AgCrTiS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form TiS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. In the second Ti site, Ti(2) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the second Cr site, Cr(2) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and two equivalent S(7) atoms. In the second Ag site, Ag(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), two equivalent S(6), and two equivalent S(8) atoms. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ti(1), two equivalent Cr(2), and two equivalent Ag(2) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ti(2), one Cr(1), and one Ag(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Ti(1), one Cr(1), and two equivalent Ag(2) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ti(1), two equivalent Cr(1), and two equivalent Ag(1) atoms. In the fifth S site, S(5) is bonded to one Ti(2), two equivalent Cr(2), and two equivalent Ag(1) atoms to form distorted STiCr2Ag2 trigonal bipyramids that share edges with two equivalent S(6)Ti2CrAg2 square pyramids and edges with two equivalent S(5)TiCr2Ag2 trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Ti(2), one Cr(2), and two equivalent Ag(2) atoms to form distorted STi2CrAg2 square pyramids that share edges with two equivalent S(6)Ti2CrAg2 square pyramids and edges with two equivalent S(5)TiCr2Ag2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Cr(1), and two equivalent Ag(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to two equivalent Ti(1), one Cr(2), and two equivalent Ag(2) atoms.
AgCrTiS4 crystallizes in the orthorhombic Pmc2_1 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(1), one S(4), two equivalent S(3), and two equivalent S(8) atoms to form TiS6 octahedra that share corners with four equivalent Cr(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The Ti(1)-S(1) bond length is 2.40 Å. The Ti(1)-S(4) bond length is 2.44 Å. Both Ti(1)-S(3) bond lengths are 2.45 Å. Both Ti(1)-S(8) bond lengths are 2.47 Å. In the second Ti site, Ti(2) is bonded to one S(5), one S(7), two equivalent S(2), and two equivalent S(6) atoms to form TiS6 octahedra that share corners with four equivalent Cr(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Ti(2)-S(5) bond length is 2.46 Å. The Ti(2)-S(7) bond length is 2.48 Å. Both Ti(2)-S(2) bond lengths are 2.41 Å. Both Ti(2)-S(6) bond lengths are 2.45 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(2), one S(3), two equivalent S(4), and two equivalent S(7) atoms to form CrS6 octahedra that share corners with four equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The Cr(1)-S(2) bond length is 2.45 Å. The Cr(1)-S(3) bond length is 2.35 Å. Both Cr(1)-S(4) bond lengths are 2.40 Å. Both Cr(1)-S(7) bond lengths are 2.42 Å. In the second Cr site, Cr(2) is bonded to one S(6), one S(8), two equivalent S(1), and two equivalent S(5) atoms to form CrS6 octahedra that share corners with four equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, and edges with two equivalent Cr(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 47-52°. The Cr(2)-S(6) bond length is 2.38 Å. The Cr(2)-S(8) bond length is 2.50 Å. Both Cr(2)-S(1) bond lengths are 2.39 Å. Both Cr(2)-S(5) bond lengths are 2.39 Å. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(5), and two equivalent S(7) atoms. The Ag(1)-S(2) bond length is 2.78 Å. Both Ag(1)-S(4) bond lengths are 2.90 Å. Both Ag(1)-S(5) bond lengths are 2.95 Å. Both Ag(1)-S(7) bond lengths are 2.91 Å. In the second Ag site, Ag(2) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(3), two equivalent S(6), and two equivalent S(8) atoms. There is one shorter (2.82 Å) and one longer (3.14 Å) Ag(2)-S(1) bond length. Both Ag(2)-S(3) bond lengths are 2.94 Å. Both Ag(2)-S(6) bond lengths are 2.96 Å. Both Ag(2)-S(8) bond lengths are 2.80 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ti(1), two equivalent Cr(2), and two equivalent Ag(2) atoms. In the second S site, S(2) is bonded in a 4-coordinate geometry to two equivalent Ti(2), one Cr(1), and one Ag(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Ti(1), one Cr(1), and two equivalent Ag(2) atoms. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Ti(1), two equivalent Cr(1), and two equivalent Ag(1) atoms. In the fifth S site, S(5) is bonded to one Ti(2), two equivalent Cr(2), and two equivalent Ag(1) atoms to form distorted STiCr2Ag2 trigonal bipyramids that share edges with two equivalent S(6)Ti2CrAg2 square pyramids and edges with two equivalent S(5)TiCr2Ag2 trigonal bipyramids. In the sixth S site, S(6) is bonded to two equivalent Ti(2), one Cr(2), and two equivalent Ag(2) atoms to form distorted STi2CrAg2 square pyramids that share edges with two equivalent S(6)Ti2CrAg2 square pyramids and edges with two equivalent S(5)TiCr2Ag2 trigonal bipyramids. In the seventh S site, S(7) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Cr(1), and two equivalent Ag(1) atoms. In the eighth S site, S(8) is bonded in a 5-coordinate geometry to two equivalent Ti(1), one Cr(2), and two equivalent Ag(2) atoms.