Ca(CrS2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CaS6 octahedra that share corners with six equivalent Cr(1)S4 tetrahedra, edges with two equivalent Ca(1)S6 octahedra, and edges with four equivalent Cr(2)S6 octahedra. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form CrS4 tetrahedra that share corners with six equivalent Ca(1)S6 octahedra and corners with six equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. In the second Cr site, Cr(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with six equivalent Cr(1)S4 tetrahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with four equivalent Ca(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Cr(1), and two equivalent Cr(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1), one Cr(1), and one Cr(2) atom.
Ca(CrS2)2 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. Ca(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CaS6 octahedra that share corners with six equivalent Cr(1)S4 tetrahedra, edges with two equivalent Ca(1)S6 octahedra, and edges with four equivalent Cr(2)S6 octahedra. Both Ca(1)-S(1) bond lengths are 2.74 Å. All Ca(1)-S(2) bond lengths are 2.71 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form CrS4 tetrahedra that share corners with six equivalent Ca(1)S6 octahedra and corners with six equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-65°. Both Cr(1)-S(1) bond lengths are 2.34 Å. Both Cr(1)-S(2) bond lengths are 2.26 Å. In the second Cr site, Cr(2) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form CrS6 octahedra that share corners with six equivalent Cr(1)S4 tetrahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with four equivalent Ca(1)S6 octahedra. Both Cr(2)-S(2) bond lengths are 2.44 Å. All Cr(2)-S(1) bond lengths are 2.49 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Ca(1), one Cr(1), and two equivalent Cr(2) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Ca(1), one Cr(1), and one Cr(2) atom.