Cs2LiF3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form CsF6 octahedra that share corners with two equivalent Cs(2)F8 hexagonal bipyramids, corners with two equivalent Cs(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, edges with five equivalent Cs(2)F8 hexagonal bipyramids, edges with six equivalent Cs(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. In the second Cs site, Cs(2) is bonded to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms to form distorted CsF8 hexagonal bipyramids that share corners with six equivalent Cs(2)F8 hexagonal bipyramids, corners with two equivalent Cs(1)F6 octahedra, edges with two equivalent Cs(2)F8 hexagonal bipyramids, edges with five equivalent Cs(1)F6 octahedra, edges with six equivalent Li(1)F4 tetrahedra, and faces with two equivalent Cs(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 3°. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with two equivalent Cs(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, edges with six equivalent Cs(2)F8 hexagonal bipyramids, and  an edgeedge with one Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles are 25°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Li(1) atoms. In the second F site, F(2) is bonded in a linear geometry to four equivalent Cs(2) and two equivalent Li(1) atoms. In the third F site, F(3) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form a mixture of edge and corner-sharing FCs6 octahedra. The corner-sharing octahedral tilt angles are 3°.
Cs2LiF3 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form CsF6 octahedra that share corners with two equivalent Cs(2)F8 hexagonal bipyramids, corners with two equivalent Cs(1)F6 octahedra, corners with two equivalent Li(1)F4 tetrahedra, edges with five equivalent Cs(2)F8 hexagonal bipyramids, edges with six equivalent Cs(1)F6 octahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. Both Cs(1)-F(1) bond lengths are 3.08 Å. There are two shorter (2.92 Å) and two longer (3.10 Å) Cs(1)-F(3) bond lengths. In the second Cs site, Cs(2) is bonded to two equivalent F(1), two equivalent F(3), and four equivalent F(2) atoms to form distorted CsF8 hexagonal bipyramids that share corners with six equivalent Cs(2)F8 hexagonal bipyramids, corners with two equivalent Cs(1)F6 octahedra, edges with two equivalent Cs(2)F8 hexagonal bipyramids, edges with five equivalent Cs(1)F6 octahedra, edges with six equivalent Li(1)F4 tetrahedra, and faces with two equivalent Cs(2)F8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 3°. Both Cs(2)-F(1) bond lengths are 3.10 Å. Both Cs(2)-F(3) bond lengths are 3.14 Å. All Cs(2)-F(2) bond lengths are 3.08 Å. Li(1) is bonded to two equivalent F(1) and two equivalent F(2) atoms to form LiF4 tetrahedra that share corners with two equivalent Cs(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, edges with six equivalent Cs(2)F8 hexagonal bipyramids, and  an edgeedge with one Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles are 25°. Both Li(1)-F(1) bond lengths are 2.16 Å. Both Li(1)-F(2) bond lengths are 1.86 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Li(1) atoms. In the second F site, F(2) is bonded in a linear geometry to four equivalent Cs(2) and two equivalent Li(1) atoms. In the third F site, F(3) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form a mixture of edge and corner-sharing FCs6 octahedra. The corner-sharing octahedral tilt angles are 3°.