Li2VO3 is Caswellsilverite-like 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(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)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 Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)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 Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent Li(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Li2VO3 is Caswellsilverite-like 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(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.21 Å. The Li(1)-O(4) bond length is 2.21 Å. The Li(1)-O(5) bond length is 2.17 Å. The Li(1)-O(6) bond length is 2.17 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. The Li(2)-O(1) bond length is 2.17 Å. The Li(2)-O(2) bond length is 2.17 Å. The Li(2)-O(3) bond length is 2.05 Å. The Li(2)-O(4) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.15 Å. The Li(2)-O(6) bond length is 2.15 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)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 Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. The Li(3)-O(1) bond length is 2.12 Å. The Li(3)-O(2) bond length is 2.16 Å. The Li(3)-O(3) bond length is 2.20 Å. The Li(3)-O(4) bond length is 2.05 Å. The Li(3)-O(5) bond length is 2.25 Å. The Li(3)-O(6) bond length is 2.11 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, edges with two equivalent Li(2)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 Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. The Li(4)-O(1) bond length is 2.16 Å. The Li(4)-O(2) bond length is 2.12 Å. The Li(4)-O(3) bond length is 2.05 Å. The Li(4)-O(4) bond length is 2.22 Å. The Li(4)-O(5) bond length is 2.11 Å. The Li(4)-O(6) bond length is 2.23 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent Li(2)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The V(1)-O(1) bond length is 1.90 Å. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(5) bond length is 1.88 Å. The V(1)-O(6) bond length is 2.07 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)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 three equivalent Li(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-9°. The V(2)-O(1) bond length is 2.06 Å. The V(2)-O(2) bond length is 1.90 Å. The V(2)-O(3) bond length is 1.97 Å. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(5) bond length is 2.06 Å. The V(2)-O(6) bond length is 1.88 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(1), and one V(2) atom to form a mixture of edge and corner-sharing OLi4V2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.