Li2VBO4 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one B(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. B(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form BO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi2VB trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one B(1) atom to form a mixture of edge and corner-sharing OLi2VB trigonal pyramids.
Li2VBO4 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent B(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one B(1)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 2.06 Å. Both Li(1)-O(2) bond lengths are 1.98 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one V(1)O4 tetrahedra. Both Li(2)-O(1) bond lengths are 2.01 Å. Both Li(2)-O(2) bond lengths are 1.90 Å. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent B(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(2) bond lengths are 1.91 Å. B(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form BO4 tetrahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. Both B(1)-O(1) bond lengths are 1.50 Å. Both B(1)-O(2) bond lengths are 1.51 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), and one B(1) atom to form a mixture of distorted edge and corner-sharing OLi2VB trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one B(1) atom to form a mixture of edge and corner-sharing OLi2VB trigonal pyramids.