Li4V3O8 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. In the fourth Li site, Li(4) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(7) atom. In the sixth Li site, Li(6) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(6), and one O(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the second V site, V(2) 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 VO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(4)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 edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the fourth V site, V(4) 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  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(6), one V(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded to one Li(5), one V(1), one V(2), and one V(4) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with two equivalent O(4)Li3V2 trigonal bipyramids, corners with two equivalent O(5)Li3V2 trigonal bipyramids, corners with two equivalent O(7)Li3V2 trigonal bipyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid,  an edgeedge with one O(6)Li3V2 square pyramid, and  an edgeedge with one O(8)Li3V2 square pyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(5), one V(2), and one V(4) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with two equivalent O(3)Li3V2 square pyramids, corners with two equivalent O(4)Li3V2 trigonal bipyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(6)Li3V2 square pyramid,  an edgeedge with one O(8)Li3V2 square pyramid, edges with two equivalent O(5)Li3V2 trigonal bipyramids, edges with two equivalent O(7)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(6), one V(2), and one V(4) atom to form OLi3V2 trigonal bipyramids that share corners with two equivalent O(3)Li3V2 square pyramids,  a cornercorner with one O(5)Li3V2 trigonal bipyramid,  a cornercorner with one O(7)Li3V2 trigonal bipyramid, corners with two equivalent O(4)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(6)Li3V2 square pyramids, edges with two equivalent O(8)Li3V2 square pyramids,  an edgeedge with one O(5)Li3V2 trigonal bipyramid, and  an edgeedge with one O(7)Li3V2 trigonal bipyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(5), one V(2), and one V(3) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 trigonal bipyramid,  a cornercorner with one O(7)Li3V2 trigonal bipyramid, corners with three equivalent O(5)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(3)Li3V2 square pyramids,  an edgeedge with one O(4)Li3V2 trigonal bipyramid, and edges with three equivalent O(7)Li3V2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(2), one Li(4), one Li(6), one V(1), and one V(2) atom to form distorted OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with three equivalent O(6)Li3V2 square pyramids,  a cornercorner with one O(5)Li3V2 trigonal bipyramid,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, edges with three equivalent O(8)Li3V2 square pyramids, edges with two equivalent O(4)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Li(5), one V(3), and one V(4) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(8)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 trigonal bipyramid,  a cornercorner with one O(5)Li3V2 trigonal bipyramid, corners with three equivalent O(7)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(3)Li3V2 square pyramids,  an edgeedge with one O(4)Li3V2 trigonal bipyramid, and edges with three equivalent O(5)Li3V2 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one Li(6), one V(1), and one V(4) atom to form distorted OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(6)Li3V2 square pyramid, corners with three equivalent O(8)Li3V2 square pyramids,  a cornercorner with one O(7)Li3V2 trigonal bipyramid,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, edges with three equivalent O(6)Li3V2 square pyramids, edges with two equivalent O(4)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid.
Li4V3O8 crystallizes in the triclinic P-1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. Both Li(1)-O(4) bond lengths are 2.21 Å. Both Li(1)-O(5) bond lengths are 2.19 Å. Both Li(1)-O(7) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Li(2)-O(3) bond lengths are 2.19 Å. Both Li(2)-O(6) bond lengths are 2.20 Å. Both Li(2)-O(8) bond lengths are 2.21 Å. