Li4V3Mn3(WO8)2 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-67°. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-66°. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-66°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent W(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. In the second W site, W(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form WO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent W(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), one W(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Mn(1) atom to form distorted OLiMnV2 trigonal pyramids that share  a cornercorner with one O(12)LiMn2W tetrahedra, corners with three equivalent O(4)LiMnV2 tetrahedra, and edges with two equivalent O(6)LiMnVW tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), two equivalent V(1), and one Mn(1) atom to form OLiMnV2 tetrahedra that share corners with four equivalent O(6)LiMnVW tetrahedra and corners with three equivalent O(3)LiMnV2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and two equivalent Mn(2) atoms to form corner-sharing OLiMn2V tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one W(1), and one Mn(1) atom to form distorted OLiMnVW tetrahedra that share  a cornercorner with one O(6)LiMnVW tetrahedra, corners with two equivalent O(4)LiMnV2 tetrahedra,  an edgeedge with one O(6)LiMnVW tetrahedra, and  an edgeedge with one O(3)LiMnV2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent V(1), and one W(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one W(1), and two equivalent Mn(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one W(2), and one Mn(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(2), and two equivalent Mn(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one W(2), and one Mn(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one W(2), and two equivalent Mn(2) atoms to form distorted OLiMn2W tetrahedra that share corners with two equivalent O(5)LiMn2V tetrahedra and  a cornercorner with one O(3)LiMnV2 trigonal pyramid.
Li4V3Mn3(WO8)2 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and corners with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-65°. The Li(1)-O(12) bond length is 2.02 Å. The Li(1)-O(3) bond length is 1.98 Å. Both Li(1)-O(9) bond lengths are 2.08 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-67°. The Li(2)-O(5) bond length is 1.87 Å. The Li(2)-O(7) bond length is 2.08 Å. Both Li(2)-O(11) bond lengths are 2.10 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-66°. The Li(3)-O(4) bond length is 1.83 Å. The Li(3)-O(8) bond length is 2.08 Å. Both Li(3)-O(1) bond lengths are 2.09 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-66°. The Li(4)-O(10) bond length is 2.03 Å. The Li(4)-O(2) bond length is 2.10 Å. Both Li(4)-O(6) bond lengths are 2.03 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share corners with two equivalent W(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(1)-O(11) bond length is 2.20 Å. The V(1)-O(2) bond length is 2.14 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(7) bond length is 2.18 Å. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(2)O6 octahedra, edges with four equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 46°. The V(2)-O(10) bond length is 1.84 Å. The V(2)-O(5) bond length is 1.85 Å. Both V(2)-O(1) bond lengths are 2.24 Å. Both V(2)-O(9) bond lengths are 1.98 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. The W(1)-O(2) bond length is 2.02 Å. The W(1)-O(8) bond length is 1.92 Å. Both W(1)-O(1) bond lengths are 1.94 Å. Both W(1)-O(6) bond lengths are 2.04 Å. In the second W site, W(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form WO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The W(2)-O(12) bond length is 1.96 Å. The W(2)-O(7) bond length is 1.98 Å. Both W(2)-O(11) bond lengths are 1.92 Å. Both W(2)-O(9) bond lengths are 2.05 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent W(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The Mn(1)-O(3) bond length is 2.08 Å. The Mn(1)-O(4) bond length is 2.04 Å. Both Mn(1)-O(11) bond lengths are 2.24 Å. Both Mn(1)-O(6) bond lengths are 2.22 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The Mn(2)-O(1) bond length is 2.23 Å. The Mn(2)-O(10) bond length is 2.09 Å. The Mn(2)-O(12) bond length is 2.17 Å. The Mn(2)-O(5) bond length is 2.05 Å. The Mn(2)-O(8) bond length is 2.21 Å. The Mn(2)-O(9) bond length is 2.30 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), one W(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(1), and one Mn(1) atom to form distorted OLiMnV2 trigonal pyramids that share  a cornercorner with one O(12)LiMn2W tetrahedra, corners with three equivalent O(4)LiMnV2 tetrahedra, and edges with two equivalent O(6)LiMnVW tetrahedra. In the fourth O site, O(4) is bonded to one Li(3), two equivalent V(1), and one Mn(1) atom to form OLiMnV2 tetrahedra that share corners with four equivalent O(6)LiMnVW tetrahedra and corners with three equivalent O(3)LiMnV2 trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and two equivalent Mn(2) atoms to form corner-sharing OLiMn2V tetrahedra. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one W(1), and one Mn(1) atom to form distorted OLiMnVW tetrahedra that share  a cornercorner with one O(6)LiMnVW tetrahedra, corners with two equivalent O(4)LiMnV2 tetrahedra,  an edgeedge with one O(6)LiMnVW tetrahedra, and  an edgeedge with one O(3)LiMnV2 trigonal pyramid. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent V(1), and one W(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one W(1), and two equivalent Mn(2) atoms. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one W(2), and one Mn(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(2), and two equivalent Mn(2) atoms. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), one W(2), and one Mn(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one W(2), and two equivalent Mn(2) atoms to form distorted OLiMn2W tetrahedra that share corners with two equivalent O(5)LiMn2V tetrahedra and  a cornercorner with one O(3)LiMnV2 trigonal pyramid.