LaF3 crystallizes in the hexagonal P6_3/mcm space group. La(1) is bonded in a 12-coordinate geometry to two equivalent F(1), two equivalent F(2), and eight equivalent F(3) atoms. There are three inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to three equivalent La(1) atoms. In the second F site, F(3) is bonded to four equivalent La(1) atoms to form distorted FLa4 tetrahedra that share corners with three equivalent F(1)La6 octahedra, corners with nineteen equivalent F(3)La4 tetrahedra,  an edgeedge with one F(1)La6 octahedra, edges with three equivalent F(3)La4 tetrahedra,  a faceface with one F(1)La6 octahedra, and  a faceface with one F(3)La4 tetrahedra. The corner-sharing octahedral tilt angles range from 10-64°. In the third F site, F(1) is bonded to six equivalent La(1) atoms to form FLa6 octahedra that share corners with eighteen equivalent F(3)La4 tetrahedra, edges with six equivalent F(3)La4 tetrahedra, faces with two equivalent F(1)La6 octahedra, and faces with six equivalent F(3)La4 tetrahedra.
LaF3 crystallizes in the hexagonal P6_3/mcm space group. La(1) is bonded in a 12-coordinate geometry to two equivalent F(1), two equivalent F(2), and eight equivalent F(3) atoms. Both La(1)-F(1) bond lengths are 2.98 Å. Both La(1)-F(2) bond lengths are 2.44 Å. There are a spread of La(1)-F(3) bond distances ranging from 2.39-2.72 Å. There are three inequivalent F sites. In the first F site, F(2) is bonded in a trigonal planar geometry to three equivalent La(1) atoms. In the second F site, F(3) is bonded to four equivalent La(1) atoms to form distorted FLa4 tetrahedra that share corners with three equivalent F(1)La6 octahedra, corners with nineteen equivalent F(3)La4 tetrahedra,  an edgeedge with one F(1)La6 octahedra, edges with three equivalent F(3)La4 tetrahedra,  a faceface with one F(1)La6 octahedra, and  a faceface with one F(3)La4 tetrahedra. The corner-sharing octahedral tilt angles range from 10-64°. In the third F site, F(1) is bonded to six equivalent La(1) atoms to form FLa6 octahedra that share corners with eighteen equivalent F(3)La4 tetrahedra, edges with six equivalent F(3)La4 tetrahedra, faces with two equivalent F(1)La6 octahedra, and faces with six equivalent F(3)La4 tetrahedra.