LiVSi2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO5 square pyramids that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. V(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O5 square pyramids. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-59°. In the second Si site, Si(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 31-59°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Si(2) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Si(1) atom to form distorted corner-sharing OLiV2Si trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Si(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.
LiVSi2O6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted LiO5 square pyramids that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.04 Å. The Li(1)-O(4) bond length is 2.41 Å. The Li(1)-O(5) bond length is 2.11 Å. V(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O5 square pyramids. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.97 Å. There is one shorter (2.10 Å) and one longer (2.12 Å) V(1)-O(2) bond length. Both V(1)-O(3) bond lengths are 2.11 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(3), one O(5), and two equivalent O(6) atoms to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-59°. The Si(1)-O(3) bond length is 1.66 Å. The Si(1)-O(5) bond length is 1.62 Å. Both Si(1)-O(6) bond lengths are 1.65 Å. In the second Si site, Si(2) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 31-59°. The Si(2)-O(1) bond length is 1.61 Å. The Si(2)-O(2) bond length is 1.65 Å. Both Si(2)-O(4) bond lengths are 1.65 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Si(2) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Si(1) atom to form distorted corner-sharing OLiV2Si trigonal pyramids. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Si(2) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.