LiVSi3O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. V(1) is bonded to one O(1), one O(4), one O(5), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent V(1)O4 tetrahedra. In the third Si site, Si(3) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. 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(1), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), 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 Li(1), one V(1), and one Si(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Si(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one Si(2) atom.
LiVSi3O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(5) bond length is 2.17 Å. The Li(1)-O(6) bond length is 2.13 Å. V(1) is bonded to one O(1), one O(4), one O(5), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(4) bond length is 1.94 Å. The V(1)-O(5) bond length is 1.93 Å. The V(1)-O(8) bond length is 1.91 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The Si(1)-O(1) bond length is 1.62 Å. The Si(1)-O(3) bond length is 1.63 Å. The Si(1)-O(6) bond length is 1.66 Å. The Si(1)-O(7) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and corners with two equivalent V(1)O4 tetrahedra. The Si(2)-O(2) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.64 Å. The Si(2)-O(6) bond length is 1.67 Å. The Si(2)-O(8) bond length is 1.62 Å. In the third Si site, Si(3) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. The Si(3)-O(2) bond length is 1.63 Å. The Si(3)-O(3) bond length is 1.63 Å. The Si(3)-O(5) bond length is 1.62 Å. The Si(3)-O(7) bond length is 1.64 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(1), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the third O site, O(3) is bonded in a linear geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), 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 Li(1), one V(1), and one Si(3) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(1), one Si(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one V(1) and one Si(2) atom.