LiV5(BO5)2 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 60°. In the second V site, V(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one V(1)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, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-61°. In the third V site, V(3) 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(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-61°. 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 V(1), one V(2), and two equivalent V(3) atoms to form distorted OV4 tetrahedra that share corners with three equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)V4 tetrahedra, and  an edgeedge with one O(2)Li2V3 square pyramid. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share corners with two equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)V4 tetrahedra, edges with three equivalent O(2)Li2V3 square pyramids, and  an edgeedge with one O(1)V4 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one B(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one B(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one B(1) atom.
LiV5(BO5)2 crystallizes in the orthorhombic Pbam space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Li(1)-O(3) bond lengths are 2.21 Å. All Li(1)-O(2) bond lengths are 2.15 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 60°. Both V(1)-O(1) bond lengths are 2.10 Å. All V(1)-O(4) bond lengths are 2.18 Å. In the second V site, V(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one V(1)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, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-61°. The V(2)-O(1) bond length is 2.04 Å. The V(2)-O(2) bond length is 2.04 Å. Both V(2)-O(3) bond lengths are 2.12 Å. Both V(2)-O(5) bond lengths are 2.19 Å. In the third V site, V(3) 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(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-61°. The V(3)-O(4) bond length is 2.15 Å. The V(3)-O(5) bond length is 2.16 Å. Both V(3)-O(1) bond lengths are 2.05 Å. Both V(3)-O(2) bond lengths are 2.03 Å. 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 1.38 Å. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.40 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one V(1), one V(2), and two equivalent V(3) atoms to form distorted OV4 tetrahedra that share corners with three equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)V4 tetrahedra, and  an edgeedge with one O(2)Li2V3 square pyramid. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share corners with two equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)V4 tetrahedra, edges with three equivalent O(2)Li2V3 square pyramids, and  an edgeedge with one O(1)V4 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one B(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one B(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(2), and one B(1) atom.