Abstract
The reactions of CoCl2 with the alkylated aminophosphine N-alkyl-1,3,5-triaza-7-phosphaadamantane iodide [PTA-R]I (R = Me, Et) and NaSCN, in an ethanolic medium at ambient temperature, lead to the self-assembly formation of the hybrid 2:1 organic-inorganic salts [PTA-R](2)[Co(NCS)(4)] (R = Me (1); Et (2)), which have been characterized by IR spectroscopy, FAB(+)-MS, elemental and single crystal X-ray diffraction structural analyses. The molecular structures bear two cage-like [PTA-R](+) cations and one discrete tetrahedral [Co(NCS)(4)](2) anion. Adjacent anions are linked via repeating weak intermolecular S center dot center dot center dot S contacts forming 1D supramolecular inorganic networks, acting as hosts for the [PTA-R](+) guests. 1 and 2 represent the first structurally characterized examples of compounds where any uncoordinated cage-like PTA derivative acts as a component of a hybrid organic-inorganic material. (C) 2008 Elsevier B.V. All rights reserved.