Polynuclear and tetranuclear cuprous iodide complexes derived from N-(2-thienylmethylidene)-2-pyridylamine derivatives

The reaction of bidentate thienyl Schiff base derivatives, R-Th-C=N-Py (R = H, 3-Me, 5-Me, and 5-Br), with copper(l) iodide under mild conditions in acetonitrile yields (i) two one-dimensional coordination polymer chain complexes with alternating six-membered and four-membered metallocycles, [Cu-2-(C4H3SCHNC5H4N)(mu(2)-I)(mu(3)-I)](n), (1) and [Cu-2(3-Me-C4H2SCHNC5H4N)(mu(2)-I)(mu(3)-I)](n) (2), and (ii) two discrete chair-pyramidal shaped tetranuclear complexes, Cu-4(5-Me-C4H2SCHNC5H4N)(2)(mu(2)-I)(2)(mu(3)-I)(2) (3) and Cu-4(5-Br-C4H2SCHNC5H4N)(2)(mu(2)-I)2(mu(3)-I)(2) (4). These complexes are characterized spectrally. The molecular structures of 1, 2, 3 and 4 were established in detail by single-crystal X-ray diffraction analysis. The polymer chain structure of 2 is found to be extended into a two-dimensional supramolecular network through hydrogen-bonded interactions. (C) 2005 Elsevier Ltd. All rights reserved.