The complex [CuAdp(H2O)(2)] . 1/3CH(3)OH . 1/6C(2)H(5)OH (Adp = aniline-N,N-di-3-propionic acid) has been synthesized and structurally studied. The complex crystallizes in the trigonal system, space group R 3, a = 16.433(2) Angstrom, c = 32.754(7) Angstrom, V = 7660(2) Angstrom(3), Z = 18, R = 0.0445 for 3148 reflections with I greater than or equal to 2sigma(I). The tetragonal-pyramidal coordination (4 + 1) of the Cu atom is formed of two 0 atoms and the N atom of the tridentate Adp ligand, as well as the two oxygen atoms of water molecules. The aminodipropionate group of the ligand resides in the basal plane of the pyramid (average Cu-O 1.939 Angstrom, Cu-N 2.051 Angstrom), as well as one of the coordinated water molecules (Cu-O(w) 2.009 Angstrom). The apical position is occupied by the second water molecule (Cu-O(w) 2.298 Angstrom). The benzene ring of the ligand is normal to the basal plane, so that the ortho-H atom occupies the sixth coordination position (Cu-H 2.650 Angstrom). Some factors governing the copper(II) selectivity of Adp have been recognized.