Li3V3(BO5)2 crystallizes in the orthorhombic Pmc2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), two equivalent O(10), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. In the second Li site, Li(2) is bonded to one O(3), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one 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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-28°. In the third Li site, Li(3) is bonded to one O(10), one O(9), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-56°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(7), two equivalent O(3), and two equivalent O(9) atoms to form VO6 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 Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. 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 Li(2)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 21-56°. In the third V site, V(3) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)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 46-56°. There are two inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(10), one O(8), and one O(9) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to two equivalent Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with two equivalent O(7)Li4V square pyramids,  an edgeedge with one O(7)Li4V square pyramid, and edges with two equivalent O(2)Li2V3 square pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one V(2), two equivalent V(3), 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. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one V(3) atom. In the seventh O site, O(7) is bonded to two equivalent Li(2), two equivalent Li(3), and one V(1) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(2)Li2V3 square pyramids,  an edgeedge with one O(2)Li2V3 square pyramid, and edges with two equivalent O(7)Li4V square pyramids. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(3), and one B(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(1), and one B(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Li(1), and one B(2) atom.
Li3V3(BO5)2 crystallizes in the orthorhombic Pmc2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(6), two equivalent O(10), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-63°. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-O(6) bond length is 2.09 Å. Both Li(1)-O(10) bond lengths are 2.05 Å. Both Li(1)-O(5) bond lengths are 2.25 Å. In the second Li site, Li(2) is bonded to one O(3), one O(8), two equivalent O(2), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one 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(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-28°. The Li(2)-O(3) bond length is 2.20 Å. The Li(2)-O(8) bond length is 2.17 Å. Both Li(2)-O(2) bond lengths are 2.19 Å. Both Li(2)-O(7) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded to one O(10), one O(9), two equivalent O(6), and two equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-56°. The Li(3)-O(10) bond length is 1.95 Å. The Li(3)-O(9) bond length is 2.32 Å. Both Li(3)-O(6) bond lengths are 2.11 Å. Both Li(3)-O(7) bond lengths are 2.15 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(7), two equivalent O(3), and two equivalent O(9) atoms to form VO6 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 Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(7) bond length is 1.74 Å. Both V(1)-O(3) bond lengths are 2.08 Å. Both V(1)-O(9) bond lengths are 2.04 Å. 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 Li(2)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 21-56°. The V(2)-O(4) bond length is 2.17 Å. The V(2)-O(5) bond length is 2.06 Å. Both V(2)-O(1) bond lengths are 2.01 Å. Both V(2)-O(2) bond lengths are 2.05 Å. In the third V site, V(3) is bonded to one O(2), one O(6), two equivalent O(4), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(2)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 46-56°. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(6) bond length is 1.69 Å. Both V(3)-O(4) bond lengths are 2.13 Å. Both V(3)-O(8) bond lengths are 2.04 Å. There are two inequivalent B sites. In the first B site, 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 1.41 Å. The B(1)-O(4) bond length is 1.44 Å. The B(1)-O(5) bond length is 1.33 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(10), one O(8), and one O(9) atom. The B(2)-O(10) bond length is 1.31 Å. The B(2)-O(8) bond length is 1.45 Å. The B(2)-O(9) bond length is 1.43 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent V(2) atoms. In the second O site, O(2) is bonded to two equivalent Li(2), one V(3), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with two equivalent O(7)Li4V square pyramids,  an edgeedge with one O(7)Li4V square pyramid, and edges with two equivalent O(2)Li2V3 square pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(1), and one B(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one V(2), two equivalent V(3), 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. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one V(3) atom. In the seventh O site, O(7) is bonded to two equivalent Li(2), two equivalent Li(3), and one V(1) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(2)Li2V3 square pyramids,  an edgeedge with one O(2)Li2V3 square pyramid, and edges with two equivalent O(7)Li4V square pyramids. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(3), and one B(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(1), and one B(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Li(1), and one B(2) atom.