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. Both Li(3)-O(3) bond lengths are 2.08 Å. Both Li(3)-O(5) bond lengths are 2.05 Å. Both Li(3)-O(7) bond lengths are 2.07 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-15°. Both Li(4)-O(4) bond lengths are 2.06 Å. Both Li(4)-O(6) bond lengths are 2.06 Å. Both Li(4)-O(8) bond lengths are 2.08 Å. In the fifth Li site, Li(5) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(5), and one O(7) atom. The Li(5)-O(2) bond length is 1.89 Å. The Li(5)-O(3) bond length is 2.11 Å. The Li(5)-O(5) bond length is 2.04 Å. The Li(5)-O(7) bond length is 2.17 Å. In the sixth Li site, Li(6) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(4), one O(6), and one O(8) atom. The Li(6)-O(1) bond length is 1.88 Å. The Li(6)-O(4) bond length is 2.10 Å. The Li(6)-O(6) bond length is 2.11 Å. The Li(6)-O(8) bond length is 2.12 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(1)-O(2) bond lengths are 2.01 Å. Both V(1)-O(6) bond lengths are 1.88 Å. Both V(1)-O(8) bond lengths are 2.04 Å. In the second V site, V(2) 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 VO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The V(2)-O(1) bond length is 2.01 Å. The V(2)-O(2) bond length is 1.99 Å. The V(2)-O(3) bond length is 1.90 Å. The V(2)-O(4) bond length is 1.91 Å. The V(2)-O(5) bond length is 1.96 Å. The V(2)-O(6) bond length is 2.07 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 edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(3)-O(1) bond lengths are 1.99 Å. Both V(3)-O(5) bond lengths are 1.98 Å. Both V(3)-O(7) bond lengths are 1.94 Å. In the fourth V site, V(4) 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  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The V(4)-O(1) bond length is 2.00 Å. The V(4)-O(2) bond length is 1.99 Å. The V(4)-O(3) bond length is 2.02 Å. The V(4)-O(4) bond length is 2.01 Å. The V(4)-O(7) bond length is 1.95 Å. The V(4)-O(8) bond length is 1.87 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(6), one V(2), one V(3), and one V(4) atom. In the second O site, O(2) is bonded to one Li(5), one V(1), one V(2), and one V(4) atom to form distorted OLiV3 trigonal pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with two equivalent O(4)Li3V2 trigonal bipyramids, corners with two equivalent O(5)Li3V2 trigonal bipyramids, corners with two equivalent O(7)Li3V2 trigonal bipyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid,  an edgeedge with one O(6)Li3V2 square pyramid, and  an edgeedge with one O(8)Li3V2 square pyramid. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(5), one V(2), and one V(4) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with two equivalent O(3)Li3V2 square pyramids, corners with two equivalent O(4)Li3V2 trigonal bipyramids,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(6)Li3V2 square pyramid,  an edgeedge with one O(8)Li3V2 square pyramid, edges with two equivalent O(5)Li3V2 trigonal bipyramids, edges with two equivalent O(7)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(4), one Li(6), one V(2), and one V(4) atom to form OLi3V2 trigonal bipyramids that share corners with two equivalent O(3)Li3V2 square pyramids,  a cornercorner with one O(5)Li3V2 trigonal bipyramid,  a cornercorner with one O(7)Li3V2 trigonal bipyramid, corners with two equivalent O(4)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(6)Li3V2 square pyramids, edges with two equivalent O(8)Li3V2 square pyramids,  an edgeedge with one O(5)Li3V2 trigonal bipyramid, and  an edgeedge with one O(7)Li3V2 trigonal bipyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one Li(5), one V(2), and one V(3) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(6)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 trigonal bipyramid,  a cornercorner with one O(7)Li3V2 trigonal bipyramid, corners with three equivalent O(5)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(3)Li3V2 square pyramids,  an edgeedge with one O(4)Li3V2 trigonal bipyramid, and edges with three equivalent O(7)Li3V2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(2), one Li(4), one Li(6), one V(1), and one V(2) atom to form distorted OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(8)Li3V2 square pyramid, corners with three equivalent O(6)Li3V2 square pyramids,  a cornercorner with one O(5)Li3V2 trigonal bipyramid,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, edges with three equivalent O(8)Li3V2 square pyramids, edges with two equivalent O(4)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid. In the seventh O site, O(7) is bonded to one Li(1), one Li(3), one Li(5), one V(3), and one V(4) atom to form OLi3V2 trigonal bipyramids that share  a cornercorner with one O(8)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 trigonal bipyramid,  a cornercorner with one O(5)Li3V2 trigonal bipyramid, corners with three equivalent O(7)Li3V2 trigonal bipyramids, corners with two equivalent O(2)LiV3 trigonal pyramids, edges with two equivalent O(3)Li3V2 square pyramids,  an edgeedge with one O(4)Li3V2 trigonal bipyramid, and edges with three equivalent O(5)Li3V2 trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(2), one Li(4), one Li(6), one V(1), and one V(4) atom to form distorted OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(6)Li3V2 square pyramid, corners with three equivalent O(8)Li3V2 square pyramids,  a cornercorner with one O(7)Li3V2 trigonal bipyramid,  a cornercorner with one O(2)LiV3 trigonal pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, edges with three equivalent O(6)Li3V2 square pyramids, edges with two equivalent O(4)Li3V2 trigonal bipyramids, and  an edgeedge with one O(2)LiV3 trigonal pyramid.