Li3V5O12 is Esseneite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(6) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-64°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-68°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(1), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the second O site, O(2) 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(3) is bonded to one Li(1), one Li(2), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(3) atom.
Li3V5O12 is Esseneite-derived structured and crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. Both Li(1)-O(1) bond lengths are 2.36 Å. Both Li(1)-O(2) bond lengths are 2.03 Å. Both Li(1)-O(3) bond lengths are 2.28 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Li(2)-O(2) bond lengths are 2.47 Å. Both Li(2)-O(3) bond lengths are 2.04 Å. Both Li(2)-O(5) bond lengths are 2.57 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to two equivalent O(1) and two equivalent O(6) atoms. Both Li(3)-O(1) bond lengths are 2.02 Å. Both Li(3)-O(6) bond lengths are 2.33 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-64°. The V(1)-O(1) bond length is 1.75 Å. The V(1)-O(2) bond length is 1.69 Å. The V(1)-O(4) bond length is 1.77 Å. The V(1)-O(5) bond length is 1.77 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-68°. The V(2)-O(3) bond length is 1.78 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(5) bond length is 1.87 Å. The V(2)-O(6) bond length is 1.76 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Li(1)O6 octahedra. Both V(3)-O(1) bond lengths are 2.13 Å. Both V(3)-O(3) bond lengths are 2.05 Å. Both V(3)-O(6) bond lengths are 1.98 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(1), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the second O site, O(2) 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(3) is bonded to one Li(1), one Li(2), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(3), one V(2), and one V(3) atom.