K(Zr3I7)2 crystallizes in the orthorhombic Cmce space group. K(1) is bonded in an octahedral geometry to two equivalent Zr(2) and four equivalent Zr(1) atoms. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one K(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form a mixture of corner and edge-sharing ZrKI5 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. In the second Zr site, Zr(2) is bonded to one K(1), one I(5), two equivalent I(1), and two equivalent I(3) atoms to form a mixture of corner and edge-sharing ZrKI5 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. There are five inequivalent I sites. In the first I site, I(4) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the second I site, I(5) is bonded in a distorted T-shaped geometry to one Zr(2) and two equivalent Zr(1) atoms. In the third I site, I(1) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom. In the fourth I site, I(2) is bonded in an L-shaped geometry to two equivalent Zr(1) atoms. In the fifth I site, I(3) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom.
K(Zr3I7)2 crystallizes in the orthorhombic Cmce space group. K(1) is bonded in an octahedral geometry to two equivalent Zr(2) and four equivalent Zr(1) atoms. Both K(1)-Zr(2) bond lengths are 2.82 Å. All K(1)-Zr(1) bond lengths are 2.88 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one K(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form a mixture of corner and edge-sharing ZrKI5 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. The Zr(1)-I(1) bond length is 2.94 Å. The Zr(1)-I(2) bond length is 2.91 Å. The Zr(1)-I(3) bond length is 2.91 Å. The Zr(1)-I(4) bond length is 2.95 Å. The Zr(1)-I(5) bond length is 3.05 Å. In the second Zr site, Zr(2) is bonded to one K(1), one I(5), two equivalent I(1), and two equivalent I(3) atoms to form a mixture of corner and edge-sharing ZrKI5 octahedra. The corner-sharing octahedral tilt angles range from 0-48°. The Zr(2)-I(5) bond length is 3.13 Å. Both Zr(2)-I(1) bond lengths are 2.94 Å. Both Zr(2)-I(3) bond lengths are 2.93 Å. There are five inequivalent I sites. In the first I site, I(4) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the second I site, I(5) is bonded in a distorted T-shaped geometry to one Zr(2) and two equivalent Zr(1) atoms. In the third I site, I(1) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom. In the fourth I site, I(2) is bonded in an L-shaped geometry to two equivalent Zr(1) atoms. In the fifth I site, I(3) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom.