AlN5I3 crystallizes in the orthorhombic Cmcm space group. Al(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form AlN5 trigonal bipyramids that share corners with five equivalent I(1)N5 square pyramids. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one Al(1), one I(1), and two equivalent I(2) atoms. In the second N site, N(2) is bonded in a linear geometry to one Al(1) and one I(1) atom. In the third N site, N(3) is bonded in a distorted linear geometry to one Al(1) and one I(1) atom. There are two inequivalent I sites. In the first I site, I(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form distorted IN5 square pyramids that share corners with five equivalent Al(1)N5 trigonal bipyramids. In the second I site, I(2) is bonded in a distorted linear geometry to two equivalent N(1) atoms.
AlN5I3 crystallizes in the orthorhombic Cmcm space group. Al(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form AlN5 trigonal bipyramids that share corners with five equivalent I(1)N5 square pyramids. The Al(1)-N(2) bond length is 1.91 Å. Both Al(1)-N(1) bond lengths are 1.93 Å. Both Al(1)-N(3) bond lengths are 1.95 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a distorted single-bond geometry to one Al(1), one I(1), and two equivalent I(2) atoms. The N(1)-I(1) bond length is 2.27 Å. Both N(1)-I(2) bond lengths are 2.37 Å. In the second N site, N(2) is bonded in a linear geometry to one Al(1) and one I(1) atom. The N(2)-I(1) bond length is 2.00 Å. In the third N site, N(3) is bonded in a distorted linear geometry to one Al(1) and one I(1) atom. The N(3)-I(1) bond length is 2.05 Å. There are two inequivalent I sites. In the first I site, I(1) is bonded to one N(2), two equivalent N(1), and two equivalent N(3) atoms to form distorted IN5 square pyramids that share corners with five equivalent Al(1)N5 trigonal bipyramids. In the second I site, I(2) is bonded in a distorted linear geometry to two equivalent N(1) atoms.