Li3V3MnO8 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(8), and two equivalent O(3) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 5-7°. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(7), and two equivalent O(1) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the third Li site, Li(3) is bonded to one O(2), one O(5), one O(8), and two equivalent O(6) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 2-8°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(6), one O(7), 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(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, edges with two equivalent Li(3)O5 square pyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-24°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O5 square pyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 11-24°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O5 square pyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-28°. Mn(1) is bonded to one O(1), one O(3), one O(5), one O(8), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-28°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one Mn(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li2Mn2V2 octahedra, corners with two equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(5)LiMnV3 square pyramid,  a cornercorner with one O(6)Li2V3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn2V2 octahedra,  an edgeedge with one O(8)Li2MnV2 square pyramid, edges with two equivalent O(5)LiMnV3 square pyramids, edges with two equivalent O(3)Li2MnV2 trigonal bipyramids, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), one V(3), and one Mn(1) atom to form OLi2MnV2 trigonal bipyramids that share  a cornercorner with one O(4)Li2Mn2V2 octahedra,  a cornercorner with one O(8)Li2MnV2 square pyramid, corners with two equivalent O(3)Li2MnV2 trigonal bipyramids, edges with two equivalent O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(5)LiMnV3 square pyramid, edges with two equivalent O(8)Li2MnV2 square pyramids, and  an edgeedge with one O(6)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 25°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(3), and two equivalent Mn(1) atoms to form OLi2Mn2V2 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(4)Li2Mn2V2 octahedra,  a cornercorner with one O(8)Li2MnV2 square pyramid,  a cornercorner with one O(3)Li2MnV2 trigonal bipyramid,  an edgeedge with one O(2)Li3V3 octahedra, edges with two equivalent O(8)Li2MnV2 square pyramids, edges with two equivalent O(5)LiMnV3 square pyramids,  an edgeedge with one O(6)Li2V3 trigonal bipyramid, and edges with two equivalent O(3)Li2MnV2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-20°. In the fifth O site, O(5) is bonded to one Li(3), one V(2), two equivalent V(1), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(5)LiMnV3 square pyramids,  a cornercorner with one O(6)Li2V3 trigonal bipyramid, edges with two equivalent O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(8)Li2MnV2 square pyramid,  an edgeedge with one O(3)Li2MnV2 trigonal bipyramid, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 15°. In the sixth O site, O(6) is bonded to two equivalent Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(5)LiMnV3 square pyramid, corners with two equivalent O(6)Li2V3 trigonal bipyramids,  an edgeedge with one O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(8)Li2MnV2 square pyramids, edges with two equivalent O(5)LiMnV3 square pyramids, and  an edgeedge with one O(3)Li2MnV2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), two equivalent V(3), and one Mn(1) atom to form OLi2MnV2 square pyramids that share  a cornercorner with one O(4)Li2Mn2V2 octahedra, corners with two equivalent O(8)Li2MnV2 square pyramids,  a cornercorner with one O(3)Li2MnV2 trigonal bipyramid,  an edgeedge with one O(2)Li3V3 octahedra, edges with two equivalent O(4)Li2Mn2V2 octahedra,  an edgeedge with one O(5)LiMnV3 square pyramid, edges with two equivalent O(3)Li2MnV2 trigonal bipyramids, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°.
Li3V3MnO8 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(4), one O(8), and two equivalent O(3) atoms to form LiO5 square pyramids that share  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(3)O5 square pyramid. The corner-sharing octahedral tilt angles range from 5-7°. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(4) bond length is 2.26 Å. The Li(1)-O(8) bond length is 2.01 Å. Both Li(1)-O(3) bond lengths are 2.04 Å. In the second Li site, Li(2) is bonded to one O(2), one O(4), one O(7), and two equivalent O(1) atoms to form LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid, corners with two equivalent Li(1)O5 square pyramids, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 3°. The Li(2)-O(2) bond length is 2.00 Å. The Li(2)-O(4) bond length is 2.17 Å. The Li(2)-O(7) bond length is 2.05 Å. Both Li(2)-O(1) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to one O(2), one O(5), one O(8), and two equivalent O(6) atoms to form LiO5 square pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(3)O5 square pyramids,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 2-8°. The Li(3)-O(2) bond length is 2.20 Å. The