CeF3 crystallizes in the hexagonal P6_322 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), and eight equivalent F(1) atoms. In the second Ce site, Ce(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), and eight equivalent F(1) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to four Ce(1,1) atoms to form distorted FCe4 tetrahedra that share corners with three equivalent F(3)Ce6 octahedra, corners with nineteen equivalent F(1)Ce4 tetrahedra,  an edgeedge with one F(3)Ce6 octahedra, edges with three equivalent F(1)Ce4 tetrahedra,  a faceface with one F(3)Ce6 octahedra, and  a faceface with one F(1)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-64°. In the second F site, F(2) is bonded in a trigonal planar geometry to three Ce(1,1) atoms. In the third F site, F(3) is bonded to six Ce(1,1) atoms to form FCe6 octahedra that share corners with eighteen equivalent F(1)Ce4 tetrahedra, edges with six equivalent F(1)Ce4 tetrahedra, faces with two equivalent F(3)Ce6 octahedra, and faces with six equivalent F(1)Ce4 tetrahedra.
CeF3 crystallizes in the hexagonal P6_322 space group. There are two inequivalent Ce sites. In the first Ce site, Ce(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), and eight equivalent F(1) atoms. Both Ce(1)-F(2) bond lengths are 2.42 Å. Both Ce(1)-F(3) bond lengths are 2.94 Å. There are a spread of Ce(1)-F(1) bond distances ranging from 2.37-2.71 Å. In the second Ce site, Ce(1) is bonded in a 12-coordinate geometry to two equivalent F(2), two equivalent F(3), and eight equivalent F(1) atoms. Both Ce(1)-F(2) bond lengths are 2.42 Å. Both Ce(1)-F(3) bond lengths are 2.94 Å. There are a spread of Ce(1)-F(1) bond distances ranging from 2.37-2.71 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to four Ce(1,1) atoms to form distorted FCe4 tetrahedra that share corners with three equivalent F(3)Ce6 octahedra, corners with nineteen equivalent F(1)Ce4 tetrahedra,  an edgeedge with one F(3)Ce6 octahedra, edges with three equivalent F(1)Ce4 tetrahedra,  a faceface with one F(3)Ce6 octahedra, and  a faceface with one F(1)Ce4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-64°. In the second F site, F(2) is bonded in a trigonal planar geometry to three Ce(1,1) atoms. In the third F site, F(3) is bonded to six Ce(1,1) atoms to form FCe6 octahedra that share corners with eighteen equivalent F(1)Ce4 tetrahedra, edges with six equivalent F(1)Ce4 tetrahedra, faces with two equivalent F(3)Ce6 octahedra, and faces with six equivalent F(1)Ce4 tetrahedra.