CuCrZrS4 crystallizes in the monoclinic Pm space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(11), one S(7), two equivalent S(15), and two equivalent S(8) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and edges with two equivalent Cr(4)S5 square pyramids. In the second Zr site, Zr(2) is bonded to one S(16), two equivalent S(12), and two equivalent S(2) atoms to form distorted ZrS5 square pyramids that share edges with two equivalent Cr(3)S6 octahedra and edges with two equivalent Zr(2)S5 square pyramids. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one S(13), one S(7), two equivalent S(3), and two equivalent S(9) atoms. In the fourth Zr site, Zr(4) is bonded in a 5-coordinate geometry to one S(14), one S(8), two equivalent S(10), and two equivalent S(4) atoms. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(9), two equivalent S(13), and two equivalent S(6) atoms to form edge-sharing CrS6 octahedra. In the second Cr site, Cr(2) is bonded to one S(10), one S(6), two equivalent S(14), and two equivalent S(5) atoms to form edge-sharing CrS6 octahedra. In the third Cr site, Cr(3) is bonded to one S(12), one S(8), two equivalent S(16), and two equivalent S(7) atoms to form CrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and edges with two equivalent Zr(2)S5 square pyramids. In the fourth Cr site, Cr(4) is bonded to one S(15), two equivalent S(1), and two equivalent S(11) atoms to form CrS5 square pyramids that share edges with two equivalent Zr(1)S6 octahedra and edges with two equivalent Cr(4)S5 square pyramids. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(15), and two equivalent S(2) atoms. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(16) atoms. In the third Cu site, Cu(3) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(13), and two equivalent S(4) atoms. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(14), and two equivalent S(3) atoms. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cr(4), one Cu(1), and two equivalent Cu(2) atoms to form distorted SCr2Cu3 square pyramids that share corners with two equivalent S(16)ZrCr2Cu2 square pyramids,  an edgeedge with one S(16)ZrCr2Cu2 square pyramid, edges with two equivalent S(1)Cr2Cu3 square pyramids, and edges with two equivalent S(15)Zr2CrCu2 square pyramids. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to two equivalent Zr(2), one Cu(2), and two equivalent Cu(1) atoms. In the third S site, S(3) is bonded to two equivalent Zr(3), one Cu(3), and two equivalent Cu(4) atoms to form distorted SZr2Cu3 square pyramids that share corners with two equivalent S(14)ZrCr2Cu2 square pyramids,  an edgeedge with one S(14)ZrCr2Cu2 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(13)ZrCr2Cu2 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Zr(4), one Cu(4), and two equivalent Cu(3) atoms to form distorted SZr2Cu3 square pyramids that share corners with two equivalent S(13)ZrCr2Cu2 square pyramids,  an edgeedge with one S(13)ZrCr2Cu2 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(14)ZrCr2Cu2 square pyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Cr(1) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Cr(2) and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(3), and two equivalent Cr(3) atoms. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Zr(4), two equivalent Zr(1), and one Cr(3) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to two equivalent Zr(3) and one Cr(1) atom. In the tenth S site, S(10) is bonded in a distorted T-shaped geometry to two equivalent Zr(4) and one Cr(2) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Zr(1) and two equivalent Cr(4) atoms. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to two equivalent Zr(2) and one Cr(3) atom. In the thirteenth S site, S(13) is bonded to one Zr(3), two equivalent Cr(1), and two equivalent Cu(3) atoms to form SZrCr2Cu2 square pyramids that share corners with two equivalent S(4)Zr2Cu3 square pyramids,  an edgeedge with one S(4)Zr2Cu3 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, and edges with two equivalent S(13)ZrCr2Cu2 square pyramids. In the fourteenth S site, S(14) is bonded to one Zr(4), two equivalent Cr(2), and two equivalent Cu(4) atoms to form distorted SZrCr2Cu2 square pyramids that share corners with two equivalent S(3)Zr2Cu3 square pyramids,  an edgeedge with one S(3)Zr2Cu3 square pyramid, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(14)ZrCr2Cu2 square pyramids. In the fifteenth S site, S(15) is bonded to two equivalent Zr(1), one Cr(4), and two equivalent Cu(1) atoms to form SZr2CrCu2 square pyramids that share edges with two equivalent S(1)Cr2Cu3 square pyramids and edges with two equivalent S(15)Zr2CrCu2 square pyramids. In the sixteenth S site, S(16) is bonded to one Zr(2), two equivalent Cr(3), and two equivalent Cu(2) atoms to form distorted SZrCr2Cu2 square pyramids that share corners with two equivalent S(1)Cr2Cu3 square pyramids,  an edgeedge with one S(1)Cr2Cu3 square pyramid, and edges with two equivalent S(16)ZrCr2Cu2 square pyramids.
CuCrZrS4 crystallizes in the monoclinic Pm space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(11), one S(7), two equivalent S(15), and two equivalent S(8) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and edges with two equivalent Cr(4)S5 square pyramids. The Zr(1)-S(11) bond length is 2.52 Å. The Zr(1)-S(7) bond length is 2.66 Å. Both Zr(1)-S(15) bond lengths are 2.59 Å. Both Zr(1)-S(8) bond lengths are 2.55 Å. In the second Zr site, Zr(2) is bonded to one S(16), two equivalent S(12), and two equivalent S(2) atoms to form distorted ZrS5 square pyramids that share edges with two equivalent Cr(3)S6 octahedra and edges with two equivalent Zr(2)S5 square pyramids. The Zr(2)-S(16) bond length is 2.44 Å. Both Zr(2)-S(12) bond lengths are 2.50 Å. Both Zr(2)-S(2) bond lengths are 2.57 Å. In the third Zr site, Zr(3) is bonded in a 5-coordinate geometry to one S(13), one S(7), two equivalent S(3), and two equivalent S(9) atoms. The Zr(3)-S(13) bond length is 2.47 Å. The Zr(3)-S(7) bond length is 3.32 Å. Both Zr(3)-S(3) bond lengths are 2.58 Å. Both Zr(3)-S(9) bond lengths are 2.49 Å. In the fourth Zr site, Zr(4) is bonded in a 5-coordinate geometry to one S(14), one S(8), two equivalent S(10), and two equivalent S(4) atoms. The Zr(4)-S(14) bond length is 2.45 Å. The Zr(4)-S(8) bond length is 3.28 Å. Both Zr(4)-S(10) bond lengths are 2.49 Å. Both Zr(4)-S(4) bond lengths are 2.59 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(9), two equivalent S(13), and two equivalent S(6) atoms to form edge-sharing CrS6 octahedra. The Cr(1)-S(5) bond length is 2.40 Å. The Cr(1)-S(9) bond length is 2.51 Å. Both Cr(1)-S(13) bond lengths are 2.52 Å. Both Cr(1)-S(6) bond lengths are 2.38 Å. In the second Cr site, Cr(2) is bonded to one S(10), one S(6), two equivalent S(14), and two equivalent S(5) atoms to form edge-sharing CrS6 octahedra. The Cr(2)-S(10) bond length is 2.47 Å. The Cr(2)-S(6) bond length is 2.40 Å. Both Cr(2)-S(14) bond lengths are 2.53 Å. Both Cr(2)-S(5) bond lengths are 2.38 Å. In the third Cr site, Cr(3) is bonded to one S(12), one S(8), two equivalent S(16), and two equivalent S(7) atoms to form CrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and edges with two equivalent Zr(2)S5 square pyramids. The Cr(3)-S(12) bond length is 2.43 Å. The Cr(3)-S(8) bond length is 2.47 Å. Both Cr(3)-S(16) bond lengths are 2.55 Å. Both Cr(3)-S(7) bond lengths are 2.41 Å. In the fourth Cr site, Cr(4) is bonded to one S(15), two equivalent S(1), and two equivalent S(11) atoms to form CrS5 square pyramids that share edges with two equivalent Zr(1)S6 octahedra and edges with two equivalent Cr(4)S5 square pyramids. The Cr(4)-S(15) bond length is 2.37 Å. Both Cr(4)-S(1) bond lengths are 2.44 Å. Both Cr(4)-S(11) bond lengths are 2.38 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 5-coordinate geometry to one S(1), two equivalent S(15), and two equivalent S(2) atoms. The Cu(1)-S(1) bond length is 2.25 Å. Both Cu(1)-S(15) bond lengths are 2.71 Å. Both Cu(1)-S(2) bond lengths are 2.41 Å. In the second Cu site, Cu(2) is bonded in a 5-coordinate geometry to one S(2), two equivalent S(1), and two equivalent S(16) atoms. The Cu(2)-S(2) bond length is 2.36 Å. Both Cu(2)-S(1) bond lengths are 2.58 Å. Both Cu(2)-S(16) bond lengths are 2.60 Å. In the third Cu site, Cu(3) is bonded in a 5-coordinate geometry to one S(3), two equivalent S(13), and two equivalent S(4) atoms. The Cu(3)-S(3) bond length is 2.30 Å. Both Cu(3)-S(13) bond lengths are 2.48 Å. Both Cu(3)-S(4) bond lengths are 2.61 Å. In the fourth Cu site, Cu(4) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(14), and two equivalent S(3) atoms. The Cu(4)-S(4) bond length is 2.29 Å. Both Cu(4)-S(14) bond lengths are 2.55 Å. Both Cu(4)-S(3) bond lengths are 2.53 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Cr(4), one Cu(1), and two equivalent Cu(2) atoms to form distorted SCr2Cu3 square pyramids that share corners with two equivalent S(16)ZrCr2Cu2 square pyramids,  an edgeedge with one S(16)ZrCr2Cu2 square pyramid, edges with two equivalent S(1)Cr2Cu3 square pyramids, and edges with two equivalent S(15)Zr2CrCu2 square pyramids. In the second S site, S(2) is bonded in a distorted pentagonal planar geometry to two equivalent Zr(2), one Cu(2), and two equivalent Cu(1) atoms. In the third S site, S(3) is bonded to two equivalent Zr(3), one Cu(3), and two equivalent Cu(4) atoms to form distorted SZr2Cu3 square pyramids that share corners with two equivalent S(14)ZrCr2Cu2 square pyramids,  an edgeedge with one S(14)ZrCr2Cu2 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(13)ZrCr2Cu2 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Zr(4), one Cu(4), and two equivalent Cu(3) atoms to form distorted SZr2Cu3 square pyramids that share corners with two equivalent S(13)ZrCr2Cu2 square pyramids,  an edgeedge with one S(13)ZrCr2Cu2 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(14)ZrCr2Cu2 square pyramids. In the fifth S site, S(5) is bonded in a distorted T-shaped geometry to one Cr(1) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Cr(2) and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded in a distorted rectangular see-saw-like geometry to one Zr(1), one Zr(3), and two equivalent Cr(3) atoms. In the eighth S site, S(8) is bonded in a distorted rectangular see-saw-like geometry to one Zr(4), two equivalent Zr(1), and one Cr(3) atom. In the ninth S site, S(9) is bonded in a distorted T-shaped geometry to two equivalent Zr(3) and one Cr(1) atom. In the tenth S site, S(10) is bonded in a distorted T-shaped geometry to two equivalent Zr(4) and one Cr(2) atom. In the eleventh S site, S(11) is bonded in a distorted T-shaped geometry to one Zr(1) and two equivalent Cr(4) atoms. In the twelfth S site, S(12) is bonded in a distorted T-shaped geometry to two equivalent Zr(2) and one Cr(3) atom. In the thirteenth S site, S(13) is bonded to one Zr(3), two equivalent Cr(1), and two equivalent Cu(3) atoms to form SZrCr2Cu2 square pyramids that share corners with two equivalent S(4)Zr2Cu3 square pyramids,  an edgeedge with one S(4)Zr2Cu3 square pyramid, edges with two equivalent S(3)Zr2Cu3 square pyramids, and edges with two equivalent S(13)ZrCr2Cu2 square pyramids. In the fourteenth S site, S(14) is bonded to one Zr(4), two equivalent Cr(2), and two equivalent Cu(4) atoms to form distorted SZrCr2Cu2 square pyramids that share corners with two equivalent S(3)Zr2Cu3 square pyramids,  an edgeedge with one S(3)Zr2Cu3 square pyramid, edges with two equivalent S(4)Zr2Cu3 square pyramids, and edges with two equivalent S(14)ZrCr2Cu2 square pyramids. In the fifteenth S site, S(15) is bonded to two equivalent Zr(1), one Cr(4), and two equivalent Cu(1) atoms to form SZr2CrCu2 square pyramids that share edges with two equivalent S(1)Cr2Cu3 square pyramids and edges with two equivalent S(15)Zr2CrCu2 square pyramids. In the sixteenth S site, S(16) is bonded to one Zr(2), two equivalent Cr(3), and two equivalent Cu(2) atoms to form distorted SZrCr2Cu2 square pyramids that share corners with two equivalent S(1)Cr2Cu3 square pyramids,  an edgeedge with one S(1)Cr2Cu3 square pyramid, and edges with two equivalent S(16)ZrCr2Cu2 square pyramids.