CsZr6BI14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent I(4), two equivalent I(5), four equivalent I(1), and four equivalent I(3) atoms to form CsI12 cuboctahedra that share corners with eight equivalent Zr(2)BI5 octahedra and edges with four equivalent Zr(2)BI5 octahedra. The corner-sharing octahedral tilt angles range from 36-42°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to one B(1), one I(4), two equivalent I(1), and two equivalent I(3) atoms. In the second Zr site, Zr(2) is bonded to one B(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form distorted ZrBI5 octahedra that share corners with two equivalent Cs(1)I12 cuboctahedra, corners with two equivalent Zr(2)BI5 octahedra,  an edgeedge with one Cs(1)I12 cuboctahedra, and edges with two equivalent Zr(2)BI5 octahedra. The corner-sharing octahedral tilt angles range from 0-45°. B(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are five inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the second I site, I(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the third I site, I(3) is bonded in a 2-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the fourth I site, I(4) is bonded in a distorted rectangular see-saw-like geometry to one Cs(1), one Zr(1), and two equivalent Zr(2) atoms. In the fifth I site, I(5) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent Zr(2) atoms.
CsZr6BI14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent I(4), two equivalent I(5), four equivalent I(1), and four equivalent I(3) atoms to form CsI12 cuboctahedra that share corners with eight equivalent Zr(2)BI5 octahedra and edges with four equivalent Zr(2)BI5 octahedra. The corner-sharing octahedral tilt angles range from 36-42°. Both Cs(1)-I(4) bond lengths are 3.95 Å. Both Cs(1)-I(5) bond lengths are 4.08 Å. All Cs(1)-I(1) bond lengths are 4.11 Å. All Cs(1)-I(3) bond lengths are 4.43 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 5-coordinate geometry to one B(1), one I(4), two equivalent I(1), and two equivalent I(3) atoms. The Zr(1)-B(1) bond length is 2.34 Å. The Zr(1)-I(4) bond length is 3.74 Å. Both Zr(1)-I(1) bond lengths are 2.89 Å. Both Zr(1)-I(3) bond lengths are 2.89 Å. In the second Zr site, Zr(2) is bonded to one B(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form distorted ZrBI5 octahedra that share corners with two equivalent Cs(1)I12 cuboctahedra, corners with two equivalent Zr(2)BI5 octahedra,  an edgeedge with one Cs(1)I12 cuboctahedra, and edges with two equivalent Zr(2)BI5 octahedra. The corner-sharing octahedral tilt angles range from 0-45°. The Zr(2)-B(1) bond length is 2.42 Å. The Zr(2)-I(1) bond length is 2.92 Å. The Zr(2)-I(2) bond length is 3.25 Å. The Zr(2)-I(3) bond length is 2.93 Å. The Zr(2)-I(4) bond length is 2.95 Å. The Zr(2)-I(5) bond length is 2.88 Å. B(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are five inequivalent I sites. In the first I site, I(1) is bonded in a 3-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the second I site, I(2) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the third I site, I(3) is bonded in a 2-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the fourth I site, I(4) is bonded in a distorted rectangular see-saw-like geometry to one Cs(1), one Zr(1), and two equivalent Zr(2) atoms. In the fifth I site, I(5) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent Zr(2) atoms.