The complex [(PAH)(4)(Cu4Cu2Br10)-Cu-II-Br-I] (1) (PAH = picolinamide hydrazone) containing a (Cu4Cu2I)-Cu-II hexanuclear cluster, with two well-separated Cu-2(II) dinuclear centers, results from a redox reaction involving a hydrolytically unstable ligand, salicilyl picolinamide hydrazone, and CuBr2 in aqueous acetonitrile. The Cu-II centers are axially bridged via long bromine contacts, leading to ferromagnetic exchange (2J = 4.04 cm(-1)). Density functional calculations have been carried out, giving a comparable singlet-triplet splitting energy. 1 crystallizes in the triclinic system, space group P1, with a = 9.253(3) Angstrom, b = 18.159(3) Angstrom, c = 7.199(5) Angstrom, alpha = 91.31(3)degrees, beta = 107,35(4)degrees, gamma = 104.22(2)degrees, and Z = 2.