Reaction of H8L with MnCl2•4H2O in a basic dmf/MeOH mixture affords single crystals of [Mn III 4Mn II 6(L)2(µ3-OH)4(µ-OH)4(MeOH)4(dmf)4(MeCN)2]•MeCN (3, Fig. ), following vapour diffusion of MeCN into the mother liquor. The crystals were found to be in a monoclinic cell and structure solution was carried out in the space group P21/n. The asymmetric unit (ASU) comprises half of the cluster, with an inversion centre located in the middle of the Mn5-O14-Mn5'-O14' rhomb. Pertinent bond lengths and angles (Table ) and BVS calculations (Table ) are given in the supplementary information.