The initial employment of alpha-benzoin oxime (bzoxH(2)) in higher oxidation state 3d metal cluster chemistry has provided access to a new enneanuclear Mn-III complex with an unprecedented metal-core topology consisting of two triangular [Mn-3(mu(3)-O2-)(mu-ON)(3)](4+) fragments connected by a linear [Mn-3(mu-ON)(6)](3+) unit. The Mn-9(III) cluster is antiferromagnetically coupled and has an S=3 spin ground state.