LiVTeO5 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(5) atoms. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent Te(1)O5 square pyramids and  an edgeedge with one Te(1)O5 square pyramid. Te(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted TeO5 square pyramids that share corners with two equivalent Te(1)O5 square pyramids, corners with three equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Te(1) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one Te(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Te(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Te(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.
LiVTeO5 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), and two equivalent O(5) atoms. The Li(1)-O(2) bond length is 2.12 Å. The Li(1)-O(3) bond length is 2.28 Å. The Li(1)-O(4) bond length is 1.99 Å. There is one shorter (2.05 Å) and one longer (2.06 Å) Li(1)-O(5) bond length. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent Te(1)O5 square pyramids and  an edgeedge with one Te(1)O5 square pyramid. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.88 Å. The V(1)-O(4) bond length is 2.07 Å. The V(1)-O(5) bond length is 1.68 Å. Te(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted TeO5 square pyramids that share corners with two equivalent Te(1)O5 square pyramids, corners with three equivalent V(1)O5 trigonal bipyramids, and  an edgeedge with one V(1)O5 trigonal bipyramid. The Te(1)-O(2) bond length is 2.59 Å. The Te(1)-O(3) bond length is 1.95 Å. The Te(1)-O(4) bond length is 1.88 Å. There is one shorter (1.98 Å) and one longer (2.50 Å) Te(1)-O(1) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1) and two equivalent Te(1) atoms. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one Te(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Te(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Te(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(1) atom.