[Tl(Ph2pz)] (Ph2pz = 3,5-diphenylpyrazolate) crystallises in two forms. The first from benzene has trinuclear molecules [Tl3(Ph2pz)3] 1 linked by intermolecular Tl–π-η6-Ph contacts. Within 1 the three thallium atoms are different, having coordination numbers of two (but also with the Tl⋯η6-Ph contact), three and four, whilst μ-η1∶η1, μ3-η1∶η2∶η1 and (the new) μ3-η1∶η1∶η1 modes of Ph2pz coordination are observed. Crystallisation of [Tl(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 μ3-η1∶η2∶η1 and μ3-η1∶η1∶η1-pyrazolate coordination. In addition there is an intermolecular Tl–π-η3-Ph interaction linking the tetranuclear molecules into a polymer, and sundry intramolecular Tl⋯C contacts, the most important of which is an unsymmetrical Tl–π-η5-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 Tl–π-η5-Ph2pz contact. Complex 3 features three and four coordinate Tl atoms and μ3-η1∶η2∶η1 and μ3-η1∶η1∶η1-pyrazolate binding, whilst 4 has three, four and five coordinate thallium atoms and solely μ3-η1∶η2∶η1-pyrazolate ligands.
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