LiVSiO5 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. V(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. Si(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with four equivalent Li(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 59°. 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 Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi trigonal pyramids.
LiVSiO5 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. Both Li(1)-O(2) bond lengths are 2.26 Å. Both Li(1)-O(3) bond lengths are 2.03 Å. Both Li(1)-O(4) bond lengths are 2.00 Å. V(1) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The V(1)-O(1) bond length is 1.78 Å. The V(1)-O(2) bond length is 1.62 Å. The V(1)-O(4) bond length is 2.04 Å. Both V(1)-O(3) bond lengths are 1.86 Å. Si(1) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with four equivalent Li(1)O6 octahedra and corners with four equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 59°. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.62 Å. Both Si(1)-O(3) bond lengths are 1.64 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 Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi trigonal pyramids.