Li(3)-O(5) bond length is 2.21 Å. The Li(3)-O(8) bond length is 1.96 Å. Both Li(3)-O(6) bond lengths are 2.04 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(4), one O(6), one O(7), 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(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, edges with two equivalent Li(3)O5 square pyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-24°. The V(1)-O(2) bond length is 2.12 Å. The V(1)-O(4) bond length is 2.19 Å. The V(1)-O(6) bond length is 2.04 Å. The V(1)-O(7) bond length is 1.98 Å. Both V(1)-O(5) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(5), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(3)O5 square pyramid,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O5 square pyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 11-24°. The V(2)-O(1) bond length is 1.76 Å. The V(2)-O(3) bond length is 2.05 Å. The V(2)-O(5) bond length is 2.08 Å. The V(2)-O(6) bond length is 2.00 Å. Both V(2)-O(2) bond lengths are 2.05 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(6), one O(7), and two equivalent O(8) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, edges with two equivalent Li(3)O5 square pyramids, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 4-28°. The V(3)-O(3) bond length is 1.95 Å. The V(3)-O(4) bond length is 2.11 Å. The V(3)-O(6) bond length is 2.13 Å. The V(3)-O(7) bond length is 1.78 Å. Both V(3)-O(8) bond lengths are 2.05 Å. Mn(1) is bonded to one O(1), one O(3), one O(5), one O(8), and two equivalent O(4) atoms to form distorted MnO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(3)O5 square pyramid, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 13-28°. The Mn(1)-O(1) bond length is 2.08 Å. The Mn(1)-O(3) bond length is 2.13 Å. The Mn(1)-O(5) bond length is 2.32 Å. The Mn(1)-O(8) bond length is 2.23 Å. Both Mn(1)-O(4) bond lengths are 2.07 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(2), and one Mn(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(4)Li2Mn2V2 octahedra, corners with two equivalent O(2)Li3V3 octahedra,  a cornercorner with one O(5)LiMnV3 square pyramid,  a cornercorner with one O(6)Li2V3 trigonal bipyramid,  an edgeedge with one O(4)Li2Mn2V2 octahedra,  an edgeedge with one O(8)Li2MnV2 square pyramid, edges with two equivalent O(5)LiMnV3 square pyramids, edges with two equivalent O(3)Li2MnV2 trigonal bipyramids, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to two equivalent Li(1), one V(2), one V(3), and one Mn(1) atom to form OLi2MnV2 trigonal bipyramids that share  a cornercorner with one O(4)Li2Mn2V2 octahedra,  a cornercorner with one O(8)Li2MnV2 square pyramid, corners with two equivalent O(3)Li2MnV2 trigonal bipyramids, edges with two equivalent O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(5)LiMnV3 square pyramid, edges with two equivalent O(8)Li2MnV2 square pyramids, and  an edgeedge with one O(6)Li2V3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 25°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(3), and two equivalent Mn(1) atoms to form OLi2Mn2V2 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(4)Li2Mn2V2 octahedra,  a cornercorner with one O(8)Li2MnV2 square pyramid,  a cornercorner with one O(3)Li2MnV2 trigonal bipyramid,  an edgeedge with one O(2)Li3V3 octahedra, edges with two equivalent O(8)Li2MnV2 square pyramids, edges with two equivalent O(5)LiMnV3 square pyramids,  an edgeedge with one O(6)Li2V3 trigonal bipyramid, and edges with two equivalent O(3)Li2MnV2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-20°. In the fifth O site, O(5) is bonded to one Li(3), one V(2), two equivalent V(1), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(2)Li3V3 octahedra, corners with two equivalent O(5)LiMnV3 square pyramids,  a cornercorner with one O(6)Li2V3 trigonal bipyramid, edges with two equivalent O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra,  an edgeedge with one O(8)Li2MnV2 square pyramid,  an edgeedge with one O(3)Li2MnV2 trigonal bipyramid, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 15°. In the sixth O site, O(6) is bonded to two equivalent Li(3), one V(1), one V(2), and one V(3) atom to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(5)LiMnV3 square pyramid, corners with two equivalent O(6)Li2V3 trigonal bipyramids,  an edgeedge with one O(4)Li2Mn2V2 octahedra, edges with two equivalent O(2)Li3V3 octahedra, edges with two equivalent O(8)Li2MnV2 square pyramids, edges with two equivalent O(5)LiMnV3 square pyramids, and  an edgeedge with one O(3)Li2MnV2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(2), one V(1), and one V(3) atom. In the eighth O site, O(8) is bonded to one Li(1), one Li(3), two equivalent V(3), and one Mn(1) atom to form OLi2MnV2 square pyramids that share  a cornercorner with one O(4)Li2Mn2V2 octahedra, corners with two equivalent O(8)Li2MnV2 square pyramids,  a cornercorner with one O(3)Li2MnV2 trigonal bipyramid,  an edgeedge with one O(2)Li3V3 octahedra, edges with two equivalent O(4)Li2Mn2V2 octahedra,  an edgeedge with one O(5)LiMnV3 square pyramid, edges with two equivalent O(3)Li2MnV2 trigonal bipyramids, and edges with two equivalent O(6)Li2V3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 11°.