Supramolecular Assembling of Complex Tellurium Salts: Synthesis and Crystal Structures of {Cs[PhTeCl 4 ]·CH 3 OH} and Cs[PhTeBr 4 ]

The direct reaction between PhTeCl 3 and CsCl in methanol affords {Cs[PhTeCl 4 ]·CH 3 OH}. Cs[PhTeBr 4 ] was prepared by refluxing [2‐Br‐C 5 NH 5 ][PhTeBr 4 ] and CsCl in ethanol in the presence of an excess of HBr. In {Cs[PhTeCl 4 ]·CH 3 OH} the [PhTeCl 4 ] — units form dimers by secondary Te···Cl bonds with methanol molecules bridging adjacent Cs + cations. In both compounds, the alkali metal cation interacts secondarily with the chlorine and bromine Te‐ligands, achieving singular coordination polyhedrons and holding the lattices in supramolecular tridimensional assemblies. The new complexes, {Cs[PhTeCl 4 ]·CH 3 OH} and Cs[PhTeBr 4 ], crystallize in the space groups P2 1 /c and P2 1 /n, respectively. Only one such structure has been reported before.