Li2NbFe3O8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with three equivalent Nb(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 58-60°. Nb(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. In the second Fe site, Fe(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form distorted OLiFe3 tetrahedra that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(2)LiNbFe2 trigonal pyramid, and edges with two equivalent O(3)LiNbFe2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Nb(1), and two equivalent Fe(1) atoms to form distorted OLiNbFe2 trigonal pyramids that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(1)LiFe3 tetrahedra, and edges with two equivalent O(3)LiNbFe2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Nb(1), one Fe(1), and one Fe(2) atom to form distorted OLiNbFe2 trigonal pyramids that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(1)LiFe3 tetrahedra,  an edgeedge with one O(2)LiNbFe2 trigonal pyramid, and  an edgeedge with one O(3)LiNbFe2 trigonal pyramid.
Li2NbFe3O8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with three equivalent Nb(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 58-60°. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(2) bond length is 2.04 Å. Both Li(1)-O(3) bond lengths are 2.03 Å. Nb(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form NbO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. Both Nb(1)-O(2) bond lengths are 2.03 Å. All Nb(1)-O(3) bond lengths are 2.02 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, and edges with two equivalent Fe(2)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.01 Å. Both Fe(1)-O(2) bond lengths are 2.08 Å. Both Fe(1)-O(3) bond lengths are 2.08 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. Both Fe(2)-O(1) bond lengths are 2.00 Å. All Fe(2)-O(3) bond lengths are 2.08 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Fe(2), and two equivalent Fe(1) atoms to form distorted OLiFe3 tetrahedra that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(2)LiNbFe2 trigonal pyramid, and edges with two equivalent O(3)LiNbFe2 trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Nb(1), and two equivalent Fe(1) atoms to form distorted OLiNbFe2 trigonal pyramids that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(1)LiFe3 tetrahedra, and edges with two equivalent O(3)LiNbFe2 trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), one Nb(1), one Fe(1), and one Fe(2) atom to form distorted OLiNbFe2 trigonal pyramids that share corners with three equivalent O(1)LiFe3 tetrahedra, corners with three equivalent O(2)LiNbFe2 trigonal pyramids, corners with six equivalent O(3)LiNbFe2 trigonal pyramids,  an edgeedge with one O(1)LiFe3 tetrahedra,  an edgeedge with one O(2)LiNbFe2 trigonal pyramid, and  an edgeedge with one O(3)LiNbFe2 trigonal pyramid.