LiV(TeO4)3 crystallizes in the monoclinic P2 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with four equivalent Te(1)O6 octahedra,  an edgeedge with one Te(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 44°. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. There are six 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 Te(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Te(1) and one Te(3) atom. In the third O site, O(3) is bonded in a water-like geometry to one V(1) and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Te(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Te(2) and one Te(3) atom.
LiV(TeO4)3 crystallizes in the monoclinic P2 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent Te(3)O6 octahedra, corners with four equivalent Te(1)O6 octahedra,  an edgeedge with one Te(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-58°. Both Li(1)-O(1) bond lengths are 2.33 Å. Both Li(1)-O(4) bond lengths are 2.03 Å. Both Li(1)-O(5) bond lengths are 2.22 Å. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. Both V(1)-O(1) bond lengths are 1.93 Å. Both V(1)-O(3) bond lengths are 1.89 Å. Both V(1)-O(5) bond lengths are 1.91 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form TeO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with two equivalent Te(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-58°. Both Te(1)-O(1) bond lengths are 1.91 Å. Both Te(1)-O(2) bond lengths are 2.01 Å. Both Te(1)-O(4) bond lengths are 1.98 Å. In the second Te site, Te(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 44°. Both Te(2)-O(3) bond lengths are 1.93 Å. Both Te(2)-O(5) bond lengths are 1.97 Å. Both Te(2)-O(6) bond lengths are 1.97 Å. In the third Te site, Te(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form TeO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. Both Te(3)-O(2) bond lengths are 1.95 Å. Both Te(3)-O(4) bond lengths are 2.02 Å. Both Te(3)-O(6) bond lengths are 1.94 Å. There are six 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 Te(1) atom. In the second O site, O(2) is bonded in a water-like geometry to one Te(1) and one Te(3) atom. In the third O site, O(3) is bonded in a water-like geometry to one V(1) and one Te(2) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Te(1), and one Te(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one Te(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Te(2) and one Te(3) atom.