LiV3F10 crystallizes in the orthorhombic Pmma space group. Li(1) is bonded in a bent 120 degrees geometry to two equivalent F(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent V(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 15°. In the second V site, V(2) is bonded to one F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form VF7 pentagonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F7 pentagonal bipyramids, and  an edgeedge with one V(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 37°. There are five inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(2) atoms.
LiV3F10 crystallizes in the orthorhombic Pmma space group. Li(1) is bonded in a bent 120 degrees geometry to two equivalent F(5) atoms. Both Li(1)-F(5) bond lengths are 1.86 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1) and four equivalent F(3) atoms to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra and corners with four equivalent V(2)F7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 15°. Both V(1)-F(1) bond lengths are 1.99 Å. All V(1)-F(3) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to one F(2), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms to form VF7 pentagonal bipyramids that share corners with two equivalent V(1)F6 octahedra, corners with three equivalent V(2)F7 pentagonal bipyramids, and  an edgeedge with one V(2)F7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 37°. The V(2)-F(2) bond length is 1.98 Å. Both V(2)-F(3) bond lengths are 2.05 Å. Both V(2)-F(4) bond lengths are 2.00 Å. Both V(2)-F(5) bond lengths are 2.10 Å. There are five inequivalent F sites. In the first F site, F(1) is bonded in a linear geometry to two equivalent V(1) atoms. In the second F site, F(2) is bonded in a linear geometry to two equivalent V(2) atoms. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to two equivalent V(2) atoms. In the fifth F site, F(5) is bonded in a trigonal non-coplanar geometry to one Li(1) and two equivalent V(2) atoms.