New versatile organyltellurium(IV) halides: Synthesis and X-ray structural features of the telluronium tellurolate salts [PhTe(CH3)2]2[TeX6] (X = Cl, Br) and [Ph3Te][PhTeX4] (X = Cl, Br, I)

TeX4 (X = Cl, Br) react in HCl/HBr with [Ph(CH3)2Te]X (X = Cl, Br) to give [PhTe(CH3)2]2[TeCl6] (1) and [PhTe(CH3)2]2[TeBr6] (2). The reaction of PhTeX3 (X = Cl, Br, I) in cooled methanol with [(Ph)3Te]X (X = Cl, Br, I) leads to [Ph3Te][PhTeCl4] (3), [Ph3Te][PhTeBr4] (4) and [Ph3Te][PhTeI4] (5). In the lattices of the telluronium tellurolate salts 1 and 2, octahedral TeCl6 and TeBr6 dianions are linked by telluronium cations through Te⋯Cl and Te⋯Br secondary bonds, attaining bidimensional (1) and three-dimensional (2) assemblies. The complexes 3, 4 and 5 show two kinds of Te⋯halogen secondary interactions: the anion–anion interactions, which form centrosymmetric dimers, and two identical sets of three telluronium–tellurolate interactions, which accomplish the centrosymmetric fundamental moiety of the supramolecular arrays of the three compounds, with the tellurium atoms attaining distorted octahedral geometries. Also phenyl C–H⋯halogen secondary interactions are structure forming forces in the crystalline structures of compounds 3, 4 and 5.