Cs4Sc6CCl13 crystallizes in the tetragonal I4_1/amd space group. Cs(1) is bonded in a 10-coordinate geometry to one Cl(4), two equivalent Cl(3), three equivalent Cl(2), and four equivalent Cl(1) atoms. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one C(1), one Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of distorted corner and edge-sharing ScCCl5 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. In the second Sc site, Sc(2) is bonded to one C(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form a mixture of distorted corner and edge-sharing ScCCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. C(1) is bonded to two equivalent Sc(2) and four equivalent Sc(1) atoms to form CSc6 octahedra that share corners with two equivalent Cl(4)Cs4Sc2 octahedra, corners with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids, and edges with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids. The corner-sharing octahedra are not tilted. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Sc(1), and one Sc(2) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to three equivalent Cs(1) and two equivalent Sc(1) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1), one Sc(2), and two equivalent Sc(1) atoms to form distorted ClCs2Sc3 trigonal bipyramids that share  a cornercorner with one C(1)Sc6 octahedra, corners with three equivalent Cl(3)Cs2Sc3 trigonal bipyramids,  an edgeedge with one C(1)Sc6 octahedra,  an edgeedge with one Cl(3)Cs2Sc3 trigonal bipyramid, and  a faceface with one Cl(4)Cs4Sc2 octahedra. The corner-sharing octahedra are not tilted. In the fourth Cl site, Cl(4) is bonded to four equivalent Cs(1) and two equivalent Sc(2) atoms to form ClCs4Sc2 octahedra that share corners with two equivalent C(1)Sc6 octahedra and faces with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids. The corner-sharing octahedra are not tilted.
Cs4Sc6CCl13 crystallizes in the tetragonal I4_1/amd space group. Cs(1) is bonded in a 10-coordinate geometry to one Cl(4), two equivalent Cl(3), three equivalent Cl(2), and four equivalent Cl(1) atoms. The Cs(1)-Cl(4) bond length is 3.40 Å. Both Cs(1)-Cl(3) bond lengths are 3.59 Å. There are two shorter (3.85 Å) and one longer (3.96 Å) Cs(1)-Cl(2) bond length. There are two shorter (3.60 Å) and two longer (3.67 Å) Cs(1)-Cl(1) bond lengths. There are two inequivalent Sc sites. In the first Sc site, Sc(1) is bonded to one C(1), one Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form a mixture of distorted corner and edge-sharing ScCCl5 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. The Sc(1)-C(1) bond length is 2.25 Å. The Sc(1)-Cl(1) bond length is 2.63 Å. Both Sc(1)-Cl(2) bond lengths are 2.58 Å. There is one shorter (2.61 Å) and one longer (2.94 Å) Sc(1)-Cl(3) bond length. In the second Sc site, Sc(2) is bonded to one C(1), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form a mixture of distorted corner and edge-sharing ScCCl5 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. The Sc(2)-C(1) bond length is 2.25 Å. The Sc(2)-Cl(4) bond length is 3.01 Å. Both Sc(2)-Cl(1) bond lengths are 2.61 Å. Both Sc(2)-Cl(3) bond lengths are 2.61 Å. C(1) is bonded to two equivalent Sc(2) and four equivalent Sc(1) atoms to form CSc6 octahedra that share corners with two equivalent Cl(4)Cs4Sc2 octahedra, corners with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids, and edges with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids. The corner-sharing octahedra are not tilted. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Sc(1), and one Sc(2) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to three equivalent Cs(1) and two equivalent Sc(1) atoms. In the third Cl site, Cl(3) is bonded to two equivalent Cs(1), one Sc(2), and two equivalent Sc(1) atoms to form distorted ClCs2Sc3 trigonal bipyramids that share  a cornercorner with one C(1)Sc6 octahedra, corners with three equivalent Cl(3)Cs2Sc3 trigonal bipyramids,  an edgeedge with one C(1)Sc6 octahedra,  an edgeedge with one Cl(3)Cs2Sc3 trigonal bipyramid, and  a faceface with one Cl(4)Cs4Sc2 octahedra. The corner-sharing octahedra are not tilted. In the fourth Cl site, Cl(4) is bonded to four equivalent Cs(1) and two equivalent Sc(2) atoms to form ClCs4Sc2 octahedra that share corners with two equivalent C(1)Sc6 octahedra and faces with four equivalent Cl(3)Cs2Sc3 trigonal bipyramids. The corner-sharing octahedra are not tilted.