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]₂TeCl₆] (1) and PhTe(CH₃)₂]₂TeBr₆] (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.