The complex [{VO(L)}(2){VO(acac)}(2)(mu(2)-OMe)(2)1 1 can be synthesized by reaction of the Schiff base ligand N,N-bis(2-hydroxyethyl)-N’-(2-pyrrolylmethylidene)ethylenediamine (H2L) with [VO(acac)(2)] (Hacac = 2,4-pentanedione). The compound 1 . MeOH has been characterized by IR, UV/vis, and ESR spectroscopy as well as magnetic susceptibility measurements. A single-crystal diffraction study performed on 1 . MeOH gives the following crystal data : triclinic, P (1) over bar, a = 7.352(2) Angstrom, b = 12,584(4) Angstrom, c = 12.826(4) Angstrom, alpha 107.61(2)degrees, beta = 102.96(2)degrees, gamma = 95.25(2)degrees, Z = 1. The tetranuclear {(VO)(4)(mu(3)-OR)(2)(mu(2)-OR)(4)}(2+) core of 1 is composed of three different types of edge-shared binuclear units, an anti-coplanar, two syn-coplanar, and two twist configurations. Consistent with this connectivity pattern, analysis of the magnetic data reveals competing ferritmagnetic and antiferromagnetic exchange interactions within the tetranuclear con structure. Both ESR and magnetic data indicate a singlet ground state for 1. In addition, the general magnetic behavior of oxovanadium(IV) clusters is discussed on the basis of classification schemes derived from simple binuclear fragmentation patterns. Consistent with the superexchange mechanism expected to be operative for binuclear oxovanadium(IV) units with syn-coplanar configuration, the corresponding magnetic exchange parameter J(sc) of 1 (V ... V = 3.410(2) Angstrom) is determined to be antiferromagnetic at -153 cm(-1).