Li2MnBr4 crystallizes in the tetragonal P4_122 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with two equivalent Li(2)Br6 octahedra, corners with four equivalent Mn(1)Br6 octahedra, edges with two equivalent Li(1)Br6 octahedra, edges with two equivalent Mn(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. 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 two equivalent Li(1)Br6 octahedra, edges with two equivalent Li(2)Br6 octahedra, edges with four equivalent Li(1)Br6 octahedra, and edges with four equivalent Mn(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 4°. Mn(1) is bonded to two equivalent Br(1) and four equivalent Br(2) atoms to form MnBr6 octahedra that share corners with four equivalent Li(1)Br6 octahedra, edges with two equivalent Li(1)Br6 octahedra, edges with two equivalent Mn(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of edge and corner-sharing BrLi4Mn square pyramids. In the second Br site, Br(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms.
Li2MnBr4 crystallizes in the tetragonal P4_122 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent Br(2) and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with two equivalent Li(2)Br6 octahedra, corners with four equivalent Mn(1)Br6 octahedra, edges with two equivalent Li(1)Br6 octahedra, edges with two equivalent Mn(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Li(1)-Br(2) bond lengths are 2.10 Å. There are two shorter (2.06 Å) and two longer (2.10 Å) Li(1)-Br(1) bond lengths. 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 two equivalent Li(1)Br6 octahedra, edges with two equivalent Li(2)Br6 octahedra, edges with four equivalent Li(1)Br6 octahedra, and edges with four equivalent Mn(1)Br6 octahedra. The corner-sharing octahedral tilt angles are 4°. Both Li(2)-Br(2) bond lengths are 2.20 Å. There are two shorter (2.02 Å) and two longer (2.19 Å) Li(2)-Br(1) bond lengths. Mn(1) is bonded to two equivalent Br(1) and four equivalent Br(2) atoms to form MnBr6 octahedra that share corners with four equivalent Li(1)Br6 octahedra, edges with two equivalent Li(1)Br6 octahedra, edges with two equivalent Mn(1)Br6 octahedra, and edges with four equivalent Li(2)Br6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. Both Mn(1)-Br(1) bond lengths are 2.20 Å. There are two shorter (2.17 Å) and two longer (2.23 Å) Mn(1)-Br(2) bond lengths. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded to two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form a mixture of edge and corner-sharing BrLi4Mn square pyramids. In the second Br site, Br(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms.