CuCr2S4 crystallizes in the monoclinic C2/m space group. Cr(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted CrS6 octahedra that share corners with six equivalent Cu(1)S6 octahedra, edges with six equivalent Cr(1)S6 octahedra, and  a faceface with one Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. Cu(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CuS6 octahedra that share corners with twelve equivalent Cr(1)S6 octahedra, edges with two equivalent Cu(1)S6 octahedra, and faces with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to three equivalent Cr(1) and two equivalent Cu(1) atoms. In the second S site, S(1) is bonded to three equivalent Cr(1) and one Cu(1) atom to form a mixture of distorted edge and corner-sharing SCr3Cu trigonal pyramids.
CuCr2S4 crystallizes in the monoclinic C2/m space group. Cr(1) is bonded to three equivalent S(1) and three equivalent S(2) atoms to form distorted CrS6 octahedra that share corners with six equivalent Cu(1)S6 octahedra, edges with six equivalent Cr(1)S6 octahedra, and  a faceface with one Cu(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. There is one shorter (2.26 Å) and two longer (2.28 Å) Cr(1)-S(1) bond lengths. There are two shorter (2.42 Å) and one longer (2.45 Å) Cr(1)-S(2) bond length. Cu(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form CuS6 octahedra that share corners with twelve equivalent Cr(1)S6 octahedra, edges with two equivalent Cu(1)S6 octahedra, and faces with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-55°. Both Cu(1)-S(1) bond lengths are 2.36 Å. All Cu(1)-S(2) bond lengths are 2.52 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a 5-coordinate geometry to three equivalent Cr(1) and two equivalent Cu(1) atoms. In the second S site, S(1) is bonded to three equivalent Cr(1) and one Cu(1) atom to form a mixture of distorted edge and corner-sharing SCr3Cu trigonal pyramids.