KV(O4I)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one O(3), one O(8), two equivalent O(2), two equivalent O(6), and three equivalent O(1) atoms. V(1) is bonded in a distorted trigonal bipyramidal geometry to one O(2), one O(3), one O(5), one O(6), and one O(7) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to three equivalent K(1) and one I(2) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one K(1), one V(1), and one I(2) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one I(1) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to two equivalent K(1), one V(1), and one I(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(1) and one I(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent I(1) atoms. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(4), one O(7), and two equivalent O(8) atoms. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), and one O(6) atom.
KV(O4I)2 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one O(3), one O(8), two equivalent O(2), two equivalent O(6), and three equivalent O(1) atoms. The K(1)-O(3) bond length is 2.78 Å. The K(1)-O(8) bond length is 2.81 Å. There is one shorter (2.90 Å) and one longer (3.29 Å) K(1)-O(2) bond length. There is one shorter (3.00 Å) and one longer (3.24 Å) K(1)-O(6) bond length. There are a spread of K(1)-O(1) bond distances ranging from 2.80-3.08 Å. V(1) is bonded in a distorted trigonal bipyramidal geometry to one O(2), one O(3), one O(5), one O(6), and one O(7) atom. The V(1)-O(2) bond length is 1.64 Å. The V(1)-O(3) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.66 Å. The V(1)-O(6) bond length is 1.96 Å. The V(1)-O(7) bond length is 1.96 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to three equivalent K(1) and one I(2) atom. The O(1)-I(2) bond length is 1.78 Å. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent K(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one K(1), one V(1), and one I(2) atom. The O(3)-I(2) bond length is 1.85 Å. In the fourth O site, O(4) is bonded in a single-bond geometry to one I(1) atom. The O(4)-I(1) bond length is 1.81 Å. In the fifth O site, O(5) is bonded in a single-bond geometry to one V(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to two equivalent K(1), one V(1), and one I(2) atom. The O(6)-I(2) bond length is 1.85 Å. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one V(1) and one I(1) atom. The O(7)-I(1) bond length is 1.87 Å. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one K(1) and two equivalent I(1) atoms. There is one shorter (1.81 Å) and one longer (2.57 Å) O(8)-I(1) bond length. There are two inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one O(4), one O(7), and two equivalent O(8) atoms. In the second I site, I(2) is bonded in a 3-coordinate geometry to one O(1), one O(3), and one O(6) atom.