HfCrAgS4 crystallizes in the monoclinic P2 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form HfS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. In the second Hf site, Hf(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form HfS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and faces with two equivalent Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two 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 41-47°. In the second Cr site, Cr(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and faces with two equivalent Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form distorted AgS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, corners with four equivalent Hf(2)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Ag(2)S6 octahedra, and faces with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. In the second Ag site, Ag(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted AgS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Ag(1)S6 octahedra, and faces with two equivalent Hf(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Hf(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Hf(1), one Hf(2), one Cr(1), and one Ag(2) atom. In the third S site, S(3) is bonded to one Hf(1), one Hf(2), one Cr(2), one Ag(1), and one Ag(2) atom to form a mixture of distorted edge and corner-sharing SHf2CrAg2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Hf(2), one Cr(1), one Cr(2), one Ag(1), and one Ag(2) atom.
HfCrAgS4 crystallizes in the monoclinic P2 space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form HfS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-50°. Both Hf(1)-S(1) bond lengths are 2.50 Å. Both Hf(1)-S(2) bond lengths are 2.58 Å. Both Hf(1)-S(3) bond lengths are 2.55 Å. In the second Hf site, Hf(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form HfS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and faces with two equivalent Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. Both Hf(2)-S(2) bond lengths are 2.55 Å. Both Hf(2)-S(3) bond lengths are 2.61 Å. Both Hf(2)-S(4) bond lengths are 2.51 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two 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 41-47°. Both Cr(1)-S(1) bond lengths are 2.42 Å. Both Cr(1)-S(2) bond lengths are 2.45 Å. Both Cr(1)-S(4) bond lengths are 2.44 Å. In the second Cr site, Cr(2) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form CrS6 octahedra that share corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Hf(1)S6 octahedra, edges with two equivalent Hf(2)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and faces with two equivalent Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. Both Cr(2)-S(1) bond lengths are 2.44 Å. Both Cr(2)-S(3) bond lengths are 2.46 Å. Both Cr(2)-S(4) bond lengths are 2.45 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form distorted AgS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, corners with four equivalent Hf(2)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Ag(2)S6 octahedra, and faces with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 41-52°. Both Ag(1)-S(1) bond lengths are 2.71 Å. Both Ag(1)-S(3) bond lengths are 2.75 Å. Both Ag(1)-S(4) bond lengths are 2.77 Å. In the second Ag site, Ag(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form distorted AgS6 octahedra that share corners with four equivalent Hf(1)S6 octahedra, corners with four equivalent Cr(1)S6 octahedra, corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Ag(1)S6 octahedra, and faces with two equivalent Hf(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-51°. Both Ag(2)-S(2) bond lengths are 2.74 Å. Both Ag(2)-S(3) bond lengths are 2.81 Å. Both Ag(2)-S(4) bond lengths are 2.88 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Hf(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Hf(1), one Hf(2), one Cr(1), and one Ag(2) atom. In the third S site, S(3) is bonded to one Hf(1), one Hf(2), one Cr(2), one Ag(1), and one Ag(2) atom to form a mixture of distorted edge and corner-sharing SHf2CrAg2 trigonal bipyramids. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Hf(2), one Cr(1), one Cr(2), one Ag(1), and one Ag(2) atom.