Li2V5B3O13 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(7), two equivalent O(3), and two equivalent O(9) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. In the second Li site, Li(2) is bonded to one O(1), one O(9), and three equivalent O(10) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(1)O7 pentagonal bipyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent V(1)O7 pentagonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 12°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), two equivalent O(1), and three equivalent O(8) atoms to form distorted VO7 pentagonal bipyramids that share  a cornercorner with one Li(2)O5 trigonal bipyramid, edges with four equivalent V(1)O7 pentagonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. In the second V site, V(2) is bonded in a 7-coordinate geometry to one O(3), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. In the third V site, V(3) is bonded in a 7-coordinate geometry to one O(12), one O(5), one O(8), two equivalent O(11), and two equivalent O(4) atoms. In the fourth V site, V(4) is bonded to one O(12), one O(5), two equivalent O(6), and three equivalent O(13) atoms to form distorted VO7 pentagonal bipyramids that share  a cornercorner with one V(5)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with four equivalent V(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 51°. In the fifth V site, V(5) is bonded to one O(13), one O(9), two equivalent O(12), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one V(4)O7 pentagonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(4)O7 pentagonal bipyramids, and edges with two equivalent Li(1)O5 square pyramids. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(6), and one O(7) atom. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(9) atom. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent V(1), and one B(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent V(2) and one B(2) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), and one B(1) atom to form distorted OLi2VB tetrahedra that share corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(5)V4 tetrahedra, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(7)LiV2B trigonal pyramids, and  an edgeedge with one O(9)Li3VB trigonal bipyramid. 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 to one V(3), one V(4), and two equivalent V(2) atoms to form OV4 tetrahedra that share  a cornercorner with one O(8)V4 tetrahedra, corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(5)V4 tetrahedra, corners with three equivalent O(13)V4 tetrahedra, and  an edgeedge with one O(12)V4 trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(2), two equivalent V(4), and one B(2) atom. In the seventh O site, O(7) is bonded to one Li(1), two equivalent V(5), and one B(2) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(13)V4 tetrahedra, corners with two equivalent O(7)LiV2B trigonal pyramids, corners with two equivalent O(12)V4 trigonal pyramids, edges with two equivalent O(9)Li3VB trigonal bipyramids, and  an edgeedge with one O(12)V4 trigonal pyramid. In the eighth O site, O(8) is bonded to one V(3) and three equivalent V(1) atoms to form OV4 tetrahedra that share  a cornercorner with one O(5)V4 tetrahedra, corners with two equivalent O(8)V4 tetrahedra, corners with three equivalent O(10)Li3VB trigonal bipyramids,  a cornercorner with one O(12)V4 trigonal pyramid, and edges with two equivalent O(8)V4 tetrahedra. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(1), one V(5), and one B(3) atom to form distorted OLi3VB trigonal bipyramids that share  a cornercorner with one O(13)V4 tetrahedra, corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(10)Li3VB trigonal bipyramids, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(12)V4 trigonal pyramids,  an edgeedge with one O(3)Li2VB tetrahedra,  an edgeedge with one O(10)Li3VB trigonal bipyramid, and edges with two equivalent O(7)LiV2B trigonal pyramids. In the tenth O site, O(10) is bonded to three equivalent Li(2), one V(1), and one B(3) atom to form distorted OLi3VB trigonal bipyramids that share corners with three equivalent O(8)V4 tetrahedra, corners with two equivalent O(10)Li3VB trigonal bipyramids, corners with two equivalent O(9)Li3VB trigonal bipyramids,  an edgeedge with one O(9)Li3VB trigonal bipyramid, and edges with two equivalent O(10)Li3VB trigonal bipyramids. