LiV2(SiO4)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-51°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-51°. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-62°. In the second Si site, Si(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the third O site, O(3) is bonded in a distorted tetrahedral geometry to one Li(1), one V(1), one V(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one Si(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom.
LiV2(SiO4)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), one O(7), and one O(8) atom. The Li(1)-O(1) bond length is 2.28 Å. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(6) bond length is 2.31 Å. The Li(1)-O(7) bond length is 2.03 Å. The Li(1)-O(8) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-51°. The V(1)-O(3) bond length is 2.14 Å. The V(1)-O(4) bond length is 2.13 Å. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(6) bond length is 2.15 Å. The V(1)-O(7) bond length is 1.98 Å. The V(1)-O(8) bond length is 1.96 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO6 octahedra that share corners with four equivalent V(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-51°. The V(2)-O(1) bond length is 1.89 Å. The V(2)-O(2) bond length is 1.85 Å. The V(2)-O(3) bond length is 2.07 Å. The V(2)-O(4) bond length is 2.03 Å. The V(2)-O(5) bond length is 2.08 Å. The V(2)-O(6) bond length is 2.01 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-62°. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(3) bond length is 1.67 Å. The Si(1)-O(4) bond length is 1.66 Å. In the second Si site, Si(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-60°. The Si(2)-O(5) bond length is 1.67 Å. The Si(2)-O(6) bond length is 1.69 Å. The Si(2)-O(7) bond length is 1.62 Å. The Si(2)-O(8) bond length is 1.62 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the third O site, O(3) is bonded in a distorted tetrahedral geometry to one Li(1), one V(1), one V(2), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one Si(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom.