Reaction of MnCl2•4H2O with H4TBC [4] in a basic dmso/MeOH mixture affords single crystals of formula [Mn III 3Na6(TBC [4])3(CO3)(Cl)(dmso)7]•5MeCN ([Mn3Na6]; 1•5MeCN, Fig. and) following 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 C2/c with the asymmetric unit (ASU) comprising half of the formula.