KOICl4 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one Cl(2), one Cl(4), two equivalent Cl(1), and three equivalent Cl(3) atoms. O(1) is bonded in a bent 120 degrees geometry to two equivalent K(1) atoms. I(1) is bonded in a rectangular see-saw-like geometry to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to two equivalent K(1) and one I(1) atom. In the second Cl site, Cl(2) is bonded in a water-like geometry to one K(1) and one I(1) atom. In the third Cl site, Cl(3) is bonded to three equivalent K(1) and one I(1) atom to form a mixture of corner and edge-sharing ClK3I trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a water-like geometry to one K(1) and one I(1) atom.
KOICl4 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one Cl(2), one Cl(4), two equivalent Cl(1), and three equivalent Cl(3) atoms. There is one shorter (2.84 Å) and one longer (2.93 Å) K(1)-O(1) bond length. The K(1)-Cl(2) bond length is 3.24 Å. The K(1)-Cl(4) bond length is 3.19 Å. There is one shorter (3.41 Å) and one longer (3.61 Å) K(1)-Cl(1) bond length. There are a spread of K(1)-Cl(3) bond distances ranging from 3.24-3.36 Å. O(1) is bonded in a bent 120 degrees geometry to two equivalent K(1) atoms. I(1) is bonded in a rectangular see-saw-like geometry to one Cl(1), one Cl(2), one Cl(3), and one Cl(4) atom. The I(1)-Cl(1) bond length is 2.53 Å. The I(1)-Cl(2) bond length is 2.51 Å. The I(1)-Cl(3) bond length is 2.62 Å. The I(1)-Cl(4) bond length is 2.45 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted T-shaped geometry to two equivalent K(1) and one I(1) atom. In the second Cl site, Cl(2) is bonded in a water-like geometry to one K(1) and one I(1) atom. In the third Cl site, Cl(3) is bonded to three equivalent K(1) and one I(1) atom to form a mixture of corner and edge-sharing ClK3I trigonal pyramids. In the fourth Cl site, Cl(4) is bonded in a water-like geometry to one K(1) and one I(1) atom.