NbCr3(AgS4)2 crystallizes in the monoclinic Pm space group. Nb(1) is bonded to one S(2), one S(7), two equivalent S(3), and two equivalent S(6) atoms to form distorted NbS6 octahedra that share corners with two equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Nb(1)S6 octahedra, edges with four equivalent Cr(2)S6 octahedra, and  a faceface with one Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(8) atoms to form distorted CrS6 octahedra that share corners with two equivalent Ag(2)S6 octahedra, corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Cr(3)S6 octahedra, and  a faceface with one Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. In the second Cr site, Cr(2) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with two equivalent Ag(2)S6 octahedra, corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Nb(1)S6 octahedra, and  a faceface with one Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. In the third Cr site, Cr(3) is bonded to one S(1), one S(8), two equivalent S(4), and two equivalent S(5) atoms to form distorted CrS6 octahedra that share corners with two equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and  a faceface with one Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form distorted AgS6 octahedra that share corners with two equivalent Nb(1)S6 octahedra, corners with two equivalent Cr(3)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,  a faceface with one Nb(1)S6 octahedra, and  a faceface with one Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. In the second Ag site, Ag(2) is bonded to one S(3), one S(4), two equivalent S(7), and two equivalent S(8) atoms to form distorted AgS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, corners with four equivalent Nb(1)S6 octahedra, corners with four equivalent Cr(3)S6 octahedra, edges with two equivalent Ag(2)S6 octahedra,  a faceface with one Cr(1)S6 octahedra, and  a faceface with one Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Cr(3), two equivalent Cr(1), and one Ag(1) atom to form distorted SCr3Ag trigonal pyramids that share  a cornercorner with one S(2)NbCr2Ag trigonal pyramid, corners with two equivalent S(1)Cr3Ag trigonal pyramids, and edges with two equivalent S(4)Cr3Ag trigonal pyramids. In the second S site, S(2) is bonded to one Nb(1), two equivalent Cr(2), and one Ag(1) atom to form distorted SNbCr2Ag trigonal pyramids that share corners with three equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(1)Cr3Ag trigonal pyramid, corners with two equivalent S(2)NbCr2Ag trigonal pyramids,  an edgeedge with one S(7)NbCr2Ag2 trigonal bipyramid, and edges with two equivalent S(3)Nb2CrAg trigonal pyramids. In the third S site, S(3) is bonded to two equivalent Nb(1), one Cr(2), and one Ag(2) atom to form distorted SNb2CrAg trigonal pyramids that share corners with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(4)Cr3Ag trigonal pyramid, corners with two equivalent S(3)Nb2CrAg trigonal pyramids, edges with two equivalent S(7)NbCr2Ag2 trigonal bipyramids, and edges with two equivalent S(2)NbCr2Ag trigonal pyramids. In the fourth S site, S(4) is bonded to one Cr(1), two equivalent Cr(3), and one Ag(2) atom to form distorted SCr3Ag trigonal pyramids that share corners with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(3)Nb2CrAg trigonal pyramid, corners with two equivalent S(4)Cr3Ag trigonal pyramids, and edges with two equivalent S(1)Cr3Ag trigonal pyramids. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Cr(1), two equivalent Cr(3), and two equivalent Ag(1) atoms. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Nb(1), one Cr(2), and two equivalent Ag(1) atoms. In the seventh S site, S(7) is bonded to one Nb(1), two equivalent Cr(2), and two equivalent Ag(2) atoms to form distorted SNbCr2Ag2 trigonal bipyramids that share corners with two equivalent S(4)Cr3Ag trigonal pyramids, corners with two equivalent S(3)Nb2CrAg trigonal pyramids, corners with three equivalent S(2)NbCr2Ag trigonal pyramids, edges with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  an edgeedge with one S(2)NbCr2Ag trigonal pyramid, and edges with two equivalent S(3)Nb2CrAg trigonal pyramids. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Cr(3), two equivalent Cr(1), and two equivalent Ag(2) atoms.
