Li2VFe3O8 is Hausmannite-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-64°. In the second Li site, Li(2) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. V(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO6 octahedra that share corners with two equivalent Fe(2)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 Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the second Fe site, Fe(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(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°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded to one Li(1), one V(1), one Fe(1), and one Fe(2) atom to form distorted OLiVFe2 trigonal pyramids that share  a cornercorner with one O(6)LiVFe2 tetrahedra, corners with two equivalent O(4)LiFe3 tetrahedra,  a cornercorner with one O(2)LiVFe2 trigonal pyramid,  an edgeedge with one O(6)LiVFe2 tetrahedra, and  an edgeedge with one O(2)LiVFe2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(2), one Fe(2), and two equivalent Fe(1) atoms to form corner-sharing OLiFe3 tetrahedra. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), and two equivalent Fe(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one V(1), and two equivalent Fe(1) atoms to form distorted OLiVFe2 tetrahedra that share corners with two equivalent O(4)LiFe3 tetrahedra, corners with two equivalent O(2)LiVFe2 trigonal pyramids, and edges with two equivalent O(2)LiVFe2 trigonal pyramids.
Li2VFe3O8 is Hausmannite-derived structured and crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(6), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra, and corners with six equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-64°. The Li(1)-O(3) bond length is 1.94 Å. The Li(1)-O(6) bond length is 1.97 Å. Both Li(1)-O(2) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded to one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra,  an edgeedge with one Fe(2)O6 octahedra, and edges with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-67°. The Li(2)-O(4) bond length is 1.80 Å. The Li(2)-O(5) bond length is 1.99 Å. Both Li(2)-O(1) bond lengths are 2.03 Å. V(1) is bonded to one O(5), one O(6), two equivalent O(1), and two equivalent O(2) atoms to form distorted VO6 octahedra that share corners with two equivalent Fe(2)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 Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-53°. The V(1)-O(5) bond length is 1.85 Å. The V(1)-O(6) bond length is 2.00 Å. Both V(1)-O(1) bond lengths are 1.84 Å. Both V(1)-O(2) bond lengths are 2.07 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-53°. The Fe(1)-O(1) bond length is 2.19 Å. The Fe(1)-O(2) bond length is 1.99 Å. The Fe(1)-O(3) bond length is 1.96 Å. The Fe(1)-O(4) bond length is 1.95 Å. The Fe(1)-O(5) bond length is 2.14 Å. The Fe(1)-O(6) bond length is 2.03 Å. In the second Fe site, Fe(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form FeO6 octahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(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 Fe(2)-O(3) bond length is 1.91 Å. The Fe(2)-O(4) bond length is 1.91 Å. Both Fe(2)-O(1) bond lengths are 2.10 Å. Both Fe(2)-O(2) bond lengths are 1.95 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded to one Li(1), one V(1), one Fe(1), and one Fe(2) atom to form distorted OLiVFe2 trigonal pyramids that share  a cornercorner with one O(6)LiVFe2 tetrahedra, corners with two equivalent O(4)LiFe3 tetrahedra,  a cornercorner with one O(2)LiVFe2 trigonal pyramid,  an edgeedge with one O(6)LiVFe2 tetrahedra, and  an edgeedge with one O(2)LiVFe2 trigonal pyramid. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Fe(2), and two equivalent Fe(1) atoms. In the fourth O site, O(4) is bonded to one Li(2), one Fe(2), and two equivalent Fe(1) atoms to form corner-sharing OLiFe3 tetrahedra. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one V(1), and two equivalent Fe(1) atoms. In the sixth O site, O(6) is bonded to one Li(1), one V(1), and two equivalent Fe(1) atoms to form distorted OLiVFe2 tetrahedra that share corners with two equivalent O(4)LiFe3 tetrahedra, corners with two equivalent O(2)LiVFe2 trigonal pyramids, and edges with two equivalent O(2)LiVFe2 trigonal pyramids.