Li2TiV5O12 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(17), one O(19), and one O(9) atom to form LiO4 tetrahedra that share corners with two equivalent V(6)O6 pentagonal pyramids,  a cornercorner with one V(3)O5 trigonal bipyramid, and  a cornercorner with one V(8)O5 trigonal bipyramid. In the second Li site, Li(2) is bonded to one O(10), one O(12), one O(18), and one O(20) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(7)O6 pentagonal pyramids,  a cornercorner with one V(3)O5 trigonal bipyramid, corners with two equivalent V(5)O5 trigonal bipyramids, and  an edgeedge with one Ti(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(15), one O(21), and one O(3) atom. In the fourth Li site, Li(4) is bonded to one O(14), one O(16), one O(2), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(5)O5 trigonal bipyramid and  an edgeedge with one V(6)O6 pentagonal pyramid. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(10), one O(12), one O(21), one O(23), and one O(3) atom to form distorted TiO6 octahedra that share  a cornercorner with one V(5)O5 trigonal bipyramid, corners with two equivalent V(3)O5 trigonal bipyramids, edges with two equivalent V(7)O6 pentagonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one V(8)O5 trigonal bipyramid. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one O(11), one O(2), one O(22), one O(24), one O(4), and one O(9) atom. There are ten inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(14), one O(18), one O(2), one O(24), and one O(6) atom. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(15), one O(19), one O(22), one O(4), and one O(7) atom. In the third V site, V(3) is bonded to one O(10), one O(13), one O(17), one O(21), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent V(8)O5 trigonal bipyramids, and  an edgeedge with one V(7)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 37-53°. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(14), one O(18), one O(22), one O(7), and one O(9) atom. In the fifth V site, V(5) is bonded to one O(12), one O(16), one O(20), one O(24), and one O(6) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one V(7)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 63°. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(4), one O(5), one O(7), and one O(9) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one V(8)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O4 tetrahedra. In the seventh V site, V(7) is bonded to one O(1), one O(10), one O(12), one O(3), one O(6), and one O(8) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra,  a cornercorner with one V(8)O5 trigonal bipyramid, edges with two equivalent Ti(1)O6 octahedra,  an edgeedge with one V(3)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. In the eighth V site, V(8) is bonded to one O(1), one O(13), one O(17), one O(23), and one O(5) atom to form VO5 trigonal bipyramids that share  a cornercorner with one V(6)O6 pentagonal pyramid,  a cornercorner with one V(7)O6 pentagonal pyramid,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent V(3)O5 trigonal bipyramids, and  an edgeedge with one Ti(1)O6 octahedra. In the ninth V site, V(9) is bonded in a 4-coordinate geometry to one O(16), one O(20), one O(3), one O(6), and one O(8) atom. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(19), one O(22), one O(23), and one O(5) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Ti(1), one V(7), and one V(8) atom to form distorted OLiTiV2 trigonal pyramids that share  a cornercorner with one O(3)LiTiV2 tetrahedra, corners with two equivalent O(10)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(3)LiTiV2 tetrahedra. In the second O site, O(2) is bonded to one Li(4), one Ti(2), one V(1), and one V(6) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(4)LiTiV2 tetrahedra, corners with two equivalent O(9)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(4)LiTiV2 tetrahedra. In the third O site, O(3) is bonded to one Li(3), one Ti(1), one V(7), and one V(9) atom to form OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiTiV2 tetrahedra,  a cornercorner with one O(1)LiTiV2 trigonal pyramid,  an edgeedge with one O(10)LiTiV2 tetrahedra,  an edgeedge with one O(1)LiTiV2 trigonal pyramid, and  an edgeedge with one O(6)V4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(4), one Ti(2), one V(2), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(10), one V(6), and one V(8) atom. In the sixth O site, O(6) is bonded to one V(1), one V(5), one V(7), and one V(9) atom to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(7), and one V(9) atom. