LiVSi3O8 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(7) atom. V(1) is bonded to one O(1), one O(4), one O(7), one O(8), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-64°. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. In the third Si site, Si(3) is bonded to one O(2), one O(3), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-39°. 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(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) 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(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one Si(2), and one Si(3) atom.
LiVSi3O8 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(4), one O(5), and one O(7) atom. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(4) bond length is 2.24 Å. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(7) bond length is 2.12 Å. V(1) is bonded to one O(1), one O(4), one O(7), one O(8), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(4) bond length is 2.01 Å. The V(1)-O(7) bond length is 1.98 Å. The V(1)-O(8) bond length is 2.18 Å. There is one shorter (2.14 Å) and one longer (2.28 Å) V(1)-O(5) bond length. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-64°. The Si(1)-O(2) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(5) bond length is 1.65 Å. The Si(1)-O(6) bond length is 1.62 Å. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 43°. The Si(2)-O(1) bond length is 1.61 Å. The Si(2)-O(4) bond length is 1.63 Å. The Si(2)-O(6) bond length is 1.63 Å. The Si(2)-O(8) bond length is 1.69 Å. In the third Si site, Si(3) is bonded to one O(2), one O(3), one O(7), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-39°. The Si(3)-O(2) bond length is 1.62 Å. The Si(3)-O(3) bond length is 1.64 Å. The Si(3)-O(7) bond length is 1.62 Å. The Si(3)-O(8) bond length is 1.66 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(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) 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(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one V(1), one Si(2), and one Si(3) atom.