CuCrTiS4 crystallizes in the orthorhombic Pmn2_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 two equivalent Ti(2)S6 octahedra, corners with two 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 48-58°. In the second Ti site, Ti(2) is bonded to one S(6), one S(7), two equivalent S(1), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two 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 48-59°. 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 two equivalent Ti(2)S6 octahedra, corners with two 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 50-59°. In the second Cr site, Cr(2) is bonded to one S(5), one S(8), two equivalent S(2), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two 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 50-58°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. In the second Cu site, Cu(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), 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 to one Ti(1), two equivalent Ti(2), and one Cu(1) atom to form distorted STi3Cu tetrahedra that share corners with two equivalent S(1)Ti3Cu tetrahedra,  a cornercorner with one S(4)TiCr2Cu2 trigonal bipyramid, corners with four equivalent S(5)Ti2CrCu2 trigonal bipyramids,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(7)TiCr2Cu2 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(1), two equivalent Cr(2), and one Cu(2) atom to form SCr3Cu tetrahedra that share corners with two equivalent S(2)Cr3Cu tetrahedra,  a cornercorner with one S(3)Ti2CrCu2 trigonal bipyramid, corners with two equivalent S(5)Ti2CrCu2 trigonal bipyramids, corners with two equivalent S(7)TiCr2Cu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent Ti(1), one Cr(1), and two equivalent Cu(1) atoms to form distorted STi2CrCu2 trigonal bipyramids that share  a cornercorner with one S(2)Cr3Cu tetrahedra, corners with two equivalent S(5)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(7)TiCr2Cu2 trigonal bipyramids, edges with two equivalent S(1)Ti3Cu tetrahedra,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ti(1), two equivalent Cr(1), and two equivalent Cu(2) atoms to form distorted STiCr2Cu2 trigonal bipyramids that share  a cornercorner with one S(1)Ti3Cu tetrahedra, corners with two equivalent S(7)TiCr2Cu2 trigonal bipyramids, edges with two equivalent S(2)Cr3Cu tetrahedra,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the fifth S site, S(5) is bonded to two equivalent Ti(2), one Cr(2), and two equivalent Cu(1) atoms to form distorted STi2CrCu2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Cu tetrahedra, corners with four equivalent S(1)Ti3Cu tetrahedra, corners with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(7)TiCr2Cu2 trigonal bipyramids,  an edgeedge with one S(1)Ti3Cu tetrahedra,  an edgeedge with one S(3)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, and edges with two equivalent S(5)Ti2CrCu2 trigonal bipyramids. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Cr(2), and two equivalent Cu(2) atoms. In the seventh S site, S(7) is bonded to one Ti(2), two equivalent Cr(1), and two equivalent Cu(1) atoms to form distorted STiCr2Cu2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Cu tetrahedra, corners with two equivalent S(4)TiCr2Cu2 trigonal bipyramids, corners with four equivalent S(3)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(5)Ti2CrCu2 trigonal bipyramids, edges with two equivalent S(1)Ti3Cu tetrahedra,  an edgeedge with one S(3)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(4)TiCr2Cu2 trigonal bipyramid, and edges with two equivalent S(7)TiCr2Cu2 trigonal bipyramids. 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 Cu(2) atoms.
