Li4Ti3VO8 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(7), one O(8), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, edges with two equivalent Ti(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(1), one O(5), one O(6), and two equivalent O(3) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, edges with two equivalent Ti(1)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(8), and two equivalent O(6) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Ti(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(5), and two equivalent O(7) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Ti(1)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(7), one O(8), and two equivalent O(1) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. In the second Ti site, Ti(2) is bonded to one O(2), one O(5), one O(6), and two equivalent O(4) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. In the third Ti site, Ti(3) is bonded to one O(3), one O(4), one O(7), and two equivalent O(5) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Ti(2)O5 trigonal bipyramids. V(1) is bonded to one O(1), one O(2), one O(6), and two equivalent O(8) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, and edges with two equivalent Ti(1)O5 trigonal bipyramids. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), two equivalent Ti(1), and one V(1) atom to form OLi2Ti2V trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, edges with two equivalent O(3)Li3Ti2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(1), one Ti(2), and one V(1) atom to form OLi3TiV trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Ti(1), and one Ti(3) atom to form OLi3Ti2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(3), and two equivalent Ti(2) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, edges with two equivalent O(2)Li3TiV trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(3)Li3Ti2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(3), one Ti(2), and one V(1) atom to form OLi3TiV trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, and edges with two equivalent O(3)Li3Ti2 trigonal bipyramids. In the seventh O site, O(7) is bonded to one Li(1), two equivalent Li(4), one Ti(1), and one Ti(3) atom to form OLi3Ti2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, and edges with two equivalent O(2)Li3TiV trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Ti(1), and two equivalent V(1) atoms to form OLi2TiV2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(2)Li3TiV trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids.
Li4Ti3VO8 crystallizes in the monoclinic Pm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(7), one O(8), and two equivalent O(2) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, edges with two equivalent Ti(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The Li(1)-O(4) bond length is 2.09 Å. The Li(1)-O(7) bond length is 2.11 Å. The Li(1)-O(8) bond length is 2.13 Å. Both Li(1)-O(2) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one O(1), one O(5), one O(6), and two equivalent O(3) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, edges with two equivalent Ti(1)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-O(5) bond length is 2.06 Å. The Li(2)-O(6) bond length is 2.00 Å. Both Li(2)-O(3) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(8), and two equivalent O(6) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Ti(2)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The Li(3)-O(3) bond length is 2.09 Å. The Li(3)-O(4) bond length is 2.06 Å. The Li(3)-O(8) bond length is 2.12 Å. Both Li(3)-O(6) bond lengths are 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(5), and two equivalent O(7) atoms to form LiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Ti(1)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. The Li(4)-O(1) bond length is 2.01 Å. The Li(4)-O(2) bond length is 1.97 Å. The Li(4)-O(5) bond length is 2.09 Å. Both Li(4)-O(7) bond lengths are 2.09 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(3), one O(7), one O(8), and two equivalent O(1) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The Ti(1)-O(3) bond length is 1.93 Å. The Ti(1)-O(7) bond length is 1.92 Å. The Ti(1)-O(8) bond length is 1.91 Å. Both Ti(1)-O(1) bond lengths are 2.07 Å. In the second Ti site, Ti(2) is bonded to one O(2), one O(5), one O(6), and two equivalent O(4) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, and edges with two equivalent Ti(3)O5 trigonal bipyramids. The Ti(2)-O(2) bond length is 1.88 Å. The Ti(2)-O(5) bond length is 2.00 Å. The Ti(2)-O(6) bond length is 1.89 Å. Both Ti(2)-O(4) bond lengths are 2.07 Å. In the third Ti site, Ti(3) is bonded to one O(3), one O(4), one O(7), and two equivalent O(5) atoms to form TiO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 trigonal bipyramids, corners with two equivalent Li(3)O5 trigonal bipyramids, corners with two equivalent Ti(1)O5 trigonal bipyramids, corners with two equivalent Ti(3)O5 trigonal bipyramids, edges with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent Li(4)O5 trigonal bipyramids, and edges with two equivalent Ti(2)O5 trigonal bipyramids. The Ti(3)-O(3) bond length is 1.93 Å. The Ti(3)-O(4) bond length is 1.96 Å. The Ti(3)-O(7) bond length is 1.95 Å. Both Ti(3)-O(5) bond lengths are 2.07 Å. V(1) is bonded to one O(1), one O(2), one O(6), and two equivalent O(8) atoms to form VO5 trigonal bipyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, corners with two equivalent Li(4)O5 trigonal bipyramids, corners with two equivalent Ti(2)O5 trigonal bipyramids, corners with two equivalent V(1)O5 trigonal bipyramids, edges with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Li(3)O5 trigonal bipyramids, and edges with two equivalent Ti(1)O5 trigonal bipyramids. The V(1)-O(1) bond length is 2.12 Å. The V(1)-O(2) bond length is 2.11 Å. The V(1)-O(6) bond length is 2.08 Å. Both V(1)-O(8) bond lengths are 2.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), two equivalent Ti(1), and one V(1) atom to form OLi2Ti2V trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, edges with two equivalent O(3)Li3Ti2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(4), two equivalent Li(1), one Ti(2), and one V(1) atom to form OLi3TiV trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(2), one Ti(1), and one Ti(3) atom to form OLi3Ti2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(3), and two equivalent Ti(2) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, edges with two equivalent O(2)Li3TiV trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(2), one Li(4), one Ti(2), and two equivalent Ti(3) atoms to form OLi2Ti3 trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(3)Li3Ti2 trigonal bipyramids, and edges with two equivalent O(7)Li3Ti2 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Li(3), one Ti(2), and one V(1) atom to form OLi3TiV trigonal bipyramids that share corners with two equivalent O(1)Li2Ti2V trigonal bipyramids, corners with two equivalent O(5)Li2Ti3 trigonal bipyramids, corners with two equivalent O(2)Li3TiV trigonal bipyramids, corners with two equivalent O(6)Li3TiV trigonal bipyramids, edges with two equivalent O(4)Li2Ti3 trigonal bipyramids, edges with two equivalent O(8)Li2TiV2 trigonal bipyramids, and edges with two equivalent O(3)Li3Ti2 trigonal bipyramids. In the seventh O site, O(7) is bonded to one Li(1), two equivalent Li(4), one Ti(1), and one Ti(3) atom to form OLi3Ti2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(5)Li2Ti3 trigonal bipyramids, and edges with two equivalent O(2)Li3TiV trigonal bipyramids. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Ti(1), and two equivalent V(1) atoms to form OLi2TiV2 trigonal bipyramids that share corners with two equivalent O(4)Li2Ti3 trigonal bipyramids, corners with two equivalent O(8)Li2TiV2 trigonal bipyramids, corners with two equivalent O(3)Li3Ti2 trigonal bipyramids, corners with two equivalent O(7)Li3Ti2 trigonal bipyramids, edges with two equivalent O(1)Li2Ti2V trigonal bipyramids, edges with two equivalent O(2)Li3TiV trigonal bipyramids, and edges with two equivalent O(6)Li3TiV trigonal bipyramids.