Zr6GeI14 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Ge(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form a mixture of edge and corner-sharing ZrGeI5 octahedra. The corner-sharing octahedral tilt angles range from 0-47°. In the second Zr site, Zr(2) is bonded to one Ge(1), one I(5), two equivalent I(1), and two equivalent I(2) atoms to form a mixture of distorted edge and corner-sharing ZrGeI5 octahedra. The corner-sharing octahedral tilt angles range from 0-46°. Ge(1) is bonded in an octahedral geometry to two equivalent Zr(2) and four equivalent Zr(1) atoms. There are five inequivalent I sites. In the first I site, I(2) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom. In the second I site, I(3) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the third I site, I(4) is bonded in an L-shaped geometry to two equivalent Zr(1) atoms. In the fourth I site, I(5) is bonded in a 3-coordinate geometry to one Zr(2) and two equivalent Zr(1) atoms. In the fifth I site, I(1) is bonded in a distorted L-shaped geometry to one Zr(1) and one Zr(2) atom.
Zr6GeI14 crystallizes in the orthorhombic Cmce space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Ge(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form a mixture of edge and corner-sharing ZrGeI5 octahedra. The corner-sharing octahedral tilt angles range from 0-47°. The Zr(1)-Ge(1) bond length is 2.61 Å. The Zr(1)-I(1) bond length is 2.91 Å. The Zr(1)-I(2) bond length is 2.92 Å. The Zr(1)-I(3) bond length is 3.09 Å. The Zr(1)-I(4) bond length is 2.89 Å. The Zr(1)-I(5) bond length is 2.99 Å. In the second Zr site, Zr(2) is bonded to one Ge(1), one I(5), two equivalent I(1), and two equivalent I(2) atoms to form a mixture of distorted edge and corner-sharing ZrGeI5 octahedra. The corner-sharing octahedral tilt angles range from 0-46°. The Zr(2)-Ge(1) bond length is 2.55 Å. The Zr(2)-I(5) bond length is 3.42 Å. Both Zr(2)-I(1) bond lengths are 2.90 Å. Both Zr(2)-I(2) bond lengths are 2.90 Å. Ge(1) is bonded in an octahedral geometry to two equivalent Zr(2) and four equivalent Zr(1) atoms. There are five inequivalent I sites. In the first I site, I(2) is bonded in an L-shaped geometry to one Zr(1) and one Zr(2) atom. In the second I site, I(3) is bonded in a bent 120 degrees geometry to two equivalent Zr(1) atoms. In the third I site, I(4) is bonded in an L-shaped geometry to two equivalent Zr(1) atoms. In the fourth I site, I(5) is bonded in a 3-coordinate geometry to one Zr(2) and two equivalent Zr(1) atoms. In the fifth I site, I(1) is bonded in a distorted L-shaped geometry to one Zr(1) and one Zr(2) atom.