Supramolecular architectures in novel diphenyl(aryl)tin(IV) chlorides

Abstract

The diphenyl(aryl)tin(IV) chloride [2-{(CH2O)2CH)}C6H4]SnPh2Cl (1) was prepared reacting [2-{(CH2O)2CH)}C6H4]Li with Ph2SnCl2. Hydrolysis of 1 with p-toluenesulfonic acid as a proton source gave [2-(OCH)C6H4]SnPh2Cl (2), which in turn was reacted with 2-(aminomethyl)pyridine, benzidine, 1-aminopyrene, in the absence of a solvent or catalyst, to afford the mono- or bimetallic species [2-(2′-PyCH2NCH)C6H4]SnPh2Cl (3), ClSnPh2[2-C6H4(4-CHN-1,1′-C6H4C6H4-4′-NCH)-2′-C6H4]Ph2SnCl (4) and [2-(C16H12NCH)C6H4]SnPh2Cl (5) (Py = pyridyl, C16H12 = pyrene). The compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry in solution and IR spectroscopy in solid state. The molecular structures for compounds 1–5 were established by single-crystal X-ray diffraction. For all compounds the metal center is pentacoordinated with a distorted trigonal bipyramidal geometry and a (C,E)C2SnX core (E = O, Nimine) as a result of intramolecular E→Sn interactions. The presence of CH···Cl and CH···π (Phcentroid, Pycentroid, Pyrenecentroid) intermolecular interaction led to the formation of supramolecular associations in solid state for all compounds, thus, ribbon-like polymer occurs in crystal of 1, 2D layers arise in the case of 2 and 4, and complex 3D architectures are found in 3 and 5.