HfCrAgS4 crystallizes in the orthorhombic Pnma space group. Hf(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form HfS6 octahedra that share corners with three equivalent Cr(1)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 56-58°. Cr(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(2) atoms to form CrS6 octahedra that share corners with three equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with four equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. Ag(1) is bonded in a 7-coordinate geometry to two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Hf(1) and three equivalent Ag(1) atoms to form distorted SHf2Ag3 square pyramids that share corners with two equivalent S(4)HfCr2Ag2 square pyramids, corners with six equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with two equivalent S(2)HfCr3 trigonal pyramids, edges with three equivalent S(4)HfCr2Ag2 square pyramids, edges with four equivalent S(1)Hf2Ag3 square pyramids, and edges with two equivalent S(3)Hf2CrAg2 trigonal bipyramids. In the second S site, S(2) is bonded to one Hf(1) and three equivalent Cr(1) atoms to form distorted SHfCr3 trigonal pyramids that share corners with two equivalent S(1)Hf2Ag3 square pyramids, corners with five equivalent S(4)HfCr2Ag2 square pyramids, corners with five equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with two equivalent S(2)HfCr3 trigonal pyramids,  an edgeedge with one S(4)HfCr2Ag2 square pyramid, and edges with two equivalent S(2)HfCr3 trigonal pyramids. In the third S site, S(3) is bonded to two equivalent Hf(1), one Cr(1), and two equivalent Ag(1) atoms to form distorted SHf2CrAg2 trigonal bipyramids that share corners with two equivalent S(4)HfCr2Ag2 square pyramids, corners with six equivalent S(1)Hf2Ag3 square pyramids, corners with five equivalent S(2)HfCr3 trigonal pyramids, edges with two equivalent S(1)Hf2Ag3 square pyramids, edges with three equivalent S(4)HfCr2Ag2 square pyramids, and edges with two equivalent S(3)Hf2CrAg2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Hf(1), two equivalent Cr(1), and two equivalent Ag(1) atoms to form distorted SHfCr2Ag2 square pyramids that share corners with two equivalent S(1)Hf2Ag3 square pyramids, corners with two equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with five equivalent S(2)HfCr3 trigonal pyramids, edges with two equivalent S(4)HfCr2Ag2 square pyramids, edges with three equivalent S(1)Hf2Ag3 square pyramids, edges with three equivalent S(3)Hf2CrAg2 trigonal bipyramids, and  an edgeedge with one S(2)HfCr3 trigonal pyramid.
HfCrAgS4 crystallizes in the orthorhombic Pnma space group. Hf(1) is bonded to one S(2), one S(4), two equivalent S(1), and two equivalent S(3) atoms to form HfS6 octahedra that share corners with three equivalent Cr(1)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 56-58°. The Hf(1)-S(2) bond length is 2.66 Å. The Hf(1)-S(4) bond length is 2.61 Å. Both Hf(1)-S(1) bond lengths are 2.50 Å. Both Hf(1)-S(3) bond lengths are 2.57 Å. Cr(1) is bonded to one S(3), two equivalent S(4), and three equivalent S(2) atoms to form CrS6 octahedra that share corners with three equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, and edges with four equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 56-58°. The Cr(1)-S(3) bond length is 2.48 Å. Both Cr(1)-S(4) bond lengths are 2.39 Å. There are two shorter (2.49 Å) and one longer (2.50 Å) Cr(1)-S(2) bond length. Ag(1) is bonded in a 7-coordinate geometry to two equivalent S(3), two equivalent S(4), and three equivalent S(1) atoms. Both Ag(1)-S(3) bond lengths are 2.83 Å. Both Ag(1)-S(4) bond lengths are 2.81 Å. There is one shorter (2.76 Å) and two longer (2.85 Å) Ag(1)-S(1) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Hf(1) and three equivalent Ag(1) atoms to form distorted SHf2Ag3 square pyramids that share corners with two equivalent S(4)HfCr2Ag2 square pyramids, corners with six equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with two equivalent S(2)HfCr3 trigonal pyramids, edges with three equivalent S(4)HfCr2Ag2 square pyramids, edges with four equivalent S(1)Hf2Ag3 square pyramids, and edges with two equivalent S(3)Hf2CrAg2 trigonal bipyramids. In the second S site, S(2) is bonded to one Hf(1) and three equivalent Cr(1) atoms to form distorted SHfCr3 trigonal pyramids that share corners with two equivalent S(1)Hf2Ag3 square pyramids, corners with five equivalent S(4)HfCr2Ag2 square pyramids, corners with five equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with two equivalent S(2)HfCr3 trigonal pyramids,  an edgeedge with one S(4)HfCr2Ag2 square pyramid, and edges with two equivalent S(2)HfCr3 trigonal pyramids. In the third S site, S(3) is bonded to two equivalent Hf(1), one Cr(1), and two equivalent Ag(1) atoms to form distorted SHf2CrAg2 trigonal bipyramids that share corners with two equivalent S(4)HfCr2Ag2 square pyramids, corners with six equivalent S(1)Hf2Ag3 square pyramids, corners with five equivalent S(2)HfCr3 trigonal pyramids, edges with two equivalent S(1)Hf2Ag3 square pyramids, edges with three equivalent S(4)HfCr2Ag2 square pyramids, and edges with two equivalent S(3)Hf2CrAg2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Hf(1), two equivalent Cr(1), and two equivalent Ag(1) atoms to form distorted SHfCr2Ag2 square pyramids that share corners with two equivalent S(1)Hf2Ag3 square pyramids, corners with two equivalent S(3)Hf2CrAg2 trigonal bipyramids, corners with five equivalent S(2)HfCr3 trigonal pyramids, edges with two equivalent S(4)HfCr2Ag2 square pyramids, edges with three equivalent S(1)Hf2Ag3 square pyramids, edges with three equivalent S(3)Hf2CrAg2 trigonal bipyramids, and  an edgeedge with one S(2)HfCr3 trigonal pyramid.