LiVO2 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the third V site, V(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(2), and two equivalent V(3) atoms to form OLi2V4 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(5)Li4V2 octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(3)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(2) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(3)Li2V4 octahedra,  an edgeedge with one O(3)Li2V4 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to two equivalent Li(2), one V(1), one V(2), and two equivalent V(3) atoms to form OLi2V4 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fourth O site, O(4) 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  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(4)Li3V3 octahedra, edges with three equivalent O(1)Li2V4 octahedra, edges with three equivalent O(3)Li2V4 octahedra, edges with three equivalent O(2)Li4V2 octahedra, and edges with three equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), two equivalent Li(1), one V(2), and one V(3) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(1)Li2V4 octahedra,  an edgeedge with one O(5)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
LiVO2 is Caswellsilverite-like structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. The Li(1)-O(1) bond length is 2.36 Å. The Li(1)-O(4) bond length is 2.23 Å. There is one shorter (2.12 Å) and one longer (2.17 Å) Li(1)-O(2) bond length. There is one shorter (2.13 Å) and one longer (2.20 Å) Li(1)-O(5) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. The Li(2)-O(1) bond length is 2.23 Å. The Li(2)-O(2) bond length is 2.06 Å. The Li(2)-O(4) bond length is 2.17 Å. The Li(2)-O(5) bond length is 2.04 Å. Both Li(2)-O(3) bond lengths are 2.29 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. Both Li(3)-O(2) bond lengths are 2.13 Å. Both Li(3)-O(4) bond lengths are 2.19 Å. Both Li(3)-O(5) bond lengths are 2.11 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both V(1)-O(1) bond lengths are 2.09 Å. Both V(1)-O(3) bond lengths are 2.07 Å. Both V(1)-O(4) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-12°. The V(2)-O(1) bond length is 2.16 Å. The V(2)-O(3) bond length is 2.12 Å. The V(2)-O(4) bond length is 2.10 Å. The V(2)-O(5) bond length is 2.02 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) V(2)-O(2) bond length. In the third V site, V(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-12°. The V(3)-O(4) bond length is 2.01 Å. The V(3)-O(5) bond length is 1.90 Å. There is one shorter (2.08 Å) and one longer (2.10 Å) V(3)-O(1) bond length. There is one shorter (2.07 Å) and one longer (2.18 Å) V(3)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(2), and two equivalent V(3) atoms to form OLi2V4 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra, corners with two equivalent O(5)Li4V2 octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(3)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and two equivalent V(2) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(3)Li2V4 octahedra,  an edgeedge with one O(3)Li2V4 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(2)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to two equivalent Li(2), one V(1), one V(2), and two equivalent V(3) atoms to form OLi2V4 octahedra that share  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(2)Li4V2 octahedra,  an edgeedge with one O(2)Li4V2 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with two equivalent O(5)Li4V2 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fourth O site, O(4) 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  a cornercorner with one O(1)Li2V4 octahedra,  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(4)Li3V3 octahedra, edges with three equivalent O(1)Li2V4 octahedra, edges with three equivalent O(3)Li2V4 octahedra, edges with three equivalent O(2)Li4V2 octahedra, and edges with three equivalent O(5)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), two equivalent Li(1), one V(2), and one V(3) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li2V4 octahedra,  a cornercorner with one O(4)Li3V3 octahedra,  a cornercorner with one O(2)Li4V2 octahedra,  a cornercorner with one O(5)Li4V2 octahedra, corners with two equivalent O(1)Li2V4 octahedra,  an edgeedge with one O(5)Li4V2 octahedra, edges with two equivalent O(1)Li2V4 octahedra, edges with two equivalent O(3)Li2V4 octahedra, edges with three equivalent O(4)Li3V3 octahedra, and edges with four equivalent O(2)Li4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.