Li2VOSiO4 crystallizes in the orthorhombic Pmc2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 43-46°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(6), two equivalent O(4), and two equivalent O(5) atoms. Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-64°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2VSi tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one V(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2VSi tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and one V(2) atom.
Li2VOSiO4 crystallizes in the orthorhombic Pmc2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(3) atoms. The Li(1)-O(1) bond length is 1.96 Å. Both Li(1)-O(2) bond lengths are 2.05 Å. Both Li(1)-O(3) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 43-46°. The Li(2)-O(1) bond length is 2.48 Å. The Li(2)-O(2) bond length is 2.13 Å. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(4) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.11 Å. The Li(2)-O(6) bond length is 2.44 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(6) atoms. Both Li(3)-O(4) bond lengths are 2.17 Å. Both Li(3)-O(5) bond lengths are 2.13 Å. There is one shorter (2.38 Å) and one longer (2.57 Å) Li(3)-O(6) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Si(1)O4 tetrahedra, and edges with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 64°. The V(1)-O(1) bond length is 1.68 Å. Both V(1)-O(2) bond lengths are 2.02 Å. Both V(1)-O(3) bond lengths are 1.98 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(6), two equivalent O(4), and two equivalent O(5) atoms. The V(2)-O(6) bond length is 1.69 Å. Both V(2)-O(4) bond lengths are 1.98 Å. Both V(2)-O(5) bond lengths are 1.97 Å. Si(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with four equivalent Li(2)O6 octahedra and corners with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 61-64°. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.64 Å. The Si(1)-O(5) bond length is 1.64 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Li(1), two equivalent Li(2), and one V(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2VSi tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one Si(1) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one V(2), and one Si(1) atom to form a mixture of distorted edge and corner-sharing OLi2VSi tetrahedra. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and one V(2) atom.