Ca3C3Cl2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to three equivalent C(1), one Cl(1), and two equivalent Cl(2) atoms to form a mixture of edge and corner-sharing CaC3Cl3 octahedra. The corner-sharing octahedral tilt angles range from 0-76°. In the second Ca site, Ca(2) is bonded in a 10-coordinate geometry to two equivalent C(2), four equivalent C(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to two equivalent Ca(2), three equivalent Ca(1), and one C(2) atom. In the second C site, C(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(2) and two equivalent C(1) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Ca(1) and two equivalent Ca(2) atoms to form ClCa4 tetrahedra that share corners with two equivalent Cl(1)Ca4 tetrahedra and edges with four equivalent Cl(2)Ca6 octahedra. In the second Cl site, Cl(2) is bonded to two equivalent Ca(2) and four equivalent Ca(1) atoms to form distorted ClCa6 octahedra that share corners with two equivalent Cl(2)Ca6 octahedra, edges with two equivalent Cl(2)Ca6 octahedra, and edges with four equivalent Cl(1)Ca4 tetrahedra. The corner-sharing octahedral tilt angles are 59°.
Ca3C3Cl2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to three equivalent C(1), one Cl(1), and two equivalent Cl(2) atoms to form a mixture of edge and corner-sharing CaC3Cl3 octahedra. The corner-sharing octahedral tilt angles range from 0-76°. There is one shorter (2.49 Å) and two longer (2.58 Å) Ca(1)-C(1) bond lengths. The Ca(1)-Cl(1) bond length is 2.76 Å. Both Ca(1)-Cl(2) bond lengths are 2.93 Å. In the second Ca site, Ca(2) is bonded in a 10-coordinate geometry to two equivalent C(2), four equivalent C(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. Both Ca(2)-C(2) bond lengths are 2.52 Å. All Ca(2)-C(1) bond lengths are 2.77 Å. Both Ca(2)-Cl(1) bond lengths are 2.79 Å. Both Ca(2)-Cl(2) bond lengths are 3.31 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a 6-coordinate geometry to two equivalent Ca(2), three equivalent Ca(1), and one C(2) atom. The C(1)-C(2) bond length is 1.33 Å. In the second C site, C(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(2) and two equivalent C(1) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Ca(1) and two equivalent Ca(2) atoms to form ClCa4 tetrahedra that share corners with two equivalent Cl(1)Ca4 tetrahedra and edges with four equivalent Cl(2)Ca6 octahedra. In the second Cl site, Cl(2) is bonded to two equivalent Ca(2) and four equivalent Ca(1) atoms to form distorted ClCa6 octahedra that share corners with two equivalent Cl(2)Ca6 octahedra, edges with two equivalent Cl(2)Ca6 octahedra, and edges with four equivalent Cl(1)Ca4 tetrahedra. The corner-sharing octahedral tilt angles are 59°.