Li4V3Fe3(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 V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. 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 Fe(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. 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 V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. 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 Fe(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms 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 four equivalent Fe(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. In the second V site, V(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 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 two equivalent V(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. 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 Fe(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. 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 V(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. There are two inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 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 Fe(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the second Fe site, Fe(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form FeO6 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 V(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 Fe(2) atom. In the second O site, O(2) is bonded to one Li(4), one W(1), and two equivalent Fe(1) atoms to form distorted corner-sharing OLiFe2W tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Fe(1) atoms to form corner-sharing OLiVFe2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Fe(2) atom to form corner-sharing OLiV2Fe tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one W(1), and one Fe(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one W(2), and two equivalent Fe(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one W(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one W(2), and one Fe(2) atom to form distorted OLiVFeW trigonal pyramids that share corners with two equivalent O(5)LiV2Fe tetrahedra,  a cornercorner with one O(9)LiVFeW trigonal pyramid, and  an edgeedge with one O(9)LiVFeW trigonal pyramid. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Fe(2) atom. 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 Fe(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one W(2) atom.
Li4V3Fe3(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 V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. The Li(1)-O(12) bond length is 2.08 Å. The Li(1)-O(3) bond length is 2.04 Å. Both Li(1)-O(9) bond lengths are 2.01 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 Fe(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. The Li(2)-O(5) bond length is 1.85 Å. The Li(2)-O(7) bond length is 2.05 Å. Both Li(2)-O(11) bond lengths are 2.07 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 V(1)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-68°. The Li(3)-O(4) bond length is 1.89 Å. The Li(3)-O(8) bond length is 2.07 Å. Both Li(3)-O(1) bond lengths are 2.06 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 Fe(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-65°. The Li(4)-O(10) bond length is 1.98 Å. The Li(4)-O(2) bond length is 2.01 Å. Both Li(4)-O(6) bond lengths are 2.05 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms 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 four equivalent Fe(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. The V(1)-O(3) bond length is 1.84 Å. The V(1)-O(4) bond length is 1.87 Å. Both V(1)-O(11) bond lengths are 2.22 Å. Both V(1)-O(6) bond lengths are 1.96 Å. In the second V site, V(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 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 two equivalent V(2)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The V(2)-O(1) bond length is 2.19 Å. The V(2)-O(10) bond length is 1.98 Å. The V(2)-O(12) bond length is 2.10 Å. The V(2)-O(5) bond length is 1.98 Å. The V(2)-O(8) bond length is 2.17 Å. The V(2)-O(9) bond length is 1.99 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 Fe(2)O6 octahedra, corners with four equivalent V(2)O6 octahedra, corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The W(1)-O(2) bond length is 1.95 Å. The W(1)-O(8) bond length is 1.99 Å. Both W(1)-O(1) bond lengths are 1.91 Å. Both W(1)-O(6) bond lengths are 2.06 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 V(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. The W(2)-O(12) bond length is 2.08 Å. The W(2)-O(7) bond length is 1.88 Å. Both W(2)-O(11) bond lengths are 1.94 Å. Both W(2)-O(9) bond lengths are 2.03 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(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 FeO6 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 Fe(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The Fe(1)-O(11) bond length is 2.22 Å. The Fe(1)-O(2) bond length is 2.14 Å. The Fe(1)-O(3) bond length is 2.07 Å. The Fe(1)-O(4) bond length is 2.01 Å. The Fe(1)-O(6) bond length is 2.25 Å. The Fe(1)-O(7) bond length is 2.21 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form FeO6 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 V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. The Fe(2)-O(10) bond length is 2.02 Å. The Fe(2)-O(5) bond length is 2.00 Å. Both Fe(2)-O(1) bond lengths are 2.22 Å. Both Fe(2)-O(9) bond lengths are 2.22 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 Fe(2) atom. In the second O site, O(2) is bonded to one Li(4), one W(1), and two equivalent Fe(1) atoms to form distorted corner-sharing OLiFe2W tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Fe(1) atoms to form corner-sharing OLiVFe2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Fe(2) atom to form corner-sharing OLiV2Fe tetrahedra. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one V(1), one W(1), and one Fe(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one W(2), and two equivalent Fe(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one W(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one V(2), one W(2), and one Fe(2) atom to form distorted OLiVFeW trigonal pyramids that share corners with two equivalent O(5)LiV2Fe tetrahedra,  a cornercorner with one O(9)LiVFeW trigonal pyramid, and  an edgeedge with one O(9)LiVFeW trigonal pyramid. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Fe(2) atom. 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 Fe(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(2), and one W(2) atom.