CsZr6MnCl14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent Cl(2), two equivalent Cl(4), four equivalent Cl(1), and four equivalent Cl(5) atoms to form CsCl12 cuboctahedra that share corners with eight equivalent Zr(2)MnCl5 octahedra, edges with two equivalent Zr(1)MnCl5 octahedra, edges with four equivalent Zr(2)MnCl5 octahedra, and faces with two equivalent Zr(1)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Mn(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(5) atoms to form ZrMnCl5 octahedra that share  a cornercorner with one Zr(1)MnCl5 octahedra, corners with two equivalent Zr(2)MnCl5 octahedra,  an edgeedge with one Cs(1)Cl12 cuboctahedra, edges with four equivalent Zr(2)MnCl5 octahedra, and  a faceface with one Cs(1)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-46°. In the second Zr site, Zr(2) is bonded to one Mn(1), one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form ZrMnCl5 octahedra that share corners with two equivalent Cs(1)Cl12 cuboctahedra,  a cornercorner with one Zr(1)MnCl5 octahedra, corners with two equivalent Zr(2)MnCl5 octahedra,  an edgeedge with one Cs(1)Cl12 cuboctahedra, edges with two equivalent Zr(1)MnCl5 octahedra, and edges with two equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-46°. Mn(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted L-shaped geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the second Cl site, Cl(2) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Zr(2) atoms. In the third Cl site, Cl(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the fourth Cl site, Cl(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 Cl site, Cl(5) is bonded in a distorted L-shaped geometry to one Cs(1), one Zr(1), and one Zr(2) atom.
CsZr6MnCl14 crystallizes in the orthorhombic Cmce space group. Cs(1) is bonded to two equivalent Cl(2), two equivalent Cl(4), four equivalent Cl(1), and four equivalent Cl(5) atoms to form CsCl12 cuboctahedra that share corners with eight equivalent Zr(2)MnCl5 octahedra, edges with two equivalent Zr(1)MnCl5 octahedra, edges with four equivalent Zr(2)MnCl5 octahedra, and faces with two equivalent Zr(1)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 41-42°. Both Cs(1)-Cl(2) bond lengths are 3.69 Å. Both Cs(1)-Cl(4) bond lengths are 3.60 Å. All Cs(1)-Cl(1) bond lengths are 3.90 Å. All Cs(1)-Cl(5) bond lengths are 3.75 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one Mn(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(5) atoms to form ZrMnCl5 octahedra that share  a cornercorner with one Zr(1)MnCl5 octahedra, corners with two equivalent Zr(2)MnCl5 octahedra,  an edgeedge with one Cs(1)Cl12 cuboctahedra, edges with four equivalent Zr(2)MnCl5 octahedra, and  a faceface with one Cs(1)Cl12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-46°. The Zr(1)-Mn(1) bond length is 2.40 Å. The Zr(1)-Cl(4) bond length is 3.02 Å. Both Zr(1)-Cl(1) bond lengths are 2.58 Å. Both Zr(1)-Cl(5) bond lengths are 2.58 Å. In the second Zr site, Zr(2) is bonded to one Mn(1), one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form ZrMnCl5 octahedra that share corners with two equivalent Cs(1)Cl12 cuboctahedra,  a cornercorner with one Zr(1)MnCl5 octahedra, corners with two equivalent Zr(2)MnCl5 octahedra,  an edgeedge with one Cs(1)Cl12 cuboctahedra, edges with two equivalent Zr(1)MnCl5 octahedra, and edges with two equivalent Zr(2)MnCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-46°. The Zr(2)-Mn(1) bond length is 2.46 Å. The Zr(2)-Cl(1) bond length is 2.60 Å. The Zr(2)-Cl(2) bond length is 2.56 Å. The Zr(2)-Cl(3) bond length is 2.69 Å. The Zr(2)-Cl(4) bond length is 2.67 Å. The Zr(2)-Cl(5) bond length is 2.60 Å. Mn(1) is bonded in an octahedral geometry to two equivalent Zr(1) and four equivalent Zr(2) atoms. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted L-shaped geometry to one Cs(1), one Zr(1), and one Zr(2) atom. In the second Cl site, Cl(2) is bonded in a distorted L-shaped geometry to one Cs(1) and two equivalent Zr(2) atoms. In the third Cl site, Cl(3) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the fourth Cl site, Cl(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 Cl site, Cl(5) is bonded in a distorted L-shaped geometry to one Cs(1), one Zr(1), and one Zr(2) atom.