Li4TiV3O8 is Caswellsilverite-derived structured and 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(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Ti(1), one V(1), and one V(3) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(6)Li3V3 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, and edges with two equivalent O(8)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one Ti(1), one V(1), and one V(2) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(4), one Ti(1), one V(1), and one V(2) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(3)Li3V3 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, and edges with two equivalent O(8)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(4), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Li(4), one Ti(1), one V(1), and one V(3) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li4TiV3O8 is Caswellsilverite-derived structured and 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(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-O(3) bond length is 2.31 Å. The Li(1)-O(4) bond length is 2.06 Å. The Li(1)-O(5) bond length is 2.04 Å. The Li(1)-O(6) bond length is 2.28 Å. The Li(1)-O(8) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(2)-O(2) bond length is 2.18 Å. The Li(2)-O(3) bond length is 2.00 Å. The Li(2)-O(4) bond length is 2.42 Å. The Li(2)-O(5) bond length is 2.36 Å. The Li(2)-O(6) bond length is 2.02 Å. The Li(2)-O(7) bond length is 2.17 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. The Li(3)-O(1) bond length is 2.43 Å. The Li(3)-O(2) bond length is 2.05 Å. The Li(3)-O(3) bond length is 2.25 Å. The Li(3)-O(6) bond length is 2.20 Å. The Li(3)-O(7) bond length is 2.09 Å. The Li(3)-O(8) bond length is 2.39 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. The Li(4)-O(1) bond length is 1.97 Å. The Li(4)-O(2) bond length is 2.28 Å. The Li(4)-O(4) bond length is 2.12 Å. The Li(4)-O(5) bond length is 2.14 Å. The Li(4)-O(7) bond length is 2.31 Å. The Li(4)-O(8) bond length is 1.98 Å. Ti(1) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form TiO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. The Ti(1)-O(1) bond length is 2.31 Å. The Ti(1)-O(2) bond length is 1.96 Å. The Ti(1)-O(4) bond length is 2.12 Å. The Ti(1)-O(5) bond length is 2.12 Å. The Ti(1)-O(7) bond length is 1.95 Å. The Ti(1)-O(8) bond length is 2.31 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-18°. The V(1)-O(1) bond length is 2.07 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 2.23 Å. The V(1)-O(5) bond length is 2.23 Å. The V(1)-O(6) bond length is 1.97 Å. The V(1)-O(8) bond length is 2.08 Å. In the second V site, V(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The V(2)-O(2) bond length is 2.06 Å. The V(2)-O(3) bond length is 2.26 Å. The V(2)-O(4) bond length is 1.86 Å. The V(2)-O(5) bond length is 1.86 Å. The V(2)-O(6) bond length is 2.26 Å. The V(2)-O(7) bond length is 2.05 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. The V(3)-O(1) bond length is 1.86 Å. The V(3)-O(2) bond length is 2.18 Å. The V(3)-O(3) bond length is 2.01 Å. The V(3)-O(6) bond length is 2.01 Å. The V(3)-O(7) bond length is 2.20 Å. The V(3)-O(8) bond length is 1.85 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Ti(1), one V(1), and one V(3) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(2), one Li(3), one Li(4), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(6)Li3V3 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, and edges with two equivalent O(8)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(4), one Ti(1), one V(1), and one V(2) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(4), one Ti(1), one V(1), and one V(2) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form OLi3V3 octahedra that share corners with six equivalent O(3)Li3V3 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, and edges with two equivalent O(8)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the seventh O site, O(7) is bonded to one Li(2), one Li(3), one Li(4), one Ti(1), one V(2), and one V(3) atom to form OLi3TiV2 octahedra that share corners with six equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(8)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), one Li(4), one Ti(1), one V(1), and one V(3) atom to form distorted OLi3TiV2 octahedra that share corners with six equivalent O(1)Li3TiV2 octahedra, edges with two equivalent O(2)Li3TiV2 octahedra, edges with two equivalent O(4)Li3TiV2 octahedra, edges with two equivalent O(5)Li3TiV2 octahedra, edges with two equivalent O(7)Li3TiV2 octahedra, edges with two equivalent O(3)Li3V3 octahedra, and edges with two equivalent O(6)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.