The binuclear antiferromagnetically superexchange-coupled aquabis(N-salicylidene-β-alaninato)dicopper(II) monohydrate reacts with NaSCN to yield a complex cuprate(II) of stoichiometry Na2Cu(sal-β-ala)(NCS)2 · 2 H2O. The compound has a magnetic moment μ/eff = 1.85. μΒ (Τ = 295 K), and an axial EPR spectrum with g11 > g⊥.The crystal and molecular structure of the title compound has been determined and refined to R = 0.055 (Rw = 0.062) for 1535 observed reflections, [I > 2σ(I)]. The crystals are triclinic, space group P1̅, with cell dimensions: a = 6.989(3), b = 10.445(5), c = 12.692(6)Å; α = 84.88(5), β = 70.13(4), and γ = 86.72(6)°, V = 869 Å3; Z = 2. The coordination environment of the Cu(II) atom is axially distorted square pyramidal (4 + 1). The basal plane of the pyramid is formed by the 01, Ν 1, and O 2 donor atoms of the tridentate sal-β-ala(2—) Schiff base ligand and by the N 2 atom of the additional NCS(1—) ligand. The apex of the pyramid is occupied by the weakly contacting S l′ atom of the bridging —NCS— ligand, Cu—S 1′ = 2.933(2) Å, thereby giving rise to [Cu2(sal-β-ala)2(μ-NCS)2]2- centrosymmetric binuclear complex anion. The remaining components of the crystal structure are SCN- (uncoordinated to Cu2+), Na+ ions, and H2O molecules.