CuCrTiS4 crystallizes in the orthorhombic Pmn2_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 two equivalent Ti(2)S6 octahedra, corners with two 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 48-58°. The Ti(1)-S(1) bond length is 2.51 Å. The Ti(1)-S(4) bond length is 2.36 Å. Both Ti(1)-S(3) bond lengths are 2.46 Å. Both Ti(1)-S(8) bond lengths are 2.42 Å. In the second Ti site, Ti(2) is bonded to one S(6), one S(7), two equivalent S(1), and two equivalent S(5) atoms to form TiS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two 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 48-59°. The Ti(2)-S(6) bond length is 2.34 Å. The Ti(2)-S(7) bond length is 2.68 Å. Both Ti(2)-S(1) bond lengths are 2.41 Å. Both Ti(2)-S(5) bond lengths are 2.43 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 two equivalent Ti(2)S6 octahedra, corners with two 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 50-59°. The Cr(1)-S(2) bond length is 2.42 Å. The Cr(1)-S(3) bond length is 2.39 Å. Both Cr(1)-S(4) bond lengths are 2.45 Å. Both Cr(1)-S(7) bond lengths are 2.37 Å. In the second Cr site, Cr(2) is bonded to one S(5), one S(8), two equivalent S(2), and two equivalent S(6) atoms to form CrS6 octahedra that share corners with two equivalent Ti(1)S6 octahedra, corners with two 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 50-58°. The Cr(2)-S(5) bond length is 2.37 Å. The Cr(2)-S(8) bond length is 2.58 Å. Both Cr(2)-S(2) bond lengths are 2.33 Å. Both Cr(2)-S(6) bond lengths are 2.43 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 7-coordinate geometry to one S(1), two equivalent S(3), two equivalent S(5), and two equivalent S(7) atoms. The Cu(1)-S(1) bond length is 2.32 Å. Both Cu(1)-S(3) bond lengths are 2.64 Å. Both Cu(1)-S(5) bond lengths are 2.79 Å. Both Cu(1)-S(7) bond lengths are 2.73 Å. In the second Cu site, Cu(2) is bonded in a 7-coordinate geometry to one S(2), two equivalent S(4), two equivalent S(6), and two equivalent S(8) atoms. The Cu(2)-S(2) bond length is 2.31 Å. Both Cu(2)-S(4) bond lengths are 2.52 Å. Both Cu(2)-S(6) bond lengths are 2.86 Å. Both Cu(2)-S(8) bond lengths are 2.85 Å. There are eight inequivalent S sites. In the first S site, S(1) is bonded to one Ti(1), two equivalent Ti(2), and one Cu(1) atom to form distorted STi3Cu tetrahedra that share corners with two equivalent S(1)Ti3Cu tetrahedra,  a cornercorner with one S(4)TiCr2Cu2 trigonal bipyramid, corners with four equivalent S(5)Ti2CrCu2 trigonal bipyramids,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(7)TiCr2Cu2 trigonal bipyramids. In the second S site, S(2) is bonded to one Cr(1), two equivalent Cr(2), and one Cu(2) atom to form SCr3Cu tetrahedra that share corners with two equivalent S(2)Cr3Cu tetrahedra,  a cornercorner with one S(3)Ti2CrCu2 trigonal bipyramid, corners with two equivalent S(5)Ti2CrCu2 trigonal bipyramids, corners with two equivalent S(7)TiCr2Cu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the third S site, S(3) is bonded to two equivalent Ti(1), one Cr(1), and two equivalent Cu(1) atoms to form distorted STi2CrCu2 trigonal bipyramids that share  a cornercorner with one S(2)Cr3Cu tetrahedra, corners with two equivalent S(5)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(7)TiCr2Cu2 trigonal bipyramids, edges with two equivalent S(1)Ti3Cu tetrahedra,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the fourth S site, S(4) is bonded to one Ti(1), two equivalent Cr(1), and two equivalent Cu(2) atoms to form distorted STiCr2Cu2 trigonal bipyramids that share  a cornercorner with one S(1)Ti3Cu tetrahedra, corners with two equivalent S(7)TiCr2Cu2 trigonal bipyramids, edges with two equivalent S(2)Cr3Cu tetrahedra,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, edges with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, and edges with two equivalent S(4)TiCr2Cu2 trigonal bipyramids. In the fifth S site, S(5) is bonded to two equivalent Ti(2), one Cr(2), and two equivalent Cu(1) atoms to form distorted STi2CrCu2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Cu tetrahedra, corners with four equivalent S(1)Ti3Cu tetrahedra, corners with two equivalent S(3)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(7)TiCr2Cu2 trigonal bipyramids,  an edgeedge with one S(1)Ti3Cu tetrahedra,  an edgeedge with one S(3)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(7)TiCr2Cu2 trigonal bipyramid, and edges with two equivalent S(5)Ti2CrCu2 trigonal bipyramids. In the sixth S site, S(6) is bonded in a 5-coordinate geometry to one Ti(2), two equivalent Cr(2), and two equivalent Cu(2) atoms. In the seventh S site, S(7) is bonded to one Ti(2), two equivalent Cr(1), and two equivalent Cu(1) atoms to form distorted STiCr2Cu2 trigonal bipyramids that share corners with two equivalent S(2)Cr3Cu tetrahedra, corners with two equivalent S(4)TiCr2Cu2 trigonal bipyramids, corners with four equivalent S(3)Ti2CrCu2 trigonal bipyramids, corners with four equivalent S(5)Ti2CrCu2 trigonal bipyramids, edges with two equivalent S(1)Ti3Cu tetrahedra,  an edgeedge with one S(3)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(5)Ti2CrCu2 trigonal bipyramid,  an edgeedge with one S(4)TiCr2Cu2 trigonal bipyramid, and edges with two equivalent S(7)TiCr2Cu2 trigonal bipyramids. 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 Cu(2) atoms.