LiV3O4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(8), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)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, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second Li site, Li(2) is bonded to one O(6), one O(7), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(6)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third V site, V(3) is bonded to one O(1), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four 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 V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fourth V site, V(4) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent V(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the fifth V site, V(5) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the sixth V site, V(6) is bonded to one O(2), one O(3), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(3), one V(5), and two equivalent V(4) atoms to form OLi2V4 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with four equivalent O(1)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(3)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to two equivalent Li(2), one V(2), one V(6), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with four equivalent O(2)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(4)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), one V(6), and two equivalent V(4) atoms to form OLi2V4 octahedra that share corners with two equivalent O(2)Li2V4 octahedra, corners with four equivalent O(3)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(3), one V(5), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with two equivalent O(1)Li2V4 octahedra, corners with four equivalent O(4)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(2)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent V(5) atoms to form OLiV5 octahedra that share corners with two equivalent O(8)LiV5 octahedra, corners with four equivalent O(5)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(7)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the sixth O site, O(6) is bonded to one Li(2), one V(4), two equivalent V(3), and two equivalent V(6) atoms to form OLiV5 octahedra that share corners with two equivalent O(7)LiV5 octahedra, corners with four equivalent O(6)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(8)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the seventh O site, O(7) is bonded to one Li(2), one V(4), two equivalent V(2), and two equivalent V(5) atoms to form OLiV5 octahedra that share corners with two equivalent O(6)LiV5 octahedra, corners with four equivalent O(7)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(5)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the eighth O site, O(8) is bonded to one Li(1), one V(1), two equivalent V(3), and two equivalent V(6) atoms to form OLiV5 octahedra that share corners with two equivalent O(5)LiV5 octahedra, corners with four equivalent O(8)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(6)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
LiV3O4 is Caswellsilverite-like structured and crystallizes in the orthorhombic Pmm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), one O(8), two equivalent O(1), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent V(1)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, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Li(1)-O(5) bond length is 2.32 Å. The Li(1)-O(8) bond length is 2.19 Å. Both Li(1)-O(1) bond lengths are 2.13 Å. Both Li(1)-O(3) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded to one O(6), one O(7), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. The Li(2)-O(6) bond length is 2.23 Å. The Li(2)-O(7) bond length is 2.28 Å. Both Li(2)-O(2) bond lengths are 2.13 Å. Both Li(2)-O(4) bond lengths are 2.16 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(8), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The V(1)-O(5) bond length is 2.05 Å. The V(1)-O(8) bond length is 2.07 Å. Both V(1)-O(2) bond lengths are 2.16 Å. Both V(1)-O(4) bond lengths are 2.13 Å. In the second V site, V(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(6)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The V(2)-O(2) bond length is 2.18 Å. The V(2)-O(3) bond length is 2.16 Å. Both V(2)-O(5) bond lengths are 2.17 Å. Both V(2)-O(7) bond lengths are 2.14 Å. In the third V site, V(3) is bonded to one O(1), one O(4), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four 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 V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. The V(3)-O(1) bond length is 2.15 Å. The V(3)-O(4) bond length is 2.14 Å. Both V(3)-O(6) bond lengths are 2.16 Å. Both V(3)-O(8) bond lengths are 2.14 Å. In the fourth V site, V(4) is bonded to one O(6), one O(7), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent V(4)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. The V(4)-O(6) bond length is 2.06 Å. The V(4)-O(7) bond length is 2.05 Å. Both V(4)-O(1) bond lengths are 2.16 Å. Both V(4)-O(3) bond lengths are 2.13 Å. In the fifth V site, V(5) is bonded to one O(1), one O(4), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(5)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. The V(5)-O(1) bond length is 2.19 Å. The V(5)-O(4) bond length is 2.16 Å. Both V(5)-O(5) bond lengths are 2.14 Å. Both V(5)-O(7) bond lengths are 2.17 Å. In the sixth V site, V(6) is bonded to one O(2), one O(3), two equivalent O(6), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The V(6)-O(2) bond length is 2.14 Å. The V(6)-O(3) bond length is 2.14 Å. Both V(6)-O(6) bond lengths are 2.14 Å. Both V(6)-O(8) bond lengths are 2.16 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(3), one V(5), and two equivalent V(4) atoms to form OLi2V4 octahedra that share corners with two equivalent O(4)Li2V4 octahedra, corners with four equivalent O(1)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(3)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to two equivalent Li(2), one V(2), one V(6), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with two equivalent O(3)Li2V4 octahedra, corners with four equivalent O(2)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(4)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), one V(6), and two equivalent V(4) atoms to form OLi2V4 octahedra that share corners with two equivalent O(2)Li2V4 octahedra, corners with four equivalent O(3)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(3), one V(5), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with two equivalent O(1)Li2V4 octahedra, corners with four equivalent O(4)Li2V4 octahedra, edges with two equivalent O(5)LiV5 octahedra, edges with two equivalent O(6)LiV5 octahedra, edges with two equivalent O(7)LiV5 octahedra, edges with two equivalent O(8)LiV5 octahedra, and edges with four equivalent O(2)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-3°. In the fifth O site, O(5) is bonded to one Li(1), one V(1), two equivalent V(2), and two equivalent V(5) atoms to form OLiV5 octahedra that share corners with two equivalent O(8)LiV5 octahedra, corners with four equivalent O(5)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(7)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the sixth O site, O(6) is bonded to one Li(2), one V(4), two equivalent V(3), and two equivalent V(6) atoms to form OLiV5 octahedra that share corners with two equivalent O(7)LiV5 octahedra, corners with four equivalent O(6)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(8)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the seventh O site, O(7) is bonded to one Li(2), one V(4), two equivalent V(2), and two equivalent V(5) atoms to form OLiV5 octahedra that share corners with two equivalent O(6)LiV5 octahedra, corners with four equivalent O(7)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(5)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the eighth O site, O(8) is bonded to one Li(1), one V(1), two equivalent V(3), and two equivalent V(6) atoms to form OLiV5 octahedra that share corners with two equivalent O(5)LiV5 octahedra, corners with four equivalent O(8)LiV5 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(4)Li2V4 octahedra, and edges with four equivalent O(6)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.