K5Au(OI)2 crystallizes in the orthorhombic Pbam space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. In the second K site, K(2) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. In the third K site, K(3) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. Au(1) is bonded in a linear geometry to two equivalent O(1) atoms. O(1) is bonded to one K(3), two equivalent K(1), two equivalent K(2), and one Au(1) atom to form corner-sharing OK5Au octahedra. The corner-sharing octahedral tilt angles range from 0-12°. I(1) is bonded in a 10-coordinate geometry to two equivalent K(3), four equivalent K(1), and four equivalent K(2) atoms.
K5Au(OI)2 crystallizes in the orthorhombic Pbam space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. Both K(1)-O(1) bond lengths are 2.80 Å. There are a spread of K(1)-I(1) bond distances ranging from 3.58-3.87 Å. In the second K site, K(2) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. There is one shorter (2.70 Å) and one longer (2.76 Å) K(2)-O(1) bond length. There are two shorter (3.60 Å) and two longer (3.74 Å) K(2)-I(1) bond lengths. In the third K site, K(3) is bonded in a distorted linear geometry to two equivalent O(1) and four equivalent I(1) atoms. Both K(3)-O(1) bond lengths are 2.82 Å. All K(3)-I(1) bond lengths are 3.66 Å. Au(1) is bonded in a linear geometry to two equivalent O(1) atoms. Both Au(1)-O(1) bond lengths are 2.06 Å. O(1) is bonded to one K(3), two equivalent K(1), two equivalent K(2), and one Au(1) atom to form corner-sharing OK5Au octahedra. The corner-sharing octahedral tilt angles range from 0-12°. I(1) is bonded in a 10-coordinate geometry to two equivalent K(3), four equivalent K(1), and four equivalent K(2) atoms.