Li2VPO6 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. 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 P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the second O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP tetrahedra. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP tetrahedra.
Li2VPO6 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.58 Å. The Li(1)-O(2) bond length is 2.17 Å. The Li(1)-O(3) bond length is 2.36 Å. The Li(1)-O(4) bond length is 2.14 Å. The Li(1)-O(5) bond length is 1.99 Å. The Li(1)-O(6) bond length is 2.04 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 P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. The Li(2)-O(1) bond length is 2.25 Å. The Li(2)-O(2) bond length is 2.24 Å. The Li(2)-O(3) bond length is 2.17 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-O(5) bond length is 2.13 Å. The Li(2)-O(6) bond length is 2.16 Å. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(2) bond length is 2.04 Å. The V(1)-O(3) bond length is 2.36 Å. The V(1)-O(4) bond length is 2.24 Å. The V(1)-O(5) bond length is 1.67 Å. The V(1)-O(6) bond length is 1.66 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Li(2)O6 octahedra and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.56 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one V(1) atom. In the second O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP tetrahedra. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2VP tetrahedra.