Li3V3(BO5)2 crystallizes in the monoclinic Pm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(3), two equivalent O(19), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one 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(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-29°. In the second Li site, Li(2) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(9) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-68°. In the third Li site, Li(3) is bonded to one O(10), one O(11), two equivalent O(15), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-64°. In the fourth Li site, Li(4) is bonded to one O(13), one O(8), two equivalent O(12), and two equivalent O(9) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(6)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(6)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-25°. In the fifth Li site, Li(5) is bonded to one O(15), one O(17), two equivalent O(11), and two equivalent O(19) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-57°. In the sixth Li site, Li(6) is bonded to one O(14), one O(16), two equivalent O(12), and two equivalent O(20) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-70°. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(20), two equivalent O(16), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. In the second V site, V(2) is bonded to one O(1), one O(19), two equivalent O(17), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-68°. In the third V site, V(3) is bonded to one O(4), one O(6), two equivalent O(10), 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(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-55°. In the fourth V site, V(4) is bonded to one O(10), one O(12), two equivalent O(14), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. In the fifth V site, V(5) is bonded to one O(11), one O(9), two equivalent O(13), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. In the sixth V site, V(6) is bonded to one O(2), one O(20), two equivalent O(18), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-70°. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(8) atom. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), 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(14), one O(15), and one O(18) atom. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(13), one O(16), and one O(17) atom. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(6), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share edges with two equivalent O(2)Li2V3 square pyramids and edges with two equivalent O(18)LiV2B trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one V(3), two equivalent V(6), and one B(1) atom. In the fifth O site, O(5) 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 sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(3), one V(3), and one B(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(5), and one B(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), two equivalent V(4), and one B(1) atom. In the ninth O site, O(9) is bonded to two equivalent Li(2), two equivalent Li(4), and one V(5) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(12)Li4V square pyramids,  a cornercorner with one O(11)Li3V trigonal pyramid,  an edgeedge with one O(12)Li4V square pyramid, and edges with two equivalent O(9)Li4V square pyramids. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(4), and two equivalent V(3) atoms. In the eleventh O site, O(11) is bonded to one Li(3), two equivalent Li(5), and one V(5) atom to form distorted OLi3V trigonal pyramids that share  a cornercorner with one O(9)Li4V square pyramid and corners with two equivalent O(11)Li3V trigonal pyramids. In the twelfth O site, O(12) is bonded to two equivalent Li(4), two equivalent Li(6), and one V(4) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(9)Li4V square pyramids, corners with two equivalent O(16)LiV2B trigonal pyramids,  an edgeedge with one O(9)Li4V square pyramid, and edges with two equivalent O(12)Li4V square pyramids. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(5), and one B(4) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), two equivalent V(4), and one B(3) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent Li(3), and one B(3) atom. In the sixteenth O site, O(16) is bonded to one Li(6), two equivalent V(1), and one B(4) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(12)Li4V square pyramids and corners with two equivalent O(16)LiV2B trigonal pyramids. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent V(2), and one B(4) atom. In the eighteenth O site, O(18) is bonded to one Li(1), two equivalent V(6), and one B(3) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(18)LiV2B trigonal pyramids and edges with two equivalent O(2)Li2V3 square pyramids. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(5), and one V(2) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(6), one V(1), and one V(6) atom.
Li3V3(BO5)2 crystallizes in the monoclinic Pm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(3), two equivalent O(19), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra,  an edgeedge with one 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(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-29°. The Li(1)-O(18) bond length is 2.23 Å. The Li(1)-O(3) bond length is 2.26 Å. Both Li(1)-O(19) bond lengths are 2.05 Å. Both Li(1)-O(2) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), two equivalent O(1), and two equivalent O(9) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-68°. The Li(2)-O(5) bond length is 2.18 Å. The Li(2)-O(7) bond length is 2.07 Å. Both Li(2)-O(1) bond lengths are 2.25 Å. Both Li(2)-O(9) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded to one O(10), one O(11), two equivalent O(15), and two equivalent O(6) atoms to form LiO6 octahedra that share  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one V(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-64°. The Li(3)-O(10) bond length is 2.43 Å. The Li(3)-O(11) bond length is 2.02 Å. Both Li(3)-O(15) bond lengths are 2.06 Å. Both Li(3)-O(6) bond lengths are 2.29 Å. In the fourth Li site, Li(4) is bonded to one O(13), one O(8), two equivalent O(12), and two equivalent O(9) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(6)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(6)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-25°. The Li(4)-O(13) bond length is 2.09 Å. The Li(4)-O(8) bond length is 2.17 Å. Both Li(4)-O(12) bond lengths are 2.20 Å. Both Li(4)-O(9) bond lengths are 2.05 Å. In the fifth Li site, Li(5) is bonded to one O(15), one