Li2FeBr4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Br(1) and two equivalent Br(2) atoms to form LiBr4 tetrahedra that share corners with six equivalent Li(2)Br6 octahedra and corners with six equivalent Fe(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 56-59°. In the second Li site, Li(2) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with six equivalent Li(1)Br4 tetrahedra, edges with two equivalent Li(2)Br6 octahedra, and edges with four equivalent Fe(1)Br6 octahedra. Fe(1) is bonded to two equivalent Br(1) and four equivalent Br(2) atoms to form FeBr6 octahedra that share corners with six equivalent Li(1)Br4 tetrahedra, edges with two equivalent Fe(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing BrLi3Fe trigonal pyramids. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Fe(1) atoms.
Li2FeBr4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Br(1) and two equivalent Br(2) atoms to form LiBr4 tetrahedra that share corners with six equivalent Li(2)Br6 octahedra and corners with six equivalent Fe(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 56-59°. Both Li(1)-Br(1) bond lengths are 2.52 Å. Both Li(1)-Br(2) bond lengths are 2.59 Å. In the second Li site, Li(2) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with six equivalent Li(1)Br4 tetrahedra, edges with two equivalent Li(2)Br6 octahedra, and edges with four equivalent Fe(1)Br6 octahedra. Both Li(2)-Br(2) bond lengths are 2.72 Å. All Li(2)-Br(1) bond lengths are 2.73 Å. Fe(1) is bonded to two equivalent Br(1) and four equivalent Br(2) atoms to form FeBr6 octahedra that share corners with six equivalent Li(1)Br4 tetrahedra, edges with two equivalent Fe(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. Both Fe(1)-Br(1) bond lengths are 2.60 Å. All Fe(1)-Br(2) bond lengths are 2.67 Å. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to one Li(1), two equivalent Li(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing BrLi3Fe trigonal pyramids. In the second Br site, Br(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Fe(1) atoms.