Li4V(TeO4)3 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(3), one O(5), and one O(9) atom. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(6) atom. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(4), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Te(3)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-63°. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(4), and one O(7) atom. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(11), one O(12), one O(2), one O(3), one O(8), and one O(9) atom to form TeO6 octahedra that share corners with four equivalent Te(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-45°. In the second Te site, Te(2) is bonded to one O(1), one O(10), one O(4), one O(5), one O(6), and one O(7) atom to form distorted TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-38°. In the third Te site, Te(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form TeO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-63°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one Te(2) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one Te(1), and one Te(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one Te(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Te(2), and one Te(3) atom to form distorted OLi2Te2 trigonal pyramids that share corners with two equivalent O(11)Li2VTe trigonal pyramids and corners with three equivalent O(9)Li2Te2 trigonal pyramids. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Li(3), one Te(2), and one Te(3) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one V(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one Te(1), and one Te(3) atom. In the ninth O site, O(9) is bonded to one Li(1), one Li(4), one Te(1), and one Te(3) atom to form distorted OLi2Te2 trigonal pyramids that share  a cornercorner with one O(11)Li2VTe trigonal pyramid, corners with three equivalent O(5)Li2Te2 trigonal pyramids, and  an edgeedge with one O(11)Li2VTe trigonal pyramid. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(1), and one Te(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one V(1), and one Te(1) atom to form a mixture of distorted corner and edge-sharing OLi2VTe trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one Te(1) atom.
Li4V(TeO4)3 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(3), one O(5), and one O(9) atom. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(11) bond length is 2.03 Å. The Li(1)-O(2) bond length is 2.40 Å. The Li(1)-O(3) bond length is 2.34 Å. The Li(1)-O(5) bond length is 2.36 Å. The Li(1)-O(9) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(12), one O(2), one O(4), and one O(6) atom. The Li(2)-O(1) bond length is 2.38 Å. The Li(2)-O(10) bond length is 2.00 Å. The Li(2)-O(12) bond length is 2.04 Å. The Li(2)-O(2) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.39 Å. The Li(2)-O(6) bond length is 2.33 Å. In the third Li site, Li(3) is bonded to one O(10), one O(12), one O(4), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with two equivalent Te(3)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, and edges with two equivalent Te(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-63°. The Li(3)-O(10) bond length is 2.21 Å. The Li(3)-O(12) bond length is 2.11 Å. The Li(3)-O(4) bond length is 2.28 Å. The Li(3)-O(6) bond length is 2.18 Å. The Li(3)-O(7) bond length is 2.08 Å. The Li(3)-O(8) bond length is 2.13 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(11), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. The Li(4)-O(11) bond length is 2.32 Å. The Li(4)-O(3) bond length is 2.10 Å. The Li(4)-O(5) bond length is 2.05 Å. The Li(4)-O(7) bond length is 2.02 Å. The Li(4)-O(8) bond length is 2.40 Å. The Li(4)-O(9) bond length is 2.35 Å. V(1) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(4), and one O(7) atom. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(10) bond length is 2.16 Å. The V(1)-O(11) bond length is 1.87 Å. The V(1)-O(12) bond length is 2.41 Å. The V(1)-O(4) bond length is 1.71 Å. The V(1)-O(7) bond length is 2.11 Å. There are three inequivalent Te sites. In the first Te site, Te(1) is bonded to one O(11), one O(12), one O(2), one O(3), one O(8), and one O(9) atom to form TeO6 octahedra that share corners with four equivalent Te(3)O6 octahedra and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-45°. The Te(1)-O(11) bond length is 2.11 Å. The Te(1)-O(12) bond length is 1.90 Å. The Te(1)-O(2) bond length is 1.95 Å. The Te(1)-O(3) bond length is 1.95 Å. The Te(1)-O(8) bond length is 2.02 Å. The Te(1)-O(9) bond length is 2.02 Å. In the second Te site, Te(2) is bonded to one O(1), one O(10), one O(4), one O(5), one O(6), and one O(7) atom to form distorted TeO6 octahedra that share corners with two equivalent Te(3)O6 octahedra and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-38°. The Te(2)-O(1) bond length is 2.51 Å. The Te(2)-O(10) bond length is 1.92 Å. The Te(2)-O(4) bond length is 2.46 Å. The Te(2)-O(5) bond length is 2.06 Å. The Te(2)-O(6) bond length is 2.10 Å. The Te(2)-O(7) bond length is 1.95 Å. In the third Te site, Te(3) is bonded to one O(2), one O(3), one O(5), one O(6), one O(8), and one O(9) atom to form TeO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Te(2)O6 octahedra, and corners with four equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-63°. The Te(3)-O(2) bond length is 2.18 Å. The Te(3)-O(3) bond length is 2.22 Å. The Te(3)-O(5) bond length is 2.04 Å. The Te(3)-O(6) bond length is 2.00 Å. The Te(3)-O(8) bond length is 2.06 Å. The Te(3)-O(9) bond length is 2.08 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one Te(2) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(2), one Te(1), and one Te(3) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(4), one Te(1), and one Te(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one Te(2) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(4), one Te(2), and one Te(3) atom to form distorted OLi2Te2 trigonal pyramids that share corners with two equivalent O(11)Li2VTe trigonal pyramids and corners with three equivalent O(9)Li2Te2 trigonal pyramids. In the sixth O site, O(6) is bonded in a see-saw-like geometry to one Li(2), one Li(3), one Te(2), and one Te(3) atom. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one V(1), and one Te(2) atom. In the eighth O site, O(8) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(4), one Te(1), and one Te(3) atom. In the ninth O site, O(9) is bonded to one Li(1), one Li(4), one Te(1), and one Te(3) atom to form distorted OLi2Te2 trigonal pyramids that share  a cornercorner with one O(11)Li2VTe trigonal pyramid, corners with three equivalent O(5)Li2Te2 trigonal pyramids, and  an edgeedge with one O(11)Li2VTe trigonal pyramid. In the tenth O site, O(10) is bonded in a distorted see-saw-like geometry to one Li(2), one Li(3), one V(1), and one Te(2) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one V(1), and one Te(1) atom to form a mixture of distorted corner and edge-sharing OLi2VTe trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one Te(1) atom.