Li3V(SO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. In the second V site, V(2) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-47°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(2) and one S(1) atom.
Li3V(SO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. There is one shorter (1.94 Å) and one longer (2.34 Å) Li(1)-O(2) bond length. There is one shorter (2.35 Å) and one longer (2.42 Å) Li(1)-O(3) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to six equivalent O(1) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. All V(1)-O(1) bond lengths are 2.05 Å. In the second V site, V(2) is bonded to six equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. All V(2)-O(4) bond lengths are 2.00 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and  a cornercorner with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-47°. The S(1)-O(1) bond length is 1.51 Å. The S(1)-O(2) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.46 Å. The S(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one V(2) and one S(1) atom.