CuCr2S4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with three equivalent Cu(1)S6 pentagonal pyramids, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Cr(2)S6 octahedra, and  an edgeedge with one Cu(1)S6 pentagonal pyramid. In the second Cr site, Cr(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CrS6 octahedra that share edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Cu(1)S6 pentagonal pyramids. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted CuS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with four equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Cr(2), two equivalent Cr(1), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing SCr3Cu2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Cr(1), two equivalent Cr(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cr(1), two equivalent Cr(2), and one Cu(2) atom.
CuCr2S4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with three equivalent Cu(1)S6 pentagonal pyramids, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Cr(2)S6 octahedra, and  an edgeedge with one Cu(1)S6 pentagonal pyramid. The Cr(1)-S(2) bond length is 2.36 Å. The Cr(1)-S(3) bond length is 2.39 Å. There are two shorter (2.37 Å) and two longer (2.43 Å) Cr(1)-S(1) bond lengths. In the second Cr site, Cr(2) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form CrS6 octahedra that share edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Cu(1)S6 pentagonal pyramids. Both Cr(2)-S(1) bond lengths are 2.40 Å. Both Cr(2)-S(2) bond lengths are 2.35 Å. Both Cr(2)-S(3) bond lengths are 2.38 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted CuS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with four equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. Both Cu(1)-S(2) bond lengths are 2.39 Å. All Cu(1)-S(1) bond lengths are 2.60 Å. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. Both Cu(2)-S(3) bond lengths are 2.40 Å. All Cu(2)-S(1) bond lengths are 2.66 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Cr(2), two equivalent Cr(1), one Cu(1), and one Cu(2) atom to form a mixture of distorted edge and corner-sharing SCr3Cu2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Cr(1), two equivalent Cr(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Cr(1), two equivalent Cr(2), and one Cu(2) atom.