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(4), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the tenth O site, O(10) is bonded to one Li(2), one Ti(1), one V(3), and one V(7) atom to form OLiTiV2 tetrahedra that share  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid, corners with two equivalent O(1)LiTiV2 trigonal pyramids,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(3)LiTiV2 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(1), one Ti(2), one V(10), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(2), one Ti(1), one V(5), and one V(7) atom to form OLiTiV2 tetrahedra that share  a cornercorner with one O(10)LiTiV2 tetrahedra, corners with two equivalent O(3)LiTiV2 tetrahedra,  an edgeedge with one O(10)LiTiV2 tetrahedra,  an edgeedge with one O(1)LiTiV2 trigonal pyramid, and  an edgeedge with one O(6)V4 trigonal pyramid. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one V(8) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one V(4) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(3), one V(10), and one V(2) atom. In the sixteenth O site, O(16) is bonded in a trigonal planar geometry to one Li(4), one V(5), and one V(9) atom. In the seventeenth O site, O(17) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(1), one V(10), and one V(2) atom. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Li(2), one V(5), and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Ti(1), and one V(3) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Ti(2), one V(10), one V(2), and one V(4) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Ti(1), one V(10), and one V(8) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one V(5) atom.
Li2TiV5O12 crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(17), one O(19), and one O(9) atom to form LiO4 tetrahedra that share corners with two equivalent V(6)O6 pentagonal pyramids,  a cornercorner with one V(3)O5 trigonal bipyramid, and  a cornercorner with one V(8)O5 trigonal bipyramid. The Li(1)-O(11) bond length is 2.05 Å. The Li(1)-O(17) bond length is 2.07 Å. The Li(1)-O(19) bond length is 1.97 Å. The Li(1)-O(9) bond length is 2.07 Å. In the second Li site, Li(2) is bonded to one O(10), one O(12), one O(18), and one O(20) atom to form distorted LiO4 tetrahedra that share corners with two equivalent V(7)O6 pentagonal pyramids,  a cornercorner with one V(3)O5 trigonal bipyramid, corners with two equivalent V(5)O5 trigonal bipyramids, and  an edgeedge with one Ti(1)O6 octahedra. The Li(2)-O(10) bond length is 2.10 Å. The Li(2)-O(12) bond length is 2.01 Å. The Li(2)-O(18) bond length is 2.01 Å. The Li(2)-O(20) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(1), one O(13), one O(15), one O(21), and one O(3) atom. The Li(3)-O(1) bond length is 2.13 Å. The Li(3)-O(13) bond length is 2.08 Å. The Li(3)-O(15) bond length is 2.10 Å. The Li(3)-O(21) bond length is 2.57 Å. The Li(3)-O(3) bond length is 2.10 Å. In the fourth Li site, Li(4) is bonded to one O(14), one O(16), one O(2), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(5)O5 trigonal bipyramid and  an edgeedge with one V(6)O6 pentagonal pyramid. The Li(4)-O(14) bond length is 2.01 Å. The Li(4)-O(16) bond length is 2.00 Å. The Li(4)-O(2) bond length is 2.10 Å. The Li(4)-O(4) bond length is 2.06 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(10), one O(12), one O(21), one O(23), and one O(3) atom to form distorted TiO6 octahedra that share  a cornercorner with one V(5)O5 trigonal bipyramid, corners with two equivalent V(3)O5 trigonal bipyramids, edges with two equivalent V(7)O6 pentagonal pyramids,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one V(8)O5 trigonal bipyramid. The