Li2MnBr4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to one Br(2), one Br(3), and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with six equivalent Li(1)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 range from 1-6°. Mn(1) is bonded to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(3) atoms to form MnBr6 octahedra that share corners with four equivalent Mn(1)Br6 octahedra and edges with eight equivalent Li(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Li(1) 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 square co-planar geometry to two equivalent Li(1) and two equivalent Mn(1) atoms. In the third Br site, Br(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Mn(1) atoms.
Li2MnBr4 crystallizes in the orthorhombic Imm2 space group. Li(1) is bonded to one Br(2), one Br(3), and four equivalent Br(1) atoms to form LiBr6 octahedra that share corners with six equivalent Li(1)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 range from 1-6°. The Li(1)-Br(2) bond length is 2.72 Å. The Li(1)-Br(3) bond length is 2.75 Å. There are three shorter (2.77 Å) and one longer (2.78 Å) Li(1)-Br(1) bond length. Mn(1) is bonded to two equivalent Br(1), two equivalent Br(2), and two equivalent Br(3) atoms to form MnBr6 octahedra that share corners with four equivalent Mn(1)Br6 octahedra and edges with eight equivalent Li(1)Br6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Mn(1)-Br(1) bond lengths are 2.60 Å. There is one shorter (2.71 Å) and one longer (2.83 Å) Mn(1)-Br(2) bond length. Both Mn(1)-Br(3) bond lengths are 2.77 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded to four equivalent Li(1) 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 square co-planar geometry to two equivalent Li(1) and two equivalent Mn(1) atoms. In the third Br site, Br(3) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Mn(1) atoms.