CsZr6MnI14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent I(3), two equivalent I(4), four equivalent I(1), and four equivalent I(2) atoms to form CsI12 cuboctahedra that share corners with eight equivalent Zr(2)MnI5 octahedra and edges with four equivalent Zr(2)MnI5 octahedra. The corner-sharing octahedral tilt angles range from 38-42°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to one Mn(1), one I(4), two equivalent I(1), and two equivalent I(2) atoms. In the second Zr site, Zr(2) is bonded to one Mn(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form ZrMnI5 octahedra that share corners with two equivalent Cs(1)I12 cuboctahedra, corners with two equivalent Zr(2)MnI5 octahedra,  an edgeedge with one Cs(1)I12 cuboctahedra, and edges with two equivalent Zr(2)MnI5 octahedra. The corner-sharing octahedral tilt angles range from 0-44°. Mn(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 2-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 3-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent Zr(2) atoms. 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 bent 150 degrees geometry to two equivalent Zr(2) atoms.
CsZr6MnI14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent I(3), two equivalent I(4), four equivalent I(1), and four equivalent I(2) atoms to form CsI12 cuboctahedra that share corners with eight equivalent Zr(2)MnI5 octahedra and edges with four equivalent Zr(2)MnI5 octahedra. The corner-sharing octahedral tilt angles range from 38-42°. Both Cs(1)-I(3) bond lengths are 4.13 Å. Both Cs(1)-I(4) bond lengths are 4.03 Å. All Cs(1)-I(1) bond lengths are 4.43 Å. All Cs(1)-I(2) bond lengths are 4.16 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 6-coordinate geometry to one Mn(1), one I(4), two equivalent I(1), and two equivalent I(2) atoms. The Zr(1)-Mn(1) bond length is 2.45 Å. The Zr(1)-I(4) bond length is 3.66 Å. Both Zr(1)-I(1) bond lengths are 2.92 Å. Both Zr(1)-I(2) bond lengths are 2.92 Å. In the second Zr site, Zr(2) is bonded to one Mn(1), one I(1), one I(2), one I(3), one I(4), and one I(5) atom to form ZrMnI5 octahedra that share corners with two equivalent Cs(1)I12 cuboctahedra, corners with two equivalent Zr(2)MnI5 octahedra,  an edgeedge with one Cs(1)I12 cuboctahedra, and edges with two equivalent Zr(2)MnI5 octahedra. The corner-sharing octahedral tilt angles range from 0-44°. The Zr(2)-Mn(1) bond length is 2.53 Å. The Zr(2)-I(1) bond length is 2.96 Å. The Zr(2)-I(2) bond length is 2.95 Å. The Zr(2)-I(3) bond length is 2.91 Å. The Zr(2)-I(4) bond length is 2.99 Å. The Zr(2)-I(5) bond length is 3.22 Å. Mn(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 2-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 3-coordinate geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the third I site, I(3) is bonded in a 3-coordinate geometry to one Cs(1) and two equivalent Zr(2) atoms. 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 bent 150 degrees geometry to two equivalent Zr(2) atoms.