Ti(1)-O(1) bond length is 2.10 Å. The Ti(1)-O(10) bond length is 2.04 Å. The Ti(1)-O(12) bond length is 1.97 Å. The Ti(1)-O(21) bond length is 1.86 Å. The Ti(1)-O(23) bond length is 1.92 Å. The Ti(1)-O(3) bond length is 2.01 Å. In the second Ti site, Ti(2) is bonded in a 6-coordinate geometry to one O(11), one O(2), one O(22), one O(24), one O(4), and one O(9) atom. The Ti(2)-O(11) bond length is 2.01 Å. The Ti(2)-O(2) bond length is 2.08 Å. The Ti(2)-O(22) bond length is 1.89 Å. The Ti(2)-O(24) bond length is 1.87 Å. The Ti(2)-O(4) bond length is 2.07 Å. The Ti(2)-O(9) bond length is 1.99 Å. There are ten inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(14), one O(18), one O(2), one O(24), and one O(6) atom. The V(1)-O(14) bond length is 1.78 Å. The V(1)-O(18) bond length is 1.87 Å. The V(1)-O(2) bond length is 1.94 Å. The V(1)-O(24) bond length is 2.22 Å. The V(1)-O(6) bond length is 1.89 Å. In the second V site, V(2) is bonded in a 5-coordinate geometry to one O(15), one O(19), one O(22), one O(4), and one O(7) atom. The V(2)-O(15) bond length is 1.78 Å. The V(2)-O(19) bond length is 1.87 Å. The V(2)-O(22) bond length is 2.22 Å. The V(2)-O(4) bond length is 1.96 Å. The V(2)-O(7) bond length is 1.88 Å. In the third V site, V(3) is bonded to one O(10), one O(13), one O(17), one O(21), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Ti(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent V(8)O5 trigonal bipyramids, and  an edgeedge with one V(7)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 37-53°. The V(3)-O(10) bond length is 1.91 Å. The V(3)-O(13) bond length is 2.05 Å. The V(3)-O(17) bond length is 1.78 Å. The V(3)-O(21) bond length is 1.85 Å. The V(3)-O(8) bond length is 2.00 Å. In the fourth V site, V(4) is bonded in a 5-coordinate geometry to one O(14), one O(18), one O(22), one O(7), and one O(9) atom. The V(4)-O(14) bond length is 2.01 Å. The V(4)-O(18) bond length is 1.92 Å. The V(4)-O(22) bond length is 1.97 Å. The V(4)-O(7) bond length is 2.16 Å. The V(4)-O(9) bond length is 2.00 Å. In the fifth V site, V(5) is bonded to one O(12), one O(16), one O(20), one O(24), and one O(6) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and  an edgeedge with one V(7)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 63°. The V(5)-O(12) bond length is 1.97 Å. The V(5)-O(16) bond length is 1.99 Å. The V(5)-O(20) bond length is 1.93 Å. The V(5)-O(24) bond length is 1.95 Å. The V(5)-O(6) bond length is 2.16 Å. In the sixth V site, V(6) is bonded to one O(11), one O(2), one O(4), one O(5), one O(7), and one O(9) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra,  a cornercorner with one V(8)O5 trigonal bipyramid, and  an edgeedge with one Li(4)O4 tetrahedra. The V(6)-O(11) bond length is 1.98 Å. The V(6)-O(2) bond length is 1.99 Å. The V(6)-O(4) bond length is 2.00 Å. The V(6)-O(5) bond length is 1.90 Å. The V(6)-O(7) bond length is 1.94 Å. The V(6)-O(9) bond length is 1.97 Å. In the seventh V site, V(7) is bonded to one O(1), one O(10), one O(12), one O(3), one O(6), and one O(8) atom to form distorted VO6 pentagonal pyramids that share corners with two equivalent Li(2)O4 tetrahedra,  a cornercorner with one V(8)O5 trigonal bipyramid, edges with two equivalent Ti(1)O6 octahedra,  an edgeedge with one V(3)O5 trigonal bipyramid, and  an edgeedge with one V(5)O5 trigonal bipyramid. The V(7)-O(1) bond length is 2.02 Å. The V(7)-O(10) bond length is 2.03 Å. The V(7)-O(12) bond length is 2.10 Å. The V(7)-O(3) bond length is 2.13 Å. The V(7)-O(6) bond length is 2.01 Å. The V(7)-O(8) bond length is 2.04 Å. In the eighth V site, V(8) is bonded to one O(1), one O(13), one O(17), one O(23), and one O(5) atom to form VO5 trigonal bipyramids that share  a cornercorner with one V(6)O6 pentagonal pyramid,  a cornercorner with one V(7)O6 pentagonal pyramid,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent V(3)O5 trigonal bipyramids, and  an edgeedge with one Ti(1)O6 octahedra. The V(8)-O(1) bond length is 1.88 Å. The V(8)-O(13) bond length is 1.76 Å. The V(8)-O(17) bond length is 2.02 Å. The V(8)-O(23) bond length is 2.05 Å. The V(8)-O(5) bond length is 1.88 Å. In the