HfCrCuS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(6), and four equivalent S(1) atoms. In the second Hf site, Hf(2) is bonded in a 6-coordinate geometry to one S(3), one S(6), two equivalent S(1), and two equivalent S(2) atoms. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(2), and two equivalent S(5) atoms. In the second Cr site, Cr(2) is bonded in a distorted octahedral geometry to one S(4), one S(5), two equivalent S(1), and two equivalent S(2) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(2) atoms. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(4), one S(5), and two equivalent S(1) atoms. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Hf(2), two equivalent Hf(1), one Cr(2), and one Cu(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Hf(2), one Cr(1), one Cr(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Hf(1), one Hf(2), and one Cu(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Cr(1), one Cr(2), and one Cu(2) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Cr(2), two equivalent Cr(1), and one Cu(2) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Hf(2) and two equivalent Hf(1) atoms.
HfCrCuS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(6), and four equivalent S(1) atoms. The Hf(1)-S(3) bond length is 2.58 Å. There is one shorter (2.43 Å) and one longer (2.52 Å) Hf(1)-S(6) bond length. There are two shorter (2.58 Å) and two longer (3.04 Å) Hf(1)-S(1) bond lengths. In the second Hf site, Hf(2) is bonded in a 6-coordinate geometry to one S(3), one S(6), two equivalent S(1), and two equivalent S(2) atoms. The Hf(2)-S(3) bond length is 2.39 Å. The Hf(2)-S(6) bond length is 2.50 Å. Both Hf(2)-S(1) bond lengths are 2.68 Å. Both Hf(2)-S(2) bond lengths are 2.49 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded in a 5-coordinate geometry to one S(4), two equivalent S(2), and two equivalent S(5) atoms. The Cr(1)-S(4) bond length is 2.29 Å. Both Cr(1)-S(2) bond lengths are 2.48 Å. There is one shorter (2.41 Å) and one longer (2.59 Å) Cr(1)-S(5) bond length. In the second Cr site, Cr(2) is bonded in a distorted octahedral geometry to one S(4), one S(5), two equivalent S(1), and two equivalent S(2) atoms. The Cr(2)-S(4) bond length is 2.36 Å. The Cr(2)-S(5) bond length is 2.35 Å. Both Cr(2)-S(1) bond lengths are 2.58 Å. Both Cr(2)-S(2) bond lengths are 2.49 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(2) atoms. The Cu(1)-S(3) bond length is 2.23 Å. Both Cu(1)-S(2) bond lengths are 2.32 Å. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one S(4), one S(5), and two equivalent S(1) atoms. The Cu(2)-S(4) bond length is 2.22 Å. The Cu(2)-S(5) bond length is 2.72 Å. Both Cu(2)-S(1) bond lengths are 2.34 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Hf(2), two equivalent Hf(1), one Cr(2), and one Cu(2) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Hf(2), one Cr(1), one Cr(2), and one Cu(1) atom. In the third S site, S(3) is bonded in a distorted T-shaped geometry to one Hf(1), one Hf(2), and one Cu(1) atom. In the fourth S site, S(4) is bonded in a distorted T-shaped geometry to one Cr(1), one Cr(2), and one Cu(2) atom. In the fifth S site, S(5) is bonded in a distorted rectangular see-saw-like geometry to one Cr(2), two equivalent Cr(1), and one Cu(2) atom. In the sixth S site, S(6) is bonded in a 3-coordinate geometry to one Hf(2) and two equivalent Hf(1) atoms.