Cs3LiBr4 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent Br(2) and four equivalent Br(1) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Br(3), two equivalent Br(2), and three equivalent Br(1) atoms. Li(1) is bonded to two equivalent Br(1) and two equivalent Br(3) atoms to form corner-sharing LiBr4 tetrahedra. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1), three equivalent Cs(2), and one Li(1) atom. In the second Br site, Br(2) is bonded to two equivalent Cs(1) and four equivalent Cs(2) atoms to form face-sharing BrCs6 octahedra. In the third Br site, Br(3) is bonded in a 4-coordinate geometry to two equivalent Cs(2) and two equivalent Li(1) atoms.
Cs3LiBr4 crystallizes in the orthorhombic C222_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent Br(2) and four equivalent Br(1) atoms. Both Cs(1)-Br(2) bond lengths are 3.68 Å. There are two shorter (3.83 Å) and two longer (4.21 Å) Cs(1)-Br(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Br(3), two equivalent Br(2), and three equivalent Br(1) atoms. The Cs(2)-Br(3) bond length is 3.61 Å. Both Cs(2)-Br(2) bond lengths are 3.54 Å. There are a spread of Cs(2)-Br(1) bond distances ranging from 3.61-3.87 Å. Li(1) is bonded to two equivalent Br(1) and two equivalent Br(3) atoms to form corner-sharing LiBr4 tetrahedra. Both Li(1)-Br(1) bond lengths are 2.57 Å. Both Li(1)-Br(3) bond lengths are 2.62 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1), three equivalent Cs(2), and one Li(1) atom. In the second Br site, Br(2) is bonded to two equivalent Cs(1) and four equivalent Cs(2) atoms to form face-sharing BrCs6 octahedra. In the third Br site, Br(3) is bonded in a 4-coordinate geometry to two equivalent Cs(2) and two equivalent Li(1) atoms.