NbCr3(AgS4)2 crystallizes in the monoclinic Pm space group. Nb(1) is bonded to one S(2), one S(7), two equivalent S(3), and two equivalent S(6) atoms to form distorted NbS6 octahedra that share corners with two equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Nb(1)S6 octahedra, edges with four equivalent Cr(2)S6 octahedra, and  a faceface with one Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The Nb(1)-S(2) bond length is 2.41 Å. The Nb(1)-S(7) bond length is 2.58 Å. Both Nb(1)-S(3) bond lengths are 2.44 Å. Both Nb(1)-S(6) bond lengths are 2.54 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(4), one S(5), two equivalent S(1), and two equivalent S(8) atoms to form distorted CrS6 octahedra that share corners with two equivalent Ag(2)S6 octahedra, corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, edges with four equivalent Cr(3)S6 octahedra, and  a faceface with one Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Cr(1)-S(4) bond length is 2.28 Å. The Cr(1)-S(5) bond length is 2.50 Å. Both Cr(1)-S(1) bond lengths are 2.32 Å. Both Cr(1)-S(8) bond lengths are 2.42 Å. In the second Cr site, Cr(2) is bonded to one S(3), one S(6), two equivalent S(2), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with two equivalent Ag(2)S6 octahedra, corners with four equivalent Ag(1)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with four equivalent Nb(1)S6 octahedra, and  a faceface with one Ag(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-52°. The Cr(2)-S(3) bond length is 2.40 Å. The Cr(2)-S(6) bond length is 2.41 Å. Both Cr(2)-S(2) bond lengths are 2.38 Å. Both Cr(2)-S(7) bond lengths are 2.41 Å. In the third Cr site, Cr(3) is bonded to one S(1), one S(8), two equivalent S(4), and two equivalent S(5) atoms to form distorted CrS6 octahedra that share corners with two equivalent Ag(1)S6 octahedra, corners with four equivalent Ag(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, edges with four equivalent Cr(1)S6 octahedra, and  a faceface with one Ag(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 50-53°. The Cr(3)-S(1) bond length is 2.28 Å. The Cr(3)-S(8) bond length is 2.49 Å. Both Cr(3)-S(4) bond lengths are 2.32 Å. Both Cr(3)-S(5) bond lengths are 2.43 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to one S(1), one S(2), two equivalent S(5), and two equivalent S(6) atoms to form distorted AgS6 octahedra that share corners with two equivalent Nb(1)S6 octahedra, corners with two equivalent Cr(3)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,  a faceface with one Nb(1)S6 octahedra, and  a faceface with one Cr(3)S6 octahedra. The corner-sharing octahedral tilt angles range from 48-54°. The Ag(1)-S(1) bond length is 2.73 Å. The Ag(1)-S(2) bond length is 2.68 Å. Both Ag(1)-S(5) bond lengths are 2.75 Å. Both Ag(1)-S(6) bond lengths are 2.76 Å. In the second Ag site, Ag(2) is bonded to one S(3), one S(4), two equivalent S(7), and two equivalent S(8) atoms to form distorted AgS6 octahedra that share corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, corners with four equivalent Nb(1)S6 octahedra, corners with four equivalent Cr(3)S6 octahedra, edges with two equivalent Ag(2)S6 octahedra,  a faceface with one Cr(1)S6 octahedra, and  a faceface with one Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 44-55°. The Ag(2)-S(3) bond length is 2.67 Å. The Ag(2)-S(4) bond length is 2.66 Å. Both Ag(2)-S(7) bond lengths are 2.75 Å. Both Ag(2)-S(8) bond lengths are 2.77 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Cr(3), two equivalent Cr(1), and one Ag(1) atom to form distorted SCr3Ag trigonal pyramids that share  a cornercorner with one S(2)NbCr2Ag trigonal pyramid, corners with two equivalent S(1)Cr3Ag trigonal pyramids, and edges with two equivalent S(4)Cr3Ag trigonal pyramids. In the second S site, S(2) is bonded to one Nb(1), two equivalent Cr(2), and one Ag(1) atom to form distorted SNbCr2Ag trigonal pyramids that share corners with three equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(1)Cr3Ag trigonal pyramid, corners with two equivalent S(2)NbCr2Ag trigonal pyramids,  an edgeedge with one S(7)NbCr2Ag2 trigonal bipyramid, and edges with two equivalent S(3)Nb2CrAg trigonal pyramids. In the third S site, S(3) is bonded to two equivalent Nb(1), one Cr(2), and one Ag(2) atom to form distorted SNb2CrAg trigonal pyramids that share corners with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(4)Cr3Ag trigonal pyramid, corners with two equivalent S(3)Nb2CrAg trigonal pyramids, edges with two equivalent S(7)NbCr2Ag2 trigonal bipyramids, and edges with two equivalent S(2)NbCr2Ag trigonal pyramids. In the fourth S site, S(4) is bonded to one Cr(1), two equivalent Cr(3), and one Ag(2) atom to form distorted SCr3Ag trigonal pyramids that share corners with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  a cornercorner with one S(3)Nb2CrAg trigonal pyramid, corners with two equivalent S(4)Cr3Ag trigonal pyramids, and edges with two equivalent S(1)Cr3Ag trigonal pyramids. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Cr(1), two equivalent Cr(3), and two equivalent Ag(1) atoms. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to two equivalent Nb(1), one Cr(2), and two equivalent Ag(1) atoms. In the seventh S site, S(7) is bonded to one Nb(1), two equivalent Cr(2), and two equivalent Ag(2) atoms to form distorted SNbCr2Ag2 trigonal bipyramids that share corners with two equivalent S(4)Cr3Ag trigonal pyramids, corners with two equivalent S(3)Nb2CrAg trigonal pyramids, corners with three equivalent S(2)NbCr2Ag trigonal pyramids, edges with two equivalent S(7)NbCr2Ag2 trigonal bipyramids,  an edgeedge with one S(2)NbCr2Ag trigonal pyramid, and edges with two equivalent S(3)Nb2CrAg trigonal pyramids. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to one Cr(3), two equivalent Cr(1), and two equivalent Ag(2) atoms.