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one V(1), two equivalent V(3), and one B(3) atom. In the twelfth O site, O(12) is bonded to one V(3), one V(4), and two equivalent V(5) atoms to form distorted OV4 trigonal pyramids that share  a cornercorner with one O(13)V4 tetrahedra,  a cornercorner with one O(8)V4 tetrahedra, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(7)LiV2B trigonal pyramids, corners with two equivalent O(12)V4 trigonal pyramids,  an edgeedge with one O(5)V4 tetrahedra, edges with two equivalent O(13)V4 tetrahedra, and  an edgeedge with one O(7)LiV2B trigonal pyramid. In the thirteenth O site, O(13) is bonded to one V(5) and three equivalent V(4) atoms to form OV4 tetrahedra that share corners with two equivalent O(13)V4 tetrahedra, corners with three equivalent O(5)V4 tetrahedra,  a cornercorner with one O(9)Li3VB trigonal bipyramid,  a cornercorner with one O(12)V4 trigonal pyramid, corners with two equivalent O(7)LiV2B trigonal pyramids, edges with two equivalent O(13)V4 tetrahedra, and edges with two equivalent O(12)V4 trigonal pyramids.
Li2V5B3O13 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(7), two equivalent O(3), and two equivalent O(9) atoms to form distorted LiO5 square pyramids that share corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent V(5)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The Li(1)-O(7) bond length is 1.90 Å. Both Li(1)-O(3) bond lengths are 1.99 Å. Both Li(1)-O(9) bond lengths are 2.37 Å. In the second Li site, Li(2) is bonded to one O(1), one O(9), and three equivalent O(10) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(5)O6 octahedra,  a cornercorner with one V(1)O7 pentagonal bipyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids, edges with two equivalent V(1)O7 pentagonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 12°. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(9) bond length is 2.17 Å. There are two shorter (2.00 Å) and one longer (2.19 Å) Li(2)-O(10) bond length. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), two equivalent O(1), and three equivalent O(8) atoms to form distorted VO7 pentagonal bipyramids that share  a cornercorner with one Li(2)O5 trigonal bipyramid, edges with four equivalent V(1)O7 pentagonal bipyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The V(1)-O(10) bond length is 2.23 Å. The V(1)-O(11) bond length is 2.18 Å. Both V(1)-O(1) bond lengths are 2.20 Å. There is one shorter (2.04 Å) and two longer (2.05 Å) V(1)-O(8) bond lengths. In the second V site, V(2) is bonded in a 7-coordinate geometry to one O(3), one O(4), one O(6), two equivalent O(2), and two equivalent O(5) atoms. The V(2)-O(3) bond length is 2.12 Å. The V(2)-O(4) bond length is 2.40 Å. The V(2)-O(6) bond length is 2.16 Å. Both V(2)-O(2) bond lengths are 2.17 Å. Both V(2)-O(5) bond lengths are 2.05 Å. In the third V site, V(3) is bonded in a 7-coordinate geometry to one O(12), one O(5), one O(8), two equivalent O(11), and two equivalent O(4) atoms. The V(3)-O(12) bond length is 2.01 Å. The V(3)-O(5) bond length is 2.23 Å. The V(3)-O(8) bond length is 2.08 Å. Both V(3)-O(11) bond lengths are 2.16 Å. Both V(3)-O(4) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to one O(12), one O(5), two equivalent O(6), and three equivalent O(13) atoms to form distorted VO7 pentagonal bipyramids that share  a cornercorner with one V(5)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and edges with four equivalent V(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 51°. The V(4)-O(12) bond length is 2.24 Å. The V(4)-O(5) bond length is 2.03 Å. Both V(4)-O(6) bond lengths are 2.31 Å. There are two shorter (2.06 Å) and one longer (2.09 Å) V(4)-O(13) bond length. In the fifth V site, V(5) is bonded to one O(13), one O(9), two equivalent O(12), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one V(4)O7 pentagonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(4)O7 pentagonal bipyramids, and edges with two equivalent Li(1)O5 square pyramids. The V(5)-O(13) bond length is 1.96 Å. The V(5)-O(9) bond length is 2.11 Å. Both V(5)-O(12) bond lengths are 2.04 Å. Both V(5)-O(7) bond lengths are 2.12 Å. There are three inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(1), one O(3), and one O(4) atom. The B(1)-O(1) bond length is 1.38 Å. The B(1)-O(3) bond length is 1.36 Å. The B(1)-O(4) bond length is 1.39 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(2), one O(6), and one O(7) atom. The B(2)-O(2) bond length is 1.38 Å. The B(2)-O(6) bond length is 1.39 Å. The B(2)-O(7) bond length is 1.40 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(9) atom. The B(3)-O(10) bond length is 1.37 Å. The B(3)-O(11) bond length is 1.40 Å. The B(3)-O(9) bond length is 1.37 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent V(1), and one B(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent V(2) and one B(2) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), and one B(1) atom to form distorted OLi2VB tetrahedra that share corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(5)V4 tetrahedra, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(7)LiV2B trigonal pyramids, and  an edgeedge with one O(9)Li3VB trigonal bipyramid. 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 to one V(3), one V(4), and two equivalent V(2) atoms to form OV4 tetrahedra that share  a cornercorner with one O(8)V4 tetrahedra, corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(5)V4 tetrahedra, corners with three equivalent O(13)V4 tetrahedra, and  an edgeedge with one O(12)V4 trigonal pyramid. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one V(2), two equivalent V(4), and one B(2) atom. In the seventh O site, O(7) is bonded to one Li(1), two equivalent V(5), and one B(2) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(13)V4 tetrahedra, corners with two equivalent O(7)LiV2B trigonal pyramids, corners with two equivalent O(12)V4 trigonal pyramids, edges with two equivalent O(9)Li3VB trigonal bipyramids, and  an edgeedge with one O(12)V4 trigonal pyramid. In the eighth O site, O(8) is bonded to one V(3) and three equivalent V(1) atoms to form OV4 tetrahedra that share  a cornercorner with one O(5)V4 tetrahedra, corners with two equivalent O(8)V4 tetrahedra, corners with three equivalent O(10)Li3VB trigonal bipyramids,  a cornercorner with one O(12)V4 trigonal pyramid, and edges with two equivalent O(8)V4 tetrahedra. In the ninth O site, O(9) is bonded to one Li(2), two equivalent Li(1), one V(5), and one B(3) atom to form distorted OLi3VB trigonal bipyramids that share  a cornercorner with one O(13)V4 tetrahedra, corners with two equivalent O(3)Li2VB tetrahedra, corners with two equivalent O(10)Li3VB trigonal bipyramids, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(12)V4 trigonal pyramids,  an edgeedge with one O(3)Li2VB tetrahedra,  an edgeedge with one O(10)Li3VB trigonal bipyramid, and edges with two equivalent O(7)LiV2B trigonal pyramids. In the tenth O site, O(10) is bonded to three equivalent Li(2), one V(1), and one B(3) atom to form distorted OLi3VB trigonal bipyramids that share corners with three equivalent O(8)V4 tetrahedra, corners with two equivalent O(10)Li3VB trigonal bipyramids, corners with two equivalent O(9)Li3VB trigonal bipyramids,  an edgeedge with one O(9)Li3VB trigonal bipyramid, and edges with two equivalent O(10)Li3VB trigonal bipyramids. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one V(1), two equivalent V(3), and one B(3) atom. In the twelfth O site, O(12) is bonded to one V(3), one V(4), and two equivalent V(5) atoms to form distorted OV4 trigonal pyramids that share  a cornercorner with one O(13)V4 tetrahedra,  a cornercorner with one O(8)V4 tetrahedra, corners with two equivalent O(9)Li3VB trigonal bipyramids, corners with two equivalent O(7)LiV2B trigonal pyramids, corners with two equivalent O(12)V4 trigonal pyramids,  an edgeedge with one O(5)V4 tetrahedra, edges with two equivalent O(13)V4 tetrahedra, and  an edgeedge with one O(7)LiV2B trigonal pyramid. In the thirteenth O site, O(13) is bonded to one V(5) and three equivalent V(4) atoms to form OV4 tetrahedra that share corners with two equivalent O(13)V4 tetrahedra, corners with three equivalent O(5)V4 tetrahedra,  a cornercorner with one O(9)Li3VB trigonal bipyramid,  a cornercorner with one O(12)V4 trigonal pyramid, corners with two equivalent O(7)LiV2B trigonal pyramids, edges with two equivalent O(13)V4 tetrahedra, and edges with two equivalent O(12)V4 trigonal pyramids.