CsLi3Cl4 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 4-coordinate geometry to four equivalent Cl(1) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1) and four equivalent Cl(2) atoms to form a mixture of distorted edge and corner-sharing LiCl5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one Cl(1), two equivalent Cl(3), and two equivalent Cl(4) atoms to form a mixture of edge and corner-sharing LiCl5 trigonal bipyramids. In the third Li site, Li(3) is bonded to two equivalent Cl(4) and three equivalent Cl(3) atoms to form a mixture of distorted edge and corner-sharing LiCl5 trigonal bipyramids. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Cs(1), one Li(1), and one Li(2) atom to form distorted ClCs4Li2 octahedra that share corners with four equivalent Cl(1)Cs4Li2 octahedra, corners with two equivalent Cl(3)Li5 trigonal bipyramids, and edges with four equivalent Cl(1)Cs4Li2 octahedra. The corner-sharing octahedral tilt angles are 4°. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to four equivalent Li(1) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Li(2) and three equivalent Li(3) atoms to form distorted ClLi5 trigonal bipyramids that share corners with two equivalent Cl(1)Cs4Li2 octahedra, corners with four equivalent Cl(3)Li5 trigonal bipyramids, and edges with two equivalent Cl(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 75°. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent Li(3) atoms.
CsLi3Cl4 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 4-coordinate geometry to four equivalent Cl(1) atoms. All Cs(1)-Cl(1) bond lengths are 3.49 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one Cl(1) and four equivalent Cl(2) atoms to form a mixture of distorted edge and corner-sharing LiCl5 trigonal bipyramids. The Li(1)-Cl(1) bond length is 2.40 Å. There are two shorter (2.53 Å) and two longer (2.63 Å) Li(1)-Cl(2) bond lengths. In the second Li site, Li(2) is bonded to one Cl(1), two equivalent Cl(3), and two equivalent Cl(4) atoms to form a mixture of edge and corner-sharing LiCl5 trigonal bipyramids. The Li(2)-Cl(1) bond length is 2.49 Å. Both Li(2)-Cl(3) bond lengths are 2.48 Å. Both Li(2)-Cl(4) bond lengths are 2.57 Å. In the third Li site, Li(3) is bonded to two equivalent Cl(4) and three equivalent Cl(3) atoms to form a mixture of distorted edge and corner-sharing LiCl5 trigonal bipyramids. Both Li(3)-Cl(4) bond lengths are 2.50 Å. There is one shorter (2.39 Å) and two longer (2.58 Å) Li(3)-Cl(3) bond lengths. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Cs(1), one Li(1), and one Li(2) atom to form distorted ClCs4Li2 octahedra that share corners with four equivalent Cl(1)Cs4Li2 octahedra, corners with two equivalent Cl(3)Li5 trigonal bipyramids, and edges with four equivalent Cl(1)Cs4Li2 octahedra. The corner-sharing octahedral tilt angles are 4°. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to four equivalent Li(1) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Li(2) and three equivalent Li(3) atoms to form distorted ClLi5 trigonal bipyramids that share corners with two equivalent Cl(1)Cs4Li2 octahedra, corners with four equivalent Cl(3)Li5 trigonal bipyramids, and edges with two equivalent Cl(3)Li5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 75°. In the fourth Cl site, Cl(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(2) and two equivalent Li(3) atoms.