N-(3-hydroxypyridine-2-yl)-5-hydroxysalicylideneimine(HOC6H3OHCH=NC5H3NOH) (1) and its dimethyltin(TV) complex (Me2Sn(OC6H3OHCH=NC5H3NO)) (2) were prepared and characterized by H-1-NMR, IR, mass spectroscopy and single crystal X-ray diffraction method. The complex (2) crystallizes in the space group C-2/c with cell dimensions a = 20.84](2), b = 10.646(2), c = 13.206(2) Angstrom, beta = 105.95(1)degrees with Z = 8, V = 2817.3(6) Angstrom(3). Molecular structure has been determined by standard methods and refined by full-matrix least squares (on F-2) to R value of 0.036. The studied tin(IV) complex exhibits the strongly distorted square-pyramidal geometry around tin atom. In the solid state, each distorted square-pyramidal Me2Sn(OC6H3OHCH=NC5H3NO) unit is connected to the others via dual use of hydrogen bonds and pi-pi interactions. The tautomeric effect of ligand was discussed besides the coordination geometry of the complex (2). (C) 2004 Elsevier B.V. All rights reserved.