K2AgI3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one I(2), three equivalent I(1), and three equivalent I(3) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to one I(1), two equivalent I(3), and four equivalent I(2) atoms. Ag(1) is bonded to one I(2), one I(3), and two equivalent I(1) atoms to form corner-sharing AgI4 tetrahedra. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to one K(2), three equivalent K(1), and two equivalent Ag(1) atoms. In the second I site, I(2) is bonded to one K(1), four equivalent K(2), and one Ag(1) atom to form a mixture of edge, face, and corner-sharing IK5Ag octahedra. The corner-sharing octahedral tilt angles range from 24-56°. In the third I site, I(3) is bonded to two equivalent K(2), three equivalent K(1), and one Ag(1) atom to form a mixture of distorted edge, face, and corner-sharing IK5Ag octahedra. The corner-sharing octahedral tilt angles range from 51-56°.
K2AgI3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one I(2), three equivalent I(1), and three equivalent I(3) atoms. The K(1)-I(2) bond length is 3.65 Å. There are two shorter (3.61 Å) and one longer (3.78 Å) K(1)-I(1) bond length. There are two shorter (3.50 Å) and one longer (3.77 Å) K(1)-I(3) bond length. In the second K site, K(2) is bonded in a 7-coordinate geometry to one I(1), two equivalent I(3), and four equivalent I(2) atoms. The K(2)-I(1) bond length is 3.77 Å. Both K(2)-I(3) bond lengths are 3.69 Å. There are two shorter (3.60 Å) and two longer (3.61 Å) K(2)-I(2) bond lengths. Ag(1) is bonded to one I(2), one I(3), and two equivalent I(1) atoms to form corner-sharing AgI4 tetrahedra. The Ag(1)-I(2) bond length is 2.85 Å. The Ag(1)-I(3) bond length is 2.85 Å. Both Ag(1)-I(1) bond lengths are 2.87 Å. There are three inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to one K(2), three equivalent K(1), and two equivalent Ag(1) atoms. In the second I site, I(2) is bonded to one K(1), four equivalent K(2), and one Ag(1) atom to form a mixture of edge, face, and corner-sharing IK5Ag octahedra. The corner-sharing octahedral tilt angles range from 24-56°. In the third I site, I(3) is bonded to two equivalent K(2), three equivalent K(1), and one Ag(1) atom to form a mixture of distorted edge, face, and corner-sharing IK5Ag octahedra. The corner-sharing octahedral tilt angles range from 51-56°.