CuIn2Se3I crystallizes in the monoclinic Cm space group. Cu(1) is bonded to one Se(2), two equivalent Se(3), and one I(1) atom to form CuSe3I tetrahedra that share corners with two equivalent Cu(1)Se3I tetrahedra, corners with three equivalent In(1)Se3I tetrahedra, and corners with four equivalent In(2)Se4 tetrahedra. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Se(3), two equivalent Se(1), and one I(1) atom to form InSe3I tetrahedra that share corners with two equivalent In(1)Se3I tetrahedra, corners with three equivalent Cu(1)Se3I tetrahedra, and corners with three equivalent In(2)Se4 tetrahedra. In the second In site, In(2) is bonded to one Se(1), one Se(3), and two equivalent Se(2) atoms to form InSe4 tetrahedra that share corners with two equivalent In(2)Se4 tetrahedra, corners with three equivalent In(1)Se3I tetrahedra, and corners with four equivalent Cu(1)Se3I tetrahedra. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(1) atoms. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent In(2) atoms. In the third Se site, Se(3) is bonded to two equivalent Cu(1), one In(1), and one In(2) atom to form corner-sharing SeIn2Cu2 tetrahedra. I(1) is bonded in a water-like geometry to one Cu(1) and one In(1) atom.
CuIn2Se3I crystallizes in the monoclinic Cm space group. Cu(1) is bonded to one Se(2), two equivalent Se(3), and one I(1) atom to form CuSe3I tetrahedra that share corners with two equivalent Cu(1)Se3I tetrahedra, corners with three equivalent In(1)Se3I tetrahedra, and corners with four equivalent In(2)Se4 tetrahedra. The Cu(1)-Se(2) bond length is 2.44 Å. Both Cu(1)-Se(3) bond lengths are 2.47 Å. The Cu(1)-I(1) bond length is 2.65 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to one Se(3), two equivalent Se(1), and one I(1) atom to form InSe3I tetrahedra that share corners with two equivalent In(1)Se3I tetrahedra, corners with three equivalent Cu(1)Se3I tetrahedra, and corners with three equivalent In(2)Se4 tetrahedra. The In(1)-Se(3) bond length is 2.64 Å. Both In(1)-Se(1) bond lengths are 2.66 Å. The In(1)-I(1) bond length is 2.77 Å. In the second In site, In(2) is bonded to one Se(1), one Se(3), and two equivalent Se(2) atoms to form InSe4 tetrahedra that share corners with two equivalent In(2)Se4 tetrahedra, corners with three equivalent In(1)Se3I tetrahedra, and corners with four equivalent Cu(1)Se3I tetrahedra. The In(2)-Se(1) bond length is 2.70 Å. The In(2)-Se(3) bond length is 2.69 Å. Both In(2)-Se(2) bond lengths are 2.63 Å. There are three inequivalent Se sites. In the first Se site, Se(1) is bonded in a trigonal non-coplanar geometry to one In(2) and two equivalent In(1) atoms. In the second Se site, Se(2) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent In(2) atoms. In the third Se site, Se(3) is bonded to two equivalent Cu(1), one In(1), and one In(2) atom to form corner-sharing SeIn2Cu2 tetrahedra. I(1) is bonded in a water-like geometry to one Cu(1) and one In(1) atom.