Past exam of the materials science course of the University of Cambridge / 2017 / Paper 1 / 1 / b / Solution

Each calcium cation has eight fluoride neighbours at the vertices of a cube: cubic coordination. Each fluoride anion has four calcium neighbours in tetrahedral coordination. Both unlike-neighbour Euclidean distances are $\sqrt{3}a/4$, with $a$ the conventional cubic lattice parameter.

Apply the Goldschmidt packing principle at its limiting eight-coordinate geometry: the eight surrounding anions just touch one another and also touch the central cation. The anions form a cube of edge $a/2$, so $2r_a=a/2$ and $r_a+r_c=\sqrt{3}a/4$. Eliminating $a$ givesEquivalently, $r_c/r_a=0.732$. This is a limiting radius ratio rule, rather than a measured ionic-radius ratio. It does not assume that the calcium sublattice consists of mutually touching spheres: the calcium positions have face-centred cubic symmetry, but that symmetry alone does not specify which ions touch. A different construction with touching calcium spheres and fluoride just filling their tetrahedral interstitial sites would instead give $r_a/r_c=\sqrt{3/2}-1=0.225$; that is the opposite contact limit, not the eight-coordinate anion-contact ideal used here.