TaCr3(AgS4)2 crystallizes in the monoclinic P2/c space group. Ta(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form TaS6 octahedra that share edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form CrS6 octahedra that share corners with three equivalent Ag(1)S6 pentagonal pyramids, edges with two equivalent Ta(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  an edgeedge with one Ag(1)S6 pentagonal pyramid. In the second Cr site, Cr(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Ta(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted AgS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Ta(1)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 8-11°. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ta(1), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form STaCr2Ag2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Ag2 trigonal bipyramids, corners with three equivalent S(1)TaCr2Ag2 trigonal bipyramids,  an edgeedge with one S(1)TaCr2Ag2 trigonal bipyramid, and edges with three equivalent S(2)Cr3Ag2 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(2), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form distorted SCr3Ag2 trigonal bipyramids that share corners with two equivalent S(1)TaCr2Ag2 trigonal bipyramids, corners with three equivalent S(2)Cr3Ag2 trigonal bipyramids,  an edgeedge with one S(2)Cr3Ag2 trigonal bipyramid, and edges with three equivalent S(1)TaCr2Ag2 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ta(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ta(1), one Cr(1), one Cr(2), and one Ag(2) atom.
TaCr3(AgS4)2 crystallizes in the monoclinic P2/c space group. Ta(1) is bonded to two equivalent S(1), two equivalent S(3), and two equivalent S(4) atoms to form TaS6 octahedra that share edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. Both Ta(1)-S(1) bond lengths are 2.47 Å. Both Ta(1)-S(3) bond lengths are 2.46 Å. Both Ta(1)-S(4) bond lengths are 2.45 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(3), one S(4), two equivalent S(1), and two equivalent S(2) atoms to form CrS6 octahedra that share corners with three equivalent Ag(1)S6 pentagonal pyramids, edges with two equivalent Ta(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and  an edgeedge with one Ag(1)S6 pentagonal pyramid. The Cr(1)-S(3) bond length is 2.42 Å. The Cr(1)-S(4) bond length is 2.43 Å. There is one shorter (2.41 Å) and one longer (2.46 Å) Cr(1)-S(1) bond length. There is one shorter (2.38 Å) and one longer (2.43 Å) Cr(1)-S(2) bond length. In the second Cr site, Cr(2) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form CrS6 octahedra that share edges with two equivalent Ta(1)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and edges with two equivalent Ag(1)S6 pentagonal pyramids. Both Cr(2)-S(2) bond lengths are 2.40 Å. Both Cr(2)-S(3) bond lengths are 2.41 Å. Both Cr(2)-S(4) bond lengths are 2.41 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted AgS6 pentagonal pyramids that share corners with six equivalent Cr(1)S6 octahedra, edges with two equivalent Ta(1)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 8-11°. Both Ag(1)-S(1) bond lengths are 2.80 Å. Both Ag(1)-S(2) bond lengths are 2.81 Å. Both Ag(1)-S(3) bond lengths are 2.75 Å. In the second Ag site, Ag(2) is bonded in a 6-coordinate geometry to two equivalent S(1), two equivalent S(2), and two equivalent S(4) atoms. Both Ag(2)-S(1) bond lengths are 2.81 Å. Both Ag(2)-S(2) bond lengths are 2.88 Å. Both Ag(2)-S(4) bond lengths are 2.69 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Ta(1), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form STaCr2Ag2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Ag2 trigonal bipyramids, corners with three equivalent S(1)TaCr2Ag2 trigonal bipyramids,  an edgeedge with one S(1)TaCr2Ag2 trigonal bipyramid, and edges with three equivalent S(2)Cr3Ag2 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(2), two equivalent Cr(1), one Ag(1), and one Ag(2) atom to form distorted SCr3Ag2 trigonal bipyramids that share corners with two equivalent S(1)TaCr2Ag2 trigonal bipyramids, corners with three equivalent S(2)Cr3Ag2 trigonal bipyramids,  an edgeedge with one S(2)Cr3Ag2 trigonal bipyramid, and edges with three equivalent S(1)TaCr2Ag2 trigonal bipyramids. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Ta(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one Ta(1), one Cr(1), one Cr(2), and one Ag(2) atom.