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The local coordination of Nb1 and Nb2 in CaNb5+ 2(P4O13)(P2O7)O. (a) In this structure, the two crystallographically distinct Nb5+O6 octahedra do not have equal bonds 5/6 v.u. in strength. Instead, (b) non-local bond-topological asymmetry imposes bond-valence (and thus bond-length) variability within the polyhedra, which (c) serve as starting configurations for crystallographic effects to lead to the observed local geometries. The shaded spheres represent O2−.
