Open framework materials such as zeolites and metalorganic frameworks are garnering tremendous interest because of their intriguing architecture and attractive functionalities. Thus, new types of open framework materials are highly sought after. Here, we present the discovery of completely new inorganic framework materials, where, in contrast to conventional inorganic open frameworks, the scaffold is not based on tetrahedral EO4 (E = main group element) but octahedral MO6 (M = transition metal) building blocks. These structural features place them closer to polyoxometalates than zeolites. The first representatives of this class of materials are [(R)24(NH4)14(PO(OH)2)6]·[M134(PO3(OH,F))96F120] (M = Co, R = C2Py = 1-ethylpyridinium and M = Ni, R = C4C1Py = 1-butyl-3-methylpyridinium) featuring interlinked fullerene-like nanosphere cavities. Having a transition metal building up the framework brings about interesting properties, for example, spin-glass behavior, and, with this particular topology, a hedgehog-like spin orientation.