Li2MnCl4 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 Cl(1) and two equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with six equivalent Li(2)Cl6 octahedra and corners with six equivalent Mn(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. In the second Li site, Li(2) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with four equivalent Mn(1)Cl6 octahedra. Mn(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form MnCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Mn(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Mn(1) atom.
Li2MnCl4 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 Cl(1) and two equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with six equivalent Li(2)Cl6 octahedra and corners with six equivalent Mn(1)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. Both Li(1)-Cl(1) bond lengths are 2.40 Å. Both Li(1)-Cl(2) bond lengths are 2.35 Å. In the second Li site, Li(2) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form LiCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Li(2)Cl6 octahedra, and edges with four equivalent Mn(1)Cl6 octahedra. Both Li(2)-Cl(1) bond lengths are 2.57 Å. All Li(2)-Cl(2) bond lengths are 2.54 Å. Mn(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form MnCl6 octahedra that share corners with six equivalent Li(1)Cl4 tetrahedra, edges with two equivalent Mn(1)Cl6 octahedra, and edges with four equivalent Li(2)Cl6 octahedra. Both Mn(1)-Cl(2) bond lengths are 2.49 Å. All Mn(1)-Cl(1) bond lengths are 2.56 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Mn(1) atom.