Cs2LiV3F12 crystallizes in the trigonal R-3m space group. Cs(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted CsF6 octahedra that share corners with three equivalent Li(1)F6 octahedra and corners with nine equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 67-70°. Li(1) is bonded to six equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Cs(1)F6 octahedra and corners with six equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-67°. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-70°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Cs(1), one Li(1), and one V(1) atom.
Cs2LiV3F12 crystallizes in the trigonal R-3m space group. Cs(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted CsF6 octahedra that share corners with three equivalent Li(1)F6 octahedra and corners with nine equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 67-70°. All Cs(1)-F(1) bond lengths are 3.39 Å. All Cs(1)-F(2) bond lengths are 3.13 Å. Li(1) is bonded to six equivalent F(2) atoms to form LiF6 octahedra that share corners with six equivalent Cs(1)F6 octahedra and corners with six equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 43-67°. All Li(1)-F(2) bond lengths are 2.09 Å. V(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form VF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with four equivalent V(1)F6 octahedra, and corners with six equivalent Cs(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 41-70°. Both V(1)-F(2) bond lengths are 1.91 Å. All V(1)-F(1) bond lengths are 2.02 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1) and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Cs(1), one Li(1), and one V(1) atom.