CsLi3I4 crystallizes in the monoclinic Pm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to two equivalent I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(7) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent I(1), two equivalent I(2), and two equivalent I(5) atoms. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one I(2), one I(3), and two equivalent I(4) atoms to form corner-sharing LiI4 tetrahedra. In the second Li site, Li(2) is bonded to one I(3), one I(5), and two equivalent I(6) atoms to form corner-sharing LiI4 tetrahedra. In the third Li site, Li(3) is bonded to one I(4), one I(8), and two equivalent I(5) atoms to form corner-sharing LiI4 tetrahedra. In the fourth Li site, Li(4) is bonded to one I(4), one I(6), and two equivalent I(7) atoms to form corner-sharing LiI4 tetrahedra. In the fifth Li site, Li(5) is bonded to one I(6), one I(8), and two equivalent I(1) atoms to form corner-sharing LiI4 tetrahedra. In the sixth Li site, Li(6) is bonded to one I(2), one I(7), and two equivalent I(8) atoms to form corner-sharing LiI4 tetrahedra. There are eight inequivalent I sites. In the first I site, I(1) is bonded in a distorted water-like geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Li(5) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one Li(6) atom. In the third I site, I(3) is bonded in a distorted water-like geometry to two equivalent Cs(1), one Li(1), and one Li(2) atom. In the fourth I site, I(4) is bonded to one Li(3), one Li(4), and two equivalent Li(1) atoms to form corner-sharing ILi4 tetrahedra. In the fifth I site, I(5) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(2), one Li(2), and two equivalent Li(3) atoms. In the sixth I site, I(6) is bonded to one Li(4), one Li(5), and two equivalent Li(2) atoms to form corner-sharing ILi4 tetrahedra. In the seventh I site, I(7) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(1), one Li(6), and two equivalent Li(4) atoms. In the eighth I site, I(8) is bonded to one Li(3), one Li(5), and two equivalent Li(6) atoms to form corner-sharing ILi4 tetrahedra.
CsLi3I4 crystallizes in the monoclinic Pm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a body-centered cubic geometry to two equivalent I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(7) atoms. Both Cs(1)-I(1) bond lengths are 4.06 Å. Both Cs(1)-I(2) bond lengths are 4.01 Å. Both Cs(1)-I(3) bond lengths are 3.82 Å. Both Cs(1)-I(7) bond lengths are 3.90 Å. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to two equivalent I(1), two equivalent I(2), and two equivalent I(5) atoms. Both Cs(2)-I(1) bond lengths are 3.93 Å. Both Cs(2)-I(2) bond lengths are 3.93 Å. Both Cs(2)-I(5) bond lengths are 3.90 Å. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one I(2), one I(3), and two equivalent I(4) atoms to form corner-sharing LiI4 tetrahedra. The Li(1)-I(2) bond length is 2.83 Å. The Li(1)-I(3) bond length is 2.76 Å. Both Li(1)-I(4) bond lengths are 2.80 Å. In the second Li site, Li(2) is bonded to one I(3), one I(5), and two equivalent I(6) atoms to form corner-sharing LiI4 tetrahedra. The Li(2)-I(3) bond length is 2.72 Å. The Li(2)-I(5) bond length is 2.77 Å. Both Li(2)-I(6) bond lengths are 2.78 Å. In the third Li site, Li(3) is bonded to one I(4), one I(8), and two equivalent I(5) atoms to form corner-sharing LiI4 tetrahedra. The Li(3)-I(4) bond length is 2.79 Å. The Li(3)-I(8) bond length is 2.78 Å. Both Li(3)-I(5) bond lengths are 2.80 Å. In the fourth Li site, Li(4) is bonded to one I(4), one I(6), and two equivalent I(7) atoms to form corner-sharing LiI4 tetrahedra. The Li(4)-I(4) bond length is 2.75 Å. The Li(4)-I(6) bond length is 2.75 Å. Both Li(4)-I(7) bond lengths are 2.78 Å. In the fifth Li site, Li(5) is bonded to one I(6), one I(8), and two equivalent I(1) atoms to form corner-sharing LiI4 tetrahedra. The Li(5)-I(6) bond length is 2.74 Å. The Li(5)-I(8) bond length is 2.76 Å. Both Li(5)-I(1) bond lengths are 2.82 Å. In the sixth Li site, Li(6) is bonded to one I(2), one I(7), and two equivalent I(8) atoms to form corner-sharing LiI4 tetrahedra. The Li(6)-I(2) bond length is 2.79 Å. The Li(6)-I(7) bond length is 2.76 Å. Both Li(6)-I(8) bond lengths are 2.78 Å. There are eight inequivalent I sites. In the first I site, I(1) is bonded in a distorted water-like geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Li(5) atoms. In the second I site, I(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), one Li(1), and one Li(6) atom. In the third I site, I(3) is bonded in a distorted water-like geometry to two equivalent Cs(1), one Li(1), and one Li(2) atom. In the fourth I site, I(4) is bonded to one Li(3), one Li(4), and two equivalent Li(1) atoms to form corner-sharing ILi4 tetrahedra. In the fifth I site, I(5) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(2), one Li(2), and two equivalent Li(3) atoms. In the sixth I site, I(6) is bonded to one Li(4), one Li(5), and two equivalent Li(2) atoms to form corner-sharing ILi4 tetrahedra. In the seventh I site, I(7) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Cs(1), one Li(6), and two equivalent Li(4) atoms. In the eighth I site, I(8) is bonded to one Li(3), one Li(5), and two equivalent Li(6) atoms to form corner-sharing ILi4 tetrahedra.