Novel supramolecular structures constructed through hydrogen bonding (E–H⋯Cl; E = C, N, and O) and/or halogen–halogen interactions in the products of reactions of 2-[(trimethylsilyl)methyl]pyridine with TeCl4 or TeI4

Abstract

Three new complexes, [(2-C₅H₄NH)CH₂TeI₄] (1), [2-(Me₃SiCH₂)C₅H₄NH]₂[TeCl₆] (2), and [2-(CH₃)C₅H₄NH]₂[(HO)TeCl₅] (3), were obtained by the direct reaction of 2-[(trimethylsilyl)methyl]pyridine with TeI₄ or TeCl₄ in toluene. Single-crystal X-ray diffraction analysis (SCXRD) confirms that compound 1 is the first zwitterion-type complex in the organotellurium iodide family, whereas the remaining two are ionic. The asymmetric unit in 2 has only one-half of the anionic unit of [TeCl₆]²⁻, whereas a whole unit is present in 3, because the latter anionic species loses 2₁ screw axes. A discrete organotellurium iodide complex, [(2-C₅H₄NH)CH₂TeI₄], transforms into a dimer, [(2-C₅H₄NH)CH₂TeI₄]₂, due to weak secondary Te⋯I interactions, and subsequently, it transforms into a 2D-structure, [(2-C₅H₄NH)CH₂TeI₄]_n, through iodine–iodine intermolecular interactions. The formation of 2D-supramolecular structures arises through intermolecular hydrogen bonding between a pyridinium cation and [TeCl₆]²⁻ (2)/[(HO)TeCl₅]²⁻ (3) anionic species. A weak chlorine–chlorine interaction is seen in both 2 and 3.