Gd4C2Cl3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent C(1), one Cl(2), and three equivalent Cl(1) atoms to form distorted GdC2Cl4 octahedra that share corners with two equivalent Gd(3)C3Cl3 octahedra, corners with two equivalent Gd(2)C4Cl2 octahedra,  an edgeedge with one Gd(2)C4Cl2 octahedra, edges with two equivalent Gd(4)C3Cl3 octahedra, edges with three equivalent Gd(3)C3Cl3 octahedra, and edges with four equivalent Gd(1)C2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Gd site, Gd(2) is bonded to two equivalent C(1), two equivalent C(2), and two equivalent Cl(3) atoms to form GdC4Cl2 octahedra that share corners with two equivalent Gd(1)C2Cl4 octahedra, corners with two equivalent Gd(2)C4Cl2 octahedra,  an edgeedge with one Gd(1)C2Cl4 octahedra, edges with two equivalent Gd(2)C4Cl2 octahedra, edges with four equivalent Gd(3)C3Cl3 octahedra, and edges with four equivalent Gd(4)C3Cl3 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the third Gd site, Gd(3) is bonded to one C(1), two equivalent C(2), one Cl(3), and two equivalent Cl(1) atoms to form distorted GdC3Cl3 octahedra that share corners with two equivalent Gd(1)C2Cl4 octahedra, corners with four equivalent Gd(4)C3Cl3 octahedra,  an edgeedge with one Gd(4)C3Cl3 octahedra, edges with two equivalent Gd(3)C3Cl3 octahedra, edges with three equivalent Gd(1)C2Cl4 octahedra, and edges with four equivalent Gd(2)C4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. In the fourth Gd site, Gd(4) is bonded to one C(1), two equivalent C(2), one Cl(3), and two equivalent Cl(2) atoms to form GdC3Cl3 octahedra that share corners with four equivalent Gd(3)C3Cl3 octahedra,  an edgeedge with one Gd(3)C3Cl3 octahedra, edges with two equivalent Gd(1)C2Cl4 octahedra, edges with two equivalent Gd(4)C3Cl3 octahedra, and edges with four equivalent Gd(2)C4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 1-17°. There are two inequivalent C sites. In the first C site, C(1) is bonded to one Gd(3), one Gd(4), two equivalent Gd(1), and two equivalent Gd(2) atoms to form CGd6 octahedra that share corners with two equivalent Cl(1)Gd5 square pyramids, edges with two equivalent C(1)Gd6 octahedra, edges with four equivalent C(2)Gd6 octahedra, and edges with three equivalent Cl(1)Gd5 square pyramids. In the second C site, C(2) is bonded to two equivalent Gd(2), two equivalent Gd(3), and two equivalent Gd(4) atoms to form CGd6 octahedra that share corners with two equivalent C(2)Gd6 octahedra, corners with two equivalent Cl(1)Gd5 square pyramids, edges with two equivalent C(2)Gd6 octahedra, edges with four equivalent C(1)Gd6 octahedra, and  an edgeedge with one Cl(1)Gd5 square pyramid. The corner-sharing octahedral tilt angles are 5°. There are three inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a distorted rectangular see-saw-like geometry to one Gd(3), one Gd(4), and two equivalent Gd(2) atoms. In the second Cl site, Cl(1) is bonded to two equivalent Gd(3) and three equivalent Gd(1) atoms to form distorted ClGd5 square pyramids that share corners with two equivalent C(1)Gd6 octahedra, corners with two equivalent C(2)Gd6 octahedra,  an edgeedge with one C(2)Gd6 octahedra, edges with three equivalent C(1)Gd6 octahedra, and edges with four equivalent Cl(1)Gd5 square pyramids. The corner-sharing octahedral tilt angles are 13°. In the third Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Gd(1) and two equivalent Gd(4) atoms.
