LiVPO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 72-77°. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-51°. There are two 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 P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLiV2P tetrahedra.
LiVPO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 72-77°. Both Li(1)-O(1) bond lengths are 1.97 Å. Both Li(1)-O(2) bond lengths are 2.10 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.16 Å. All V(1)-O(2) bond lengths are 2.21 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with six equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-51°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.58 Å. There are two 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 P(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one P(1) atom to form a mixture of distorted edge and corner-sharing OLiV2P tetrahedra.