Li3V3(BO5)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 71°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(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, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. In the second V site, V(2) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-61°. B(1) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent V(2) atoms to form OLi2V2 tetrahedra that share corners with three equivalent O(2)LiV4 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, and  an edgeedge with one O(2)LiV4 square pyramid. In the second O site, O(2) is bonded to one Li(2), two equivalent V(1), and two equivalent V(2) atoms to form OLiV4 square pyramids that share corners with two equivalent O(2)LiV4 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, edges with three equivalent O(2)LiV4 square pyramids, and  an edgeedge with one O(1)Li2V2 tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one B(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(2), and one B(1) atom.
Li3V3(BO5)2 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 71°. Both Li(1)-O(1) bond lengths are 2.09 Å. There are two shorter (2.14 Å) and two longer (2.18 Å) Li(1)-O(5) bond lengths. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(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, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-71°. The Li(2)-O(1) bond length is 1.99 Å. The Li(2)-O(2) bond length is 2.14 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Li(2)-O(3) bond length. There is one shorter (2.16 Å) and one longer (2.17 Å) Li(2)-O(4) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both V(1)-O(3) bond lengths are 1.98 Å. There are two shorter (2.05 Å) and two longer (2.08 Å) V(1)-O(2) bond lengths. In the second V site, V(2) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-61°. The V(2)-O(4) bond length is 1.99 Å. The V(2)-O(5) bond length is 2.01 Å. There is one shorter (1.80 Å) and one longer (1.95 Å) V(2)-O(1) bond length. There is one shorter (2.07 Å) and one longer (2.14 Å) V(2)-O(2) bond length. B(1) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. The B(1)-O(3) bond length is 1.39 Å. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.39 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent V(2) atoms to form OLi2V2 tetrahedra that share corners with three equivalent O(2)LiV4 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, and  an edgeedge with one O(2)LiV4 square pyramid. In the second O site, O(2) is bonded to one Li(2), two equivalent V(1), and two equivalent V(2) atoms to form OLiV4 square pyramids that share corners with two equivalent O(2)LiV4 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, edges with three equivalent O(2)LiV4 square pyramids, and  an edgeedge with one O(1)Li2V2 tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one B(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(2), and one B(1) atom.