Unusual trimeric and tetrameric water clusters have been observed in a complex of [Cu(DBA) (phen)(2)center dot(H2O)(4)center dot(NO3)] (1), (HDBA = benzilic acid, phen = 1,10-phenanthroline), which was prepared under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), UV-Vis spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction. In 1, a butterfly-like water-nitrate trimer formed by two water molecules and one nitrate anion, as well as a cyclic tetrameric water cluster are observed. The uncoordinated carboxylate oxygen atoms of DBA ligands, water molecules and nitrate anions interact via hydrogen bonds and extend 1 into a water-anion-cation tape, which in turn join to form a double water-anion-cation tape via pi center dot center dot center dot pi stacking interactions involving neighboring pyridyl and phenyl groups of DBA ligands. (C) 2012 Elsevier B. V. All rights reserved.