Li7V5O12 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) 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 Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(4)Li3V3 octahedra, and edges with five equivalent O(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(3) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with four equivalent O(3)Li4V2 octahedra, and edges with five equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(3) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(1)Li3V3 octahedra, and edges with eight equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(2)Li4V2 octahedra, and edges with eight equivalent O(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Li7V5O12 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-8°. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.13 Å. There is one shorter (2.22 Å) and one longer (2.27 Å) Li(1)-O(1) bond length. There is one shorter (2.06 Å) and one longer (2.08 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with six equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.18 Å. Both Li(2)-O(1) bond lengths are 2.23 Å. Both Li(2)-O(2) bond lengths are 2.08 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) 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 Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-5°. Both Li(3)-O(3) bond lengths are 2.09 Å. All Li(3)-O(2) bond lengths are 2.07 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both V(1)-O(4) bond lengths are 2.03 Å. All V(1)-O(1) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both V(2)-O(4) bond lengths are 2.04 Å. There are two shorter (2.00 Å) and two longer (2.01 Å) V(2)-O(1) bond lengths. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both V(3)-O(3) bond lengths are 1.96 Å. There are two shorter (1.98 Å) and two longer (2.02 Å) V(3)-O(2) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with four equivalent O(4)Li3V3 octahedra, and edges with five equivalent O(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(3) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra, edges with two equivalent O(1)Li3V3 octahedra, edges with four equivalent O(3)Li4V2 octahedra, and edges with five equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the third O site, O(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(3) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(1)Li3V3 octahedra, and edges with eight equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(3)Li4V2 octahedra, corners with two equivalent O(1)Li3V3 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(4)Li3V3 octahedra,  an edgeedge with one O(3)Li4V2 octahedra, edges with two equivalent O(2)Li4V2 octahedra, and edges with eight equivalent O(1)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.