Li3V5O12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) 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 V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 pentagonal pyramid,  an edgeedge with one V(4)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(5), one O(6), and one O(9) atom. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(12), one O(2), one O(7), and one O(8) atom to form distorted LiO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one V(4)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids,  a cornercorner with one V(5)O5 trigonal bipyramid, and corners with two equivalent V(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-64°. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids,  a cornercorner with one V(4)O5 trigonal bipyramid, and corners with two equivalent V(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-64°. In the third V site, V(3) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(4)O5 trigonal bipyramids, corners with two equivalent V(5)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Li(3)O6 pentagonal pyramids. In the fourth V site, V(4) is bonded to one O(11), one O(4), one O(5), one O(7), and one O(9) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-50°. In the fifth V site, V(5) is bonded to one O(10), one O(12), one O(3), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-50°. There are twelve 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 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(3), and one V(5) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(5) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(5) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(5) atom.
Li3V5O12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) 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 V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 pentagonal pyramid,  an edgeedge with one V(4)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. The Li(1)-O(1) bond length is 2.15 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(5) bond length is 2.21 Å. The Li(1)-O(6) bond length is 2.20 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(10), one O(5), one O(6), and one O(9) atom. The Li(2)-O(10) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.05 Å. The Li(2)-O(6) bond length is 2.05 Å. The Li(2)-O(9) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(12), one O(2), one O(7), and one O(8) atom to form distorted LiO6 pentagonal pyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one V(4)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(11) bond length is 2.32 Å. The Li(3)-O(12) bond length is 2.33 Å. The Li(3)-O(2) bond length is 2.19 Å. The Li(3)-O(7) bond length is 2.35 Å. The Li(3)-O(8) bond length is 2.35 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids,  a cornercorner with one V(5)O5 trigonal bipyramid, and corners with two equivalent V(4)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-64°. The V(1)-O(1) bond length is 1.74 Å. The V(1)-O(3) bond length is 1.73 Å. The V(1)-O(7) bond length is 1.74 Å. The V(1)-O(9) bond length is 1.79 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids,  a cornercorner with one V(4)O5 trigonal bipyramid, and corners with two equivalent V(5)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 47-64°. The V(2)-O(10) bond length is 1.78 Å. The V(2)-O(2) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.73 Å. The V(2)-O(8) bond length is 1.74 Å. In the third V site, V(3) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(4)O5 trigonal bipyramids, corners with two equivalent V(5)O5 trigonal bipyramids, edges with two equivalent Li(1)O6 octahedra, and edges with two equivalent Li(3)O6 pentagonal pyramids. The V(3)-O(1) bond length is 2.07 Å. The V(3)-O(11) bond length is 1.98 Å. The V(3)-O(12) bond length is 1.98 Å. The V(3)-O(2) bond length is 2.07 Å. The V(3)-O(5) bond length is 2.00 Å. The V(3)-O(6) bond length is 2.01 Å. In the fourth V site, V(4) is bonded to one O(11), one O(4), one O(5), one O(7), and one O(9) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-50°. The V(4)-O(11) bond length is 1.75 Å. The V(4)-O(4) bond length is 2.13 Å. The V(4)-O(5) bond length is 1.81 Å. The V(4)-O(7) bond length is 2.01 Å. The V(4)-O(9) bond length is 1.97 Å. In the fifth V site, V(5) is bonded to one O(10), one O(12), one O(3), one O(6), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 31-50°. The V(5)-O(10) bond length is 1.97 Å. The V(5)-O(12) bond length is 1.75 Å. The V(5)-O(3) bond length is 2.13 Å. The V(5)-O(6) bond length is 1.80 Å. The V(5)-O(8) bond length is 2.01 Å. There are twelve 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 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(2), and one V(3) atom to form a mixture of distorted corner and edge-sharing OLi2V2 tetrahedra. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one V(4) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(3), and one V(4) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(3), and one V(5) atom to form a mixture of distorted corner and edge-sharing OLi2V2 trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one V(5) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the tenth O site, O(10) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(5) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one V(5) atom.