Li3V4O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent V(6)O6 octahedra, corners with three equivalent V(7)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra,  a faceface with one Li(2)O4 tetrahedra, and  a faceface with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. In the third Li site, Li(3) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(7)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-69°. There are seven inequivalent V sites. In the first V site, 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 Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. In the sixth V site, V(6) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the seventh V site, V(7) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one V(5) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(2), one V(4), and one V(5) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(5), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), one V(5), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(2), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(3), one V(5), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(4), one V(5), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids.
Li3V4O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with three equivalent V(6)O6 octahedra, corners with three equivalent V(7)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra,  a faceface with one Li(2)O4 tetrahedra, and  a faceface with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 6-8°. The Li(1)-O(3) bond length is 2.12 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.14 Å. The Li(1)-O(7) bond length is 2.18 Å. The Li(1)-O(8) bond length is 2.16 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(7)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-70°. The Li(2)-O(1) bond length is 1.86 Å. The Li(2)-O(3) bond length is 2.07 Å. The Li(2)-O(6) bond length is 2.03 Å. The Li(2)-O(7) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(7)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-69°. The Li(3)-O(2) bond length is 1.86 Å. The Li(3)-O(4) bond length is 2.06 Å. The Li(3)-O(5) bond length is 2.04 Å. The Li(3)-O(8) bond length is 2.07 Å. There are seven inequivalent V sites. In the first V site, 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 Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. Both V(1)-O(1) bond lengths are 2.04 Å. Both V(1)-O(3) bond lengths are 2.04 Å. Both V(1)-O(5) bond lengths are 2.05 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. Both V(2)-O(2) bond lengths are 2.02 Å. Both V(2)-O(4) bond lengths are 2.08 Å. Both V(2)-O(6) bond lengths are 2.03 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(7)O6 octahedra. Both V(3)-O(1) bond lengths are 2.01 Å. Both V(3)-O(5) bond lengths are 2.03 Å. Both V(3)-O(7) bond lengths are 2.10 Å. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. Both V(4)-O(2) bond lengths are 2.02 Å. Both V(4)-O(6) bond lengths are 2.03 Å. Both V(4)-O(8) bond lengths are 2.08 Å. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(6)O6 octahedra,  an edgeedge with one V(7)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The V(5)-O(1) bond length is 1.92 Å. The V(5)-O(2) bond length is 1.91 Å. The V(5)-O(3) bond length is 2.02 Å. The V(5)-O(4) bond length is 2.01 Å. The V(5)-O(7) bond length is 2.01 Å. The V(5)-O(8) bond length is 2.03 Å. In the sixth V site, V(6) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(3)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both V(6)-O(4) bond lengths are 2.11 Å. Both V(6)-O(6) bond lengths are 2.10 Å. Both V(6)-O(8) bond lengths are 2.07 Å. In the seventh V site, V(7) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both V(7)-O(3) bond lengths are 2.15 Å. Both V(7)-O(5) bond lengths are 2.07 Å. Both V(7)-O(7) bond lengths are 2.07 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one V(3), and one V(5) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(2), one V(4), and one V(5) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(1), one V(5), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(2), one V(5), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one V(2), one V(4), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(3), one V(5), and one V(7) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one V(4), one V(5), and one V(6) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids.