NbCr3(AgS4)2 is Spinel-derived structured and crystallizes in the orthorhombic P222_1 space group. Nb(1) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form NbS6 octahedra that share corners with six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. There are three 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. In the second Cr site, Cr(2) 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. In the third Cr site, Cr(3) 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. Ag(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form AgS4 tetrahedra that share corners with three equivalent Nb(1)S6 octahedra, corners with three equivalent Cr(1)S6 octahedra, corners with three equivalent Cr(2)S6 octahedra, and corners with three equivalent Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-66°. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Cr(1), one Cr(2), one Cr(3), and one Ag(1) atom to form SCr3Ag tetrahedra that share corners with three equivalent S(1)Cr3Ag tetrahedra, corners with three equivalent S(3)NbCr2Ag trigonal pyramids, and  an edgeedge with one S(3)NbCr2Ag trigonal pyramid. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the third S site, S(3) is bonded to one Nb(1), one Cr(2), one Cr(3), and one Ag(1) atom to form distorted SNbCr2Ag trigonal pyramids that share corners with three equivalent S(1)Cr3Ag tetrahedra, corners with three equivalent S(3)NbCr2Ag trigonal pyramids, and  an edgeedge with one S(1)Cr3Ag tetrahedra. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Nb(1), one Cr(1), one Cr(3), and one Ag(1) atom.
NbCr3(AgS4)2 is Spinel-derived structured and crystallizes in the orthorhombic P222_1 space group. Nb(1) is bonded to two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms to form NbS6 octahedra that share corners with six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Cr(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. Both Nb(1)-S(2) bond lengths are 2.41 Å. Both Nb(1)-S(3) bond lengths are 2.47 Å. Both Nb(1)-S(4) bond lengths are 2.61 Å. There are three 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. Both Cr(1)-S(1) bond lengths are 2.41 Å. Both Cr(1)-S(2) bond lengths are 2.49 Å. Both Cr(1)-S(4) bond lengths are 2.41 Å. In the second Cr site, Cr(2) 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(3)S6 octahedra. Both Cr(2)-S(1) bond lengths are 2.41 Å. Both Cr(2)-S(2) bond lengths are 2.44 Å. Both Cr(2)-S(3) bond lengths are 2.44 Å. In the third Cr site, Cr(3) 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 six equivalent Ag(1)S4 tetrahedra, edges with two equivalent Nb(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. Both Cr(3)-S(1) bond lengths are 2.42 Å. Both Cr(3)-S(3) bond lengths are 2.45 Å. Both Cr(3)-S(4) bond lengths are 2.44 Å. Ag(1) is bonded to one S(1), one S(2), one S(3), and one S(4) atom to form AgS4 tetrahedra that share corners with three equivalent Nb(1)S6 octahedra, corners with three equivalent Cr(1)S6 octahedra, corners with three equivalent Cr(2)S6 octahedra, and corners with three equivalent Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-66°. The Ag(1)-S(1) bond length is 2.44 Å. The Ag(1)-S(2) bond length is 2.54 Å. The Ag(1)-S(3) bond length is 2.49 Å. The Ag(1)-S(4) bond length is 2.45 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Cr(1), one Cr(2), one Cr(3), and one Ag(1) atom to form SCr3Ag tetrahedra that share corners with three equivalent S(1)Cr3Ag tetrahedra, corners with three equivalent S(3)NbCr2Ag trigonal pyramids, and  an edgeedge with one S(3)NbCr2Ag trigonal pyramid. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Nb(1), one Cr(1), one Cr(2), and one Ag(1) atom. In the third S site, S(3) is bonded to one Nb(1), one Cr(2), one Cr(3), and one Ag(1) atom to form distorted SNbCr2Ag trigonal pyramids that share corners with three equivalent S(1)Cr3Ag tetrahedra, corners with three equivalent S(3)NbCr2Ag trigonal pyramids, and  an edgeedge with one S(1)Cr3Ag tetrahedra. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Nb(1), one Cr(1), one Cr(3), and one Ag(1) atom.