ZrCrAgS4 crystallizes in the monoclinic P2 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form ZrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Zr(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 47-51°. In the second Zr site, Zr(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form ZrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Zr(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 45-53°. 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(3) 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 Zr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 40-47°. 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 Zr(1)S6 octahedra, edges with two equivalent Zr(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 45-52°. 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 Zr(1)S6 octahedra, corners with four equivalent Zr(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 40-53°. 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 Zr(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 Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Zr(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 Zr(1), one Zr(2), one Cr(1), and one Ag(2) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Zr(2), one Cr(1), one Cr(2), one Ag(1), and one Ag(2) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Zr(1), one Zr(2), one Cr(2), one Ag(1), and one Ag(2) atom.
ZrCrAgS4 crystallizes in the monoclinic P2 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms to form ZrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Zr(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 47-51°. Both Zr(1)-S(1) bond lengths are 2.51 Å. Both Zr(1)-S(2) bond lengths are 2.61 Å. Both Zr(1)-S(4) bond lengths are 2.57 Å. In the second Zr site, Zr(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form ZrS6 octahedra that share corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Zr(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 45-53°. Both Zr(2)-S(2) bond lengths are 2.57 Å. Both Zr(2)-S(3) bond lengths are 2.52 Å. Both Zr(2)-S(4) bond lengths are 2.62 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(3) 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 Zr(1)S6 octahedra, edges with two equivalent Zr(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 40-47°. 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(3) 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 Zr(1)S6 octahedra, edges with two equivalent Zr(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 45-52°. Both Cr(2)-S(1) bond lengths are 2.43 Å. Both Cr(2)-S(3) bond lengths are 2.45 Å. Both Cr(2)-S(4) bond lengths are 2.46 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 Zr(1)S6 octahedra, corners with four equivalent Zr(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 40-53°. Both Ag(1)-S(1) bond lengths are 2.65 Å. Both Ag(1)-S(3) bond lengths are 2.76 Å. Both Ag(1)-S(4) bond lengths are 2.76 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 Zr(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 Zr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 45-52°. Both Ag(2)-S(2) bond lengths are 2.71 Å. Both Ag(2)-S(3) bond lengths are 2.88 Å. Both Ag(2)-S(4) bond lengths are 2.84 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 Zr(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 Zr(1), one Zr(2), one Cr(1), and one Ag(2) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Zr(2), one Cr(1), one Cr(2), one Ag(1), and one Ag(2) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Zr(1), one Zr(2), one Cr(2), one Ag(1), and one Ag(2) atom.