LiV2(SiO4)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-75°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), 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 three equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-55°. In the second Si site, Si(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-57°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 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 trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1) and one Si(2) 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(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one V(1), one V(2), and one Si(2) atom to form distorted edge-sharing OLiV2Si tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one V(1), one V(2), and one Si(2) atom to form distorted edge-sharing OLiV2Si tetrahedra.
LiV2(SiO4)2 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 70-75°. The Li(1)-O(1) bond length is 1.97 Å. The Li(1)-O(2) bond length is 1.91 Å. The Li(1)-O(7) bond length is 2.10 Å. The Li(1)-O(8) bond length is 2.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), 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 three equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. The V(1)-O(2) bond length is 1.98 Å. The V(1)-O(4) bond length is 1.92 Å. The V(1)-O(5) bond length is 2.12 Å. The V(1)-O(6) bond length is 2.12 Å. The V(1)-O(7) bond length is 2.17 Å. The V(1)-O(8) bond length is 2.17 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. The V(2)-O(1) bond length is 1.90 Å. The V(2)-O(3) bond length is 1.81 Å. The V(2)-O(5) bond length is 1.99 Å. The V(2)-O(6) bond length is 1.99 Å. The V(2)-O(7) bond length is 2.13 Å. The V(2)-O(8) bond length is 2.13 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(5), and one O(6) atom to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-55°. The Si(1)-O(1) bond length is 1.65 Å. The Si(1)-O(2) bond length is 1.62 Å. The Si(1)-O(5) bond length is 1.67 Å. The Si(1)-O(6) bond length is 1.67 Å. In the second Si site, Si(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-57°. The Si(2)-O(3) bond length is 1.64 Å. The Si(2)-O(4) bond length is 1.60 Å. The Si(2)-O(7) bond length is 1.67 Å. The Si(2)-O(8) bond length is 1.67 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 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 trigonal planar geometry to one Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to one V(1) and one Si(2) 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(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Si(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one V(1), one V(2), and one Si(2) atom to form distorted edge-sharing OLiV2Si tetrahedra. In the eighth O site, O(8) is bonded to one Li(1), one V(1), one V(2), and one Si(2) atom to form distorted edge-sharing OLiV2Si tetrahedra.