Li2VSiO4 crystallizes in the orthorhombic Pmn2_1 space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra and corners with four equivalent Si(1)O4 tetrahedra. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form corner-sharing OLi2VSi tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent V(1), and one Si(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi trigonal pyramids.
Li2VSiO4 crystallizes in the orthorhombic Pmn2_1 space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra and corners with four equivalent Si(1)O4 tetrahedra. The Li(1)-O(1) bond length is 1.95 Å. The Li(1)-O(2) bond length is 1.99 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) Li(1)-O(3) bond length. V(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The V(1)-O(1) bond length is 2.11 Å. There is one shorter (2.22 Å) and one longer (2.63 Å) V(1)-O(2) bond length. Both V(1)-O(3) bond lengths are 2.13 Å. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.67 Å. Both Si(1)-O(3) bond lengths are 1.65 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form corner-sharing OLi2VSi tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent V(1), and one Si(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi trigonal pyramids.