Gd4C2Cl3 crystallizes in the orthorhombic Pnma space group. There are four inequivalent Gd sites. In the first Gd site, Gd(1) is bonded to two equivalent C(1), one Cl(2), and three equivalent Cl(1) atoms to form distorted GdC2Cl4 octahedra that share corners with two equivalent Gd(3)C3Cl3 octahedra, corners with two equivalent Gd(2)C4Cl2 octahedra,  an edgeedge with one Gd(2)C4Cl2 octahedra, edges with two equivalent Gd(4)C3Cl3 octahedra, edges with three equivalent Gd(3)C3Cl3 octahedra, and edges with four equivalent Gd(1)C2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Gd(1)-C(1) bond lengths are 2.43 Å. The Gd(1)-Cl(2) bond length is 2.68 Å. There is one shorter (2.81 Å) and two longer (3.04 Å) Gd(1)-Cl(1) bond lengths. In the second Gd site, Gd(2) is bonded to two equivalent C(1), two equivalent C(2), and two equivalent Cl(3) atoms to form GdC4Cl2 octahedra that share corners with two equivalent Gd(1)C2Cl4 octahedra, corners with two equivalent Gd(2)C4Cl2 octahedra,  an edgeedge with one Gd(1)C2Cl4 octahedra, edges with two equivalent Gd(2)C4Cl2 octahedra, edges with four equivalent Gd(3)C3Cl3 octahedra, and edges with four equivalent Gd(4)C3Cl3 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. Both Gd(2)-C(1) bond lengths are 2.61 Å. There is one shorter (2.67 Å) and one longer (2.68 Å) Gd(2)-C(2) bond length. Both Gd(2)-Cl(3) bond lengths are 2.90 Å. In the third Gd site, Gd(3) is bonded to one C(1), two equivalent C(2), one Cl(3), and two equivalent Cl(1) atoms to form distorted GdC3Cl3 octahedra that share corners with two equivalent Gd(1)C2Cl4 octahedra, corners with four equivalent Gd(4)C3Cl3 octahedra,  an edgeedge with one Gd(4)C3Cl3 octahedra, edges with two equivalent Gd(3)C3Cl3 octahedra, edges with three equivalent Gd(1)C2Cl4 octahedra, and edges with four equivalent Gd(2)C4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 0-17°. The Gd(3)-C(1) bond length is 2.55 Å. Both Gd(3)-C(2) bond lengths are 2.48 Å. The Gd(3)-Cl(3) bond length is 2.82 Å. Both Gd(3)-Cl(1) bond lengths are 3.04 Å. In the fourth Gd site, Gd(4) is bonded to one C(1), two equivalent C(2), one Cl(3), and two equivalent Cl(2) atoms to form GdC3Cl3 octahedra that share corners with four equivalent Gd(3)C3Cl3 octahedra,  an edgeedge with one Gd(3)C3Cl3 octahedra, edges with two equivalent Gd(1)C2Cl4 octahedra, edges with two equivalent Gd(4)C3Cl3 octahedra, and edges with four equivalent Gd(2)C4Cl2 octahedra. The corner-sharing octahedral tilt angles range from 1-17°. The Gd(4)-C(1) bond length is 2.58 Å. Both Gd(4)-C(2) bond lengths are 2.53 Å. The Gd(4)-Cl(3) bond length is 2.84 Å. Both Gd(4)-Cl(2) bond lengths are 2.87 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded to one Gd(3), one Gd(4), two equivalent Gd(1), and two equivalent Gd(2) atoms to form CGd6 octahedra that share corners with two equivalent Cl(1)Gd5 square pyramids, edges with two equivalent C(1)Gd6 octahedra, edges with four equivalent C(2)Gd6 octahedra, and edges with three equivalent Cl(1)Gd5 square pyramids. In the second C site, C(2) is bonded to two equivalent Gd(2), two equivalent Gd(3), and two equivalent Gd(4) atoms to form CGd6 octahedra that share corners with two equivalent C(2)Gd6 octahedra, corners with two equivalent Cl(1)Gd5 square pyramids, edges with two equivalent C(2)Gd6 octahedra, edges with four equivalent C(1)Gd6 octahedra, and  an edgeedge with one Cl(1)Gd5 square pyramid. The corner-sharing octahedral tilt angles are 5°. There are three inequivalent Cl sites. In the first Cl site, Cl(3) is bonded in a distorted rectangular see-saw-like geometry to one Gd(3), one Gd(4), and two equivalent Gd(2) atoms. In the second Cl site, Cl(1) is bonded to two equivalent Gd(3) and three equivalent Gd(1) atoms to form distorted ClGd5 square pyramids that share corners with two equivalent C(1)Gd6 octahedra, corners with two equivalent C(2)Gd6 octahedra,  an edgeedge with one C(2)Gd6 octahedra, edges with three equivalent C(1)Gd6 octahedra, and edges with four equivalent Cl(1)Gd5 square pyramids. The corner-sharing octahedral tilt angles are 13°. In the third Cl site, Cl(2) is bonded in a 3-coordinate geometry to one Gd(1) and two equivalent Gd(4) atoms.