HfCrAgS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form HfS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the second Hf site, Hf(2) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form HfS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form CrS6 octahedra that share corners with four equivalent Hf(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. In the second Cr site, Cr(2) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and two equivalent S(7) atoms. In the second Ag site, Ag(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), 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 in a 5-coordinate geometry to two equivalent Hf(2), one Cr(1), and two equivalent Ag(2) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Hf(1), two equivalent Cr(2), and one Ag(1) atom. In the third S site, S(3) is bonded to one Hf(1), two equivalent Cr(1), and two equivalent Ag(2) atoms to form a mixture of distorted edge and corner-sharing SHfCr2Ag2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Hf(1), one Cr(1), and two equivalent Ag(1) atoms. In the fifth S site, S(5) is bonded to two equivalent Hf(2), one Cr(2), and two equivalent Ag(1) atoms to form distorted SHf2CrAg2 trigonal bipyramids that share edges with two equivalent S(6)HfCr2Ag2 square pyramids and edges with two equivalent S(5)Hf2CrAg2 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Hf(2), two equivalent Cr(2), and two equivalent Ag(2) atoms to form distorted SHfCr2Ag2 square pyramids that share corners with two equivalent S(3)HfCr2Ag2 trigonal bipyramids, edges with two equivalent S(6)HfCr2Ag2 square pyramids,  an edgeedge with one S(3)HfCr2Ag2 trigonal bipyramid, and edges with two equivalent S(5)Hf2CrAg2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to two equivalent Hf(1), one Cr(2), and two equivalent Ag(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Hf(2), two equivalent Cr(1), and two equivalent Ag(2) atoms.
HfCrAgS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form HfS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Hf(1)-S(2) bond length is 2.51 Å. The Hf(1)-S(3) bond length is 2.55 Å. Both Hf(1)-S(4) bond lengths are 2.55 Å. Both Hf(1)-S(7) bond lengths are 2.56 Å. In the second Hf site, Hf(2) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form HfS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Hf(2)-S(6) bond length is 2.56 Å. The Hf(2)-S(8) bond length is 2.57 Å. Both Hf(2)-S(1) bond lengths are 2.50 Å. Both Hf(2)-S(5) bond lengths are 2.54 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form CrS6 octahedra that share corners with four equivalent Hf(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-56°. The Cr(1)-S(1) bond length is 2.45 Å. The Cr(1)-S(4) bond length is 2.39 Å. Both Cr(1)-S(3) bond lengths are 2.43 Å. Both Cr(1)-S(8) bond lengths are 2.46 Å. In the second Cr site, Cr(2) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. The Cr(2)-S(5) bond length is 2.39 Å. The Cr(2)-S(7) bond length is 2.48 Å. Both Cr(2)-S(2) bond lengths are 2.41 Å. Both Cr(2)-S(6) bond lengths are 2.41 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and two equivalent S(7) atoms. The Ag(1)-S(2) bond length is 2.97 Å. Both Ag(1)-S(4) bond lengths are 2.89 Å. Both Ag(1)-S(5) bond lengths are 2.87 Å. Both Ag(1)-S(7) bond lengths are 2.92 Å. In the second Ag site, Ag(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), two equivalent S(6), and two equivalent S(8) atoms. There is one shorter (3.07 Å) and one longer (3.08 Å) Ag(2)-S(1) bond length. Both Ag(2)-S(3) bond lengths are 2.92 Å. Both Ag(2)-S(6) bond lengths are 2.92 Å. Both Ag(2)-S(8) bond lengths are 3.05 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Hf(2), one Cr(1), and two equivalent Ag(2) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to one Hf(1), two equivalent Cr(2), and one Ag(1) atom. In the third S site, S(3) is bonded to one Hf(1), two equivalent Cr(1), and two equivalent Ag(2) atoms to form a mixture of distorted edge and corner-sharing SHfCr2Ag2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent Hf(1), one Cr(1), and two equivalent Ag(1) atoms. In the fifth S site, S(5) is bonded to two equivalent Hf(2), one Cr(2), and two equivalent Ag(1) atoms to form distorted SHf2CrAg2 trigonal bipyramids that share edges with two equivalent S(6)HfCr2Ag2 square pyramids and edges with two equivalent S(5)Hf2CrAg2 trigonal bipyramids. In the sixth S site, S(6) is bonded to one Hf(2), two equivalent Cr(2), and two equivalent Ag(2) atoms to form distorted SHfCr2Ag2 square pyramids that share corners with two equivalent S(3)HfCr2Ag2 trigonal bipyramids, edges with two equivalent S(6)HfCr2Ag2 square pyramids,  an edgeedge with one S(3)HfCr2Ag2 trigonal bipyramid, and edges with two equivalent S(5)Hf2CrAg2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to two equivalent Hf(1), one Cr(2), and two equivalent Ag(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Hf(2), two equivalent Cr(1), and two equivalent Ag(2) atoms.