The synthesis, thermogravimetric and X-ray structure analysis of a highly unusual copper compound prepared from a chiral tridentate Schiff base ligand is reported. The title compound [CuL(H(2)O(2)]. CuL(H(2)O(3)].H(2)O crystallizes in the orthorhombic crystal system in space group P2(1)2(1)2(1) with Z = 4. Two independent CuL(H(2)O)(n) complexes are present in the same unit cell, one five- and the other six- coordinate. The five-coordinate copper(II) centre occupies a distorted square-pyramidal geometry whereas the six-coordinate copper(II) centre has a distorted octahedral geometry. The independent copper complexes and the uncoordinated water molecule are joined together with intermolecular hydrogen bonds in a two-dimensional supramolecular network which lies parallel to the ab plane.