Li2VSiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted VO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra and corners with eight equivalent Li(1)O4 tetrahedra. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra and corners with eight equivalent Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one Si(1) atom. In the second O site, O(2) is bonded in a tetrahedral geometry to two equivalent Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one Si(1) atom.
Li2VSiO4 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.99 Å. There is one shorter (1.99 Å) and one longer (2.01 Å) Li(1)-O(1) bond length. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted VO4 tetrahedra that share corners with four equivalent Si(1)O4 tetrahedra and corners with eight equivalent Li(1)O4 tetrahedra. The V(1)-O(2) bond length is 2.11 Å. The V(1)-O(3) bond length is 2.18 Å. Both V(1)-O(1) bond lengths are 2.12 Å. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra and corners with eight equivalent Li(1)O4 tetrahedra. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.67 Å. Both Si(1)-O(1) bond lengths are 1.65 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one Si(1) atom. In the second O site, O(2) is bonded in a tetrahedral geometry to two equivalent Li(1), one V(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one Si(1) atom.