacon, E E Delbridge, Craig M Forsyth, Brian W Skelton, Allan H White

Research output: Contribution to journalArticleResearchpeer-review

57 Citations (Scopus)


[Tl(Ph2pz)] (Ph2pz = 3,5-diphenylpyrazolate) crystallises in two forms. The first from benzene has trinuclear molecules [Tl33(Ph2pz)3] 1 linked by intermolecular Tl-jr-t|6-Ph contacts. Within 1 the three thallium atoms are different, having coordination numbers of two (but also with theTl... η)6-Ph contact), three and four, whilst u-tin1, μs21)2:1 and (the new) μs21 modes of Ph2pz coordination are observed. Crystallisation of [TI(Ph2pz)] from 1,2-dimethoxyethane (dme) gives tetranuclear molecules [Tl4(Ph2pz)4] 2 solvated by dme. Three or four coordinate Tl atoms are observed with μs21 and μs21-pyrazolate coordination. In addition there is an intermolecular Tl-μs21-Ph interaction linking the tetranuclear molecules into a polymer, and sundry intramolecular Tl ⋯C contacts, the most important of which is an unsymmetrical Tl-μs21-Ph2pz interaction. Crystallisation of [Tl(Ph2pz)] or [Tl(MePhpz)] (MePhpz = 3-methyl-5-phenylpyrazolate) from dichloromethane afforded the partially hydrolysed tetranuclear cages [Tl4(Ph2pz)3(OH)] 3 or [Tl4(MePhpz)3(OH)] 4, which associate to give a dimer and a polymer respectively owing to Tl ⋯ Tl interactions, supported for the dimer by an intercage distant μs21-Ph2pz contact. Complex 3 features three and four coordinate Tl atoms and μs21 and μs21-pyrazolate binding, whilst 4 has three, four and five coordinate thallium atoms and solely μs21-pyrazolate ligands.

Original languageEnglish
Pages (from-to)745-751
Number of pages7
Issue number5
Publication statusPublished - 1 Dec 2000

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