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Abstract. [Ni(C18H13BrN203)(H20)3].2H20, Mr = 534-0, monoclinic, P21, a = 7.379 (1), b = 7.63, (1), c =19-981(3) A, fl=99-29(1) °, V=llll.I(2)A 3, Dx =1.59/~cm -3, Z=2, F(000)=544, Cu Ka, A= 1-5418 A,/z = 37.7 cm-l, room temperature. Final R = 0.051, wR = 0.050 for 1811 observed reflections. The structure consists of discrete molecules of the complex, with the Ni n ion octahedrally coordinated to one terdentate Schiff-base moiety and three water molecules; there are two additional non-coordinated water molecules in the asymmetric unit. The crystal structure is supported by a network of hydrogen bonds, involving water molecules and the phenolic and carboxylic O atoms.Introduction. The magnetic properties of complexes of N-salicylidene-L-amino acids with transition-metal ions have been extensively investigated by variabletemperature magnetic susceptibility measurements and ESR spectroscopy. These compounds exhibit a wide range of magnetic and spectroscopic properties and have been described as monomers, dimers and