ninth V site, V(9) is bonded in a 4-coordinate geometry to one O(16), one O(20), one O(3), one O(6), and one O(8) atom. The V(9)-O(16) bond length is 1.77 Å. The V(9)-O(20) bond length is 1.82 Å. The V(9)-O(3) bond length is 1.93 Å. The V(9)-O(6) bond length is 2.42 Å. The V(9)-O(8) bond length is 1.90 Å. In the tenth V site, V(10) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(19), one O(22), one O(23), and one O(5) atom. The V(10)-O(11) bond length is 2.00 Å. The V(10)-O(15) bond length is 2.02 Å. The V(10)-O(19) bond length is 1.91 Å. The V(10)-O(22) bond length is 2.62 Å. The V(10)-O(23) bond length is 1.94 Å. The V(10)-O(5) bond length is 2.26 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Ti(1), one V(7), and one V(8) atom to form distorted OLiTiV2 trigonal pyramids that share  a cornercorner with one O(3)LiTiV2 tetrahedra, corners with two equivalent O(10)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(3)LiTiV2 tetrahedra. In the second O site, O(2) is bonded to one Li(4), one Ti(2), one V(1), and one V(6) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(4)LiTiV2 tetrahedra, corners with two equivalent O(9)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(4)LiTiV2 tetrahedra. In the third O site, O(3) is bonded to one Li(3), one Ti(1), one V(7), and one V(9) atom to form OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiTiV2 tetrahedra,  a cornercorner with one O(1)LiTiV2 trigonal pyramid,  an edgeedge with one O(10)LiTiV2 tetrahedra,  an edgeedge with one O(1)LiTiV2 trigonal pyramid, and  an edgeedge with one O(6)V4 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(4), one Ti(2), one V(2), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(10), one V(6), and one V(8) atom. In the sixth O site, O(6) is bonded to one V(1), one V(5), one V(7), and one V(9) atom to form a mixture of distorted corner and edge-sharing OV4 trigonal pyramids. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(2), one V(4), and one V(6) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(3), one V(7), and one V(9) atom. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(4), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the tenth O site, O(10) is bonded to one Li(2), one Ti(1), one V(3), and one V(7) atom to form OLiTiV2 tetrahedra that share  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(6)V4 trigonal pyramid, corners with two equivalent O(1)LiTiV2 trigonal pyramids,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(3)LiTiV2 tetrahedra. In the eleventh O site, O(11) is bonded to one Li(1), one Ti(2), one V(10), and one V(6) atom to form a mixture of corner and edge-sharing OLiTiV2 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(2), one Ti(1), one V(5), and one V(7) atom to form OLiTiV2 tetrahedra that share  a cornercorner with one O(10)LiTiV2 tetrahedra, corners with two equivalent O(3)LiTiV2 tetrahedra,  an edgeedge with one O(10)LiTiV2 tetrahedra,  an edgeedge with one O(1)LiTiV2 trigonal pyramid, and  an edgeedge with one O(6)V4 trigonal pyramid. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one V(8) atom. In the fourteenth O site, O(14) is bonded in a trigonal planar geometry to one Li(4), one V(1), and one V(4) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(3), one V(10), and one V(2) atom. In the sixteenth O site, O(16) is bonded in a trigonal planar geometry to one Li(4), one V(5), and one V(9) atom. In the seventeenth O site, O(17) is bonded in a trigonal planar geometry to one Li(1), one V(3), and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one V(4) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(1), one V(10), and one V(2) atom. In the twentieth O site, O(20) is bonded in a trigonal planar geometry to one Li(2), one V(5), and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Ti(1), and one V(3) atom. In the twenty-second O site, O(22) is bonded in a 4-coordinate geometry to one Ti(2), one V(10), one V(2), and one V(4) atom. In the twenty-third O site, O(23) is bonded in a distorted T-shaped geometry to one Ti(1), one V(10), and one V(8) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one V(5) atom.