O(17), two equivalent O(11), and two equivalent O(19) atoms to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-57°. The Li(5)-O(15) bond length is 1.99 Å. The Li(5)-O(17) bond length is 2.23 Å. Both Li(5)-O(11) bond lengths are 2.01 Å. Both Li(5)-O(19) bond lengths are 2.28 Å. In the sixth Li site, Li(6) is bonded to one O(14), one O(16), two equivalent O(12), and two equivalent O(20) atoms to form LiO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with two equivalent V(6)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-70°. The Li(6)-O(14) bond length is 2.21 Å. The Li(6)-O(16) bond length is 2.10 Å. Both Li(6)-O(12) bond lengths are 2.10 Å. Both Li(6)-O(20) bond lengths are 2.19 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(20), two equivalent O(16), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(6)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. The V(1)-O(1) bond length is 1.81 Å. The V(1)-O(20) bond length is 1.83 Å. Both V(1)-O(16) bond lengths are 2.09 Å. Both V(1)-O(5) bond lengths are 2.10 Å. In the second V site, V(2) is bonded to one O(1), one O(19), two equivalent O(17), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-68°. The V(2)-O(1) bond length is 2.01 Å. The V(2)-O(19) bond length is 1.71 Å. Both V(2)-O(17) bond lengths are 2.07 Å. Both V(2)-O(3) bond lengths are 2.07 Å. In the third V site, V(3) is bonded to one O(4), one O(6), two equivalent O(10), 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(4)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-55°. The V(3)-O(4) bond length is 2.15 Å. The V(3)-O(6) bond length is 1.98 Å. Both V(3)-O(10) bond lengths are 2.04 Å. Both V(3)-O(2) bond lengths are 2.07 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), two equivalent O(14), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(6)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. The V(4)-O(10) bond length is 1.93 Å. The V(4)-O(12) bond length is 1.74 Å. Both V(4)-O(14) bond lengths are 2.04 Å. Both V(4)-O(8) bond lengths are 2.13 Å. In the fifth V site, V(5) is bonded to one O(11), one O(9), two equivalent O(13), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. The V(5)-O(11) bond length is 1.75 Å. The V(5)-O(9) bond length is 1.82 Å. Both V(5)-O(13) bond lengths are 2.16 Å. Both V(5)-O(7) bond lengths are 2.10 Å. In the sixth V site, V(6) is bonded to one O(2), one O(20), two equivalent O(18), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(6)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-70°. The V(6)-O(2) bond length is 1.96 Å. The V(6)-O(20) bond length is 1.95 Å. Both V(6)-O(18) bond lengths are 2.04 Å. Both V(6)-O(4) bond lengths are 2.17 Å. There are four inequivalent B sites. In the first B site, B(1) is bonded in a trigonal planar geometry to one O(4), one O(5), and one O(8) atom. The B(1)-O(4) bond length is 1.40 Å. The B(1)-O(5) bond length is 1.40 Å. The B(1)-O(8) bond length is 1.38 Å. In the second B site, B(2) is bonded in a trigonal planar geometry to one O(3), one O(6), and one O(7) atom. The B(2)-O(3) bond length is 1.43 Å. The B(2)-O(6) bond length is 1.36 Å. The B(2)-O(7) bond length is 1.38 Å. In the third B site, B(3) is bonded in a trigonal planar geometry to one O(14), one O(15), and one O(18) atom. The B(3)-O(14) bond length is 1.43 Å. The B(3)-O(15) bond length is 1.31 Å. The B(3)-O(18) bond length is 1.44 Å. In the fourth B site, B(4) is bonded in a trigonal planar geometry to one O(13), one O(16), and one O(17) atom. The B(4)-O(13) bond length is 1.37 Å. The B(4)-O(16) bond length is 1.41 Å. The B(4)-O(17) bond length is 1.39 Å. There are twenty inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to two equivalent Li(1), one V(6), and two equivalent V(3) atoms to form OLi2V3 square pyramids that share edges with two equivalent O(2)Li2V3 square pyramids and edges with two equivalent O(18)LiV2B trigonal pyramids. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one B(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one V(3), two equivalent V(6), and one B(1) atom. In the fifth O site, O(5) 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 sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(3), one V(3), and one B(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), two equivalent V(5), and one B(2) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), two equivalent V(4), and one B(1) atom. In the ninth O site, O(9) is bonded to two equivalent Li(2), two equivalent Li(4), and one V(5) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(12)Li4V square pyramids,  a cornercorner with one O(11)Li3V trigonal pyramid,  an edgeedge with one O(12)Li4V square pyramid, and edges with two equivalent O(9)Li4V square pyramids. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(4), and two equivalent V(3) atoms. In the eleventh O site, O(11) is bonded to one Li(3), two equivalent Li(5), and one V(5) atom to form distorted OLi3V trigonal pyramids that share  a cornercorner with one O(9)Li4V square pyramid and corners with two equivalent O(11)Li3V trigonal pyramids. In the twelfth O site, O(12) is bonded to two equivalent Li(4), two equivalent Li(6), and one V(4) atom to form distorted OLi4V square pyramids that share corners with two equivalent O(9)Li4V square pyramids, corners with two equivalent O(16)LiV2B trigonal pyramids,  an edgeedge with one O(9)Li4V square pyramid, and edges with two equivalent O(12)Li4V square pyramids. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(5), and one B(4) atom. In the fourteenth O site, O(14) is bonded in a distorted rectangular see-saw-like geometry to one Li(6), two equivalent V(4), and one B(3) atom. In the fifteenth O site, O(15) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent Li(3), and one B(3) atom. In the sixteenth O site, O(16) is bonded to one Li(6), two equivalent V(1), and one B(4) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(12)Li4V square pyramids and corners with two equivalent O(16)LiV2B trigonal pyramids. In the seventeenth O site, O(17) is bonded in a distorted rectangular see-saw-like geometry to one Li(5), two equivalent V(2), and one B(4) atom. In the eighteenth O site, O(18) is bonded to one Li(1), two equivalent V(6), and one B(3) atom to form distorted OLiV2B trigonal pyramids that share corners with two equivalent O(18)LiV2B trigonal pyramids and edges with two equivalent O(2)Li2V3 square pyramids. In the nineteenth O site, O(19) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(5), and one V(2) atom. In the twentieth O site, O(20) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(6), one V(1), and one V(6) atom.