ZrCrAgS4 crystallizes in the orthorhombic Pmmn space group. Zr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. Cr(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with three equivalent Ag(1)S6 pentagonal pyramids, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Zr(1)S6 octahedra, and  an edgeedge with one Ag(1)S6 pentagonal pyramid. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted AgS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Zr(1), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form a mixture of edge and corner-sharing SZrCr2Ag2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1), one Cr(1), and one Ag(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1), one Cr(1), and one Ag(2) atom.
ZrCrAgS4 crystallizes in the orthorhombic Pmmn space group. Zr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form ZrS6 octahedra that share edges with two equivalent Zr(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. Both Zr(1)-S(1) bond lengths are 2.56 Å. Both Zr(1)-S(2) bond lengths are 2.56 Å. Both Zr(1)-S(3) bond lengths are 2.56 Å. Cr(1) is bonded to one S(2), one S(3), and four equivalent S(1) atoms to form CrS6 octahedra that share corners with three equivalent Ag(1)S6 pentagonal pyramids, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Zr(1)S6 octahedra, and  an edgeedge with one Ag(1)S6 pentagonal pyramid. The Cr(1)-S(2) bond length is 2.43 Å. The Cr(1)-S(3) bond length is 2.44 Å. There are two shorter (2.44 Å) and two longer (2.49 Å) Cr(1)-S(1) bond lengths. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form distorted AgS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with four equivalent Zr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Ag(1)-S(2) bond lengths are 2.76 Å. All Ag(1)-S(1) bond lengths are 2.87 Å. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent S(3) and four equivalent S(1) atoms. Both Ag(2)-S(3) bond lengths are 2.66 Å. All Ag(2)-S(1) bond lengths are 2.82 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Zr(1), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form a mixture of edge and corner-sharing SZrCr2Ag2 trigonal bipyramids. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1), one Cr(1), and one Ag(1) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1), one Cr(1), and one Ag(2) atom.