CuCrZrS4 crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(2)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. In the second Zr site, Zr(2) is bonded to one S(5), one S(8), two equivalent S(2), and two equivalent S(6) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-63°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with two equivalent Zr(2)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. In the second Cr site, Cr(2) is bonded to one S(6), one S(7), two equivalent S(1), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(1), two equivalent S(3), and two equivalent S(7) atoms. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent S(4), two equivalent S(6), and two equivalent S(8) atoms. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Zr(1), two equivalent Cr(2), and one Cu(1) atom to form SZrCr2Cu tetrahedra that share corners with two equivalent S(1)ZrCr2Cu tetrahedra,  a cornercorner with one S(4)ZrCr2Cu2 trigonal bipyramid, corners with two equivalent S(6)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to two equivalent Zr(2) and one Cr(1) atom. In the third S site, S(3) is bonded to two equivalent Zr(1), one Cr(1), and two equivalent Cu(1) atoms to form distorted SZr2CrCu2 trigonal bipyramids that share edges with two equivalent S(1)ZrCr2Cu tetrahedra, edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Zr(1), two equivalent Cr(1), and two equivalent Cu(2) atoms to form distorted SZrCr2Cu2 trigonal bipyramids that share  a cornercorner with one S(1)ZrCr2Cu tetrahedra, corners with two equivalent S(6)Zr2CrCu2 trigonal bipyramids,  an edgeedge with one S(6)Zr2CrCu2 trigonal bipyramid, edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Zr(2) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded to two equivalent Zr(2), one Cr(2), and two equivalent Cu(2) atoms to form distorted SZr2CrCu2 trigonal bipyramids that share corners with two equivalent S(1)ZrCr2Cu tetrahedra, corners with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids,  an edgeedge with one S(4)ZrCr2Cu2 trigonal bipyramid, and edges with two equivalent S(6)Zr2CrCu2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Cr(2), two equivalent Cr(1), and two equivalent Cu(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Zr(2), two equivalent Zr(1), and two equivalent Cu(2) atoms.
CuCrZrS4 crystallizes in the orthorhombic Pmn2_1 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(2)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-63°. The Zr(1)-S(1) bond length is 2.58 Å. The Zr(1)-S(4) bond length is 2.55 Å. Both Zr(1)-S(3) bond lengths are 2.57 Å. Both Zr(1)-S(8) bond lengths are 2.59 Å. In the second Zr site, Zr(2) is bonded to one S(5), one S(8), two equivalent S(2), and two equivalent S(6) atoms to form ZrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-63°. The Zr(2)-S(5) bond length is 2.51 Å. The Zr(2)-S(8) bond length is 2.71 Å. Both Zr(2)-S(2) bond lengths are 2.50 Å. Both Zr(2)-S(6) bond lengths are 2.62 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with two equivalent Zr(2)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Zr(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-59°. The Cr(1)-S(2) bond length is 2.44 Å. The Cr(1)-S(3) bond length is 2.39 Å. Both Cr(1)-S(4) bond lengths are 2.50 Å. Both Cr(1)-S(7) bond lengths are 2.41 Å. In the second Cr site, Cr(2) is bonded to one S(6), one S(7), two equivalent S(1), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with two equivalent Zr(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Cr(2)-S(6) bond length is 2.51 Å. The Cr(2)-S(7) bond length is 2.47 Å. Both Cr(2)-S(1) bond lengths are 2.38 Å. Both Cr(2)-S(5) bond lengths are 2.39 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(1), two equivalent S(3), and two equivalent S(7) atoms. The Cu(1)-S(1) bond length is 2.29 Å. Both Cu(1)-S(3) bond lengths are 2.60 Å. Both Cu(1)-S(7) bond lengths are 2.95 Å. In the second Cu site, Cu(2) is bonded in a 6-coordinate geometry to two equivalent S(4), two equivalent S(6), and two equivalent S(8) atoms. Both Cu(2)-S(4) bond lengths are 2.77 Å. Both Cu(2)-S(6) bond lengths are 2.42 Å. Both Cu(2)-S(8) bond lengths are 2.96 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Zr(1), two equivalent Cr(2), and one Cu(1) atom to form SZrCr2Cu tetrahedra that share corners with two equivalent S(1)ZrCr2Cu tetrahedra,  a cornercorner with one S(4)ZrCr2Cu2 trigonal bipyramid, corners with two equivalent S(6)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids. In the second S site, S(2) is bonded in a distorted T-shaped geometry to two equivalent Zr(2) and one Cr(1) atom. In the third S site, S(3) is bonded to two equivalent Zr(1), one Cr(1), and two equivalent Cu(1) atoms to form distorted SZr2CrCu2 trigonal bipyramids that share edges with two equivalent S(1)ZrCr2Cu tetrahedra, edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Zr(1), two equivalent Cr(1), and two equivalent Cu(2) atoms to form distorted SZrCr2Cu2 trigonal bipyramids that share  a cornercorner with one S(1)ZrCr2Cu tetrahedra, corners with two equivalent S(6)Zr2CrCu2 trigonal bipyramids,  an edgeedge with one S(6)Zr2CrCu2 trigonal bipyramid, edges with two equivalent S(3)Zr2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids. In the fifth S site, S(5) is bonded in a 3-coordinate geometry to one Zr(2) and two equivalent Cr(2) atoms. In the sixth S site, S(6) is bonded to two equivalent Zr(2), one Cr(2), and two equivalent Cu(2) atoms to form distorted SZr2CrCu2 trigonal bipyramids that share corners with two equivalent S(1)ZrCr2Cu tetrahedra, corners with two equivalent S(4)ZrCr2Cu2 trigonal bipyramids,  an edgeedge with one S(4)ZrCr2Cu2 trigonal bipyramid, and edges with two equivalent S(6)Zr2CrCu2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Cr(2), two equivalent Cr(1), and two equivalent Cu(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Zr(2), two equivalent Zr(1), and two equivalent Cu(2) atoms.