CuCrTiS4 crystallizes in the monoclinic Pm space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(10), one S(6), two equivalent S(14), and two equivalent S(5) atoms to form TiS6 octahedra that share  a cornercorner with one Ti(3)S6 octahedra, corners with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(4)S6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the second Ti site, Ti(2) is bonded to one S(15), one S(5), two equivalent S(1), and two equivalent S(11) atoms to form TiS6 octahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with two equivalent Ti(1)S6 octahedra, corners with two equivalent Cu(2)S5 square pyramids, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra,  an edgeedge with one Cu(2)S5 square pyramid, and edges with two equivalent Cu(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 53-55°. In the third Ti site, Ti(3) is bonded to one S(16), one S(6), two equivalent S(12), and two equivalent S(2) atoms to form TiS6 octahedra that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cu(1)S5 square pyramids, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra,  an edgeedge with one Cu(1)S5 square pyramid, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 54-55°. In the fourth Ti site, Ti(4) is bonded to one S(13), one S(7), two equivalent S(3), and two equivalent S(9) atoms to form TiS6 octahedra that share  a cornercorner with one Cr(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Ti(4)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-56°. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(9), two equivalent S(13), and two equivalent S(6) atoms to form CrS6 octahedra that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Ti(3)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(4)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the second Cr site, Cr(2) is bonded to one S(11), one S(7), two equivalent S(15), and two equivalent S(8) atoms to form CrS6 octahedra that share  a cornercorner with one Ti(4)S6 octahedra, corners with two equivalent Cr(4)S6 octahedra, corners with two equivalent Cu(1)S5 square pyramids, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  an edgeedge with one Cu(1)S5 square pyramid. The corner-sharing octahedral tilt angles range from 55-58°. In the third Cr site, Cr(3) is bonded to one S(12), one S(8), two equivalent S(16), and two equivalent S(7) atoms to form CrS6 octahedra that share  a cornercorner with one Cr(4)S6 octahedra, corners with two equivalent Ti(4)S6 octahedra, corners with two equivalent Cu(2)S5 square pyramids, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  an edgeedge with one Cu(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 54-56°. In the fourth Cr site, Cr(4) is bonded to one S(14), one S(8), two equivalent S(10), and two equivalent S(4) atoms to form CrS6 octahedra that share  a cornercorner with one Cr(3)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-58°. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(1), two equivalent S(15), and two equivalent S(2) atoms to form distorted CuS5 square pyramids that share corners with two equivalent Ti(3)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Cr(2)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cu(1)S5 square pyramids, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-13°. In the second Cu site, Cu(2) is bonded to one S(2), two equivalent S(1), and two equivalent S(16) atoms to form distorted CuS5 square pyramids that share corners with two equivalent Ti(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Cr(3)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cu(1)S5 square pyramids, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 9-13°. In the third Cu site, Cu(3) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(11), two equivalent S(13), and two equivalent S(4) atoms. In the fourth Cu site, Cu(4) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(12), two equivalent S(14), and two equivalent S(3) atoms. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ti(2), one Cu(1), and two equivalent Cu(2) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(16)TiCr2Cu2 square pyramids,  an edgeedge with one S(16)TiCr2Cu2 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(15)TiCr2Cu2 square pyramids. In the second S site, S(2) is bonded to two equivalent Ti(3), one Cu(2), and two equivalent Cu(1) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(15)TiCr2Cu2 square pyramids,  an edgeedge with one S(15)TiCr2Cu2 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(16)TiCr2Cu2 square pyramids. In the third S site, S(3) is bonded to two equivalent Ti(4), one Cu(3), and two equivalent Cu(4) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(14)Ti2CrCu2 square pyramids,  an edgeedge with one S(14)Ti2CrCu2 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, edges with two equivalent S(3)Ti2Cu3 square pyramids, and edges with two equivalent S(13)TiCr2Cu2 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Cr(4), one Cu(4), and two equivalent Cu(3) atoms to form SCr2Cu3 square pyramids that share corners with two equivalent S(13)TiCr2Cu2 square pyramids,  an edgeedge with one S(13)TiCr2Cu2 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, edges with two equivalent S(14)Ti2CrCu2 square pyramids, and edges with two equivalent S(3)Ti2Cu3 square pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cr(1) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(3), and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Ti(4), one Cr(2), and two equivalent Cr(3) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Cr(3), one Cr(4), and two equivalent Cr(2) atoms. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to two equivalent Ti(4) and one Cr(1) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Ti(1) and two equivalent Cr(4) atoms. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Ti(2), one Cr(2), and two equivalent Cu(3) atoms. In the twelfth S site, S(12) is bonded in a 5-coordinate geometry to two equivalent Ti(3), one Cr(3), and two equivalent Cu(4) atoms. In the thirteenth S site, S(13) is bonded to one Ti(4), two equivalent Cr(1), and two equivalent Cu(3) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(4)Cr2Cu3 square pyramids,  an edgeedge with one S(4)Cr2Cu3 square pyramid, edges with two equivalent S(3)Ti2Cu3 square pyramids, and edges with two equivalent S(13)TiCr2Cu2 square pyramids. In the fourteenth S site, S(14) is bonded to two equivalent Ti(1), one Cr(4), and two equivalent Cu(4) atoms to form STi2CrCu2 square pyramids that share corners with two equivalent S(3)Ti2Cu3 square pyramids,  an edgeedge with one S(3)Ti2Cu3 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, and edges with two equivalent S(14)Ti2CrCu2 square pyramids. In the fifteenth S site, S(15) is bonded to one Ti(2), two equivalent Cr(2), and two equivalent Cu(1) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(2)Ti2Cu3 square pyramids,  an edgeedge with one S(2)Ti2Cu3 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, and edges with two equivalent S(15)TiCr2Cu2 square pyramids. In the sixteenth S site, S(16) is bonded to one Ti(3), two equivalent Cr(3), and two equivalent Cu(2) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(1)Ti2Cu3 square pyramids,  an edgeedge with one S(1)Ti2Cu3 square pyramid, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(16)TiCr2Cu2 square pyramids.
CuCrTiS4 crystallizes in the monoclinic Pm space group. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one S(10), one S(6), two equivalent S(14), and two equivalent S(5) atoms to form TiS6 octahedra that share  a cornercorner with one Ti(3)S6 octahedra, corners with two equivalent Ti(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Cr(1)S6 octahedra, and edges with two equivalent Cr(4)S6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Ti(1)-S(10) bond length is 2.40 Å. The Ti(1)-S(6) bond length is 2.55 Å. Both Ti(1)-S(14) bond lengths are 2.42 Å. Both Ti(1)-S(5) bond lengths are 2.46 Å. In the second Ti site, Ti(2) is bonded to one S(15), one S(5), two equivalent S(1), and two equivalent S(11) atoms to form TiS6 octahedra that share  a cornercorner with one Cr(1)S6 octahedra, corners with two equivalent Ti(1)S6 octahedra, corners with two equivalent Cu(2)S5 square pyramids, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra,  an edgeedge with one Cu(2)S5 square pyramid, and edges with two equivalent Cu(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 53-55°. The Ti(2)-S(15) bond length is 2.43 Å. The Ti(2)-S(5) bond length is 2.64 Å. Both Ti(2)-S(1) bond lengths are 2.43 Å. Both Ti(2)-S(11) bond lengths are 2.41 Å. In the third Ti site, Ti(3) is bonded to one S(16), one S(6), two equivalent S(12), and two equivalent