The Zn(II) complexes of 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o- hydroxybenzylidene)-β-D-glucopyranosyl-amine have been synthesized and characterized using spectral and analytical methods and structure for one of the products was established. The geometry of the complexes vary from unusual distorted trigonal bipyramidal to pseudo-bicapped tetrahedron depending upon the extent of binding of pyranose ring oxygens to the Zn(II) ion, as evidenced from crystal structures. Such interaction is also reflected on the optical rotation and CD spectral properties of these complexes in solution. © 2003 Published by Elsevier B.V.