Reaction of the rigid angular ligand tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene, hereafter LH4, with Mn(CH3CO2)(2)center dot 2H(2)O in a basic aqueous medium, in air, affords a crystalline product of composition Na-12{[Mn(H2O)](12)L-12}center dot H2O. Single-crystal X-ray diffraction reveals the presence of large [(Mn12L12)-L-III](12-) metallocycles of roughly hexagonal appearance, somewhat resembling a doughnut in which the central hole (van der Weals surface to surface) is roughly a nanometer across. This is the first example of a metal derivative of the fully deprotonated form, L4-. Associations with equated Na+ counterions lead to a pleasingly symmetrical packing arrangement resembling honeycomb, with the central holes of individual metallocycles lined up one above the other. The ligand L4-, on account of its rigid angularity and its strong metal binding properties, promises to provide a rich source of unusual metal-containing structures, in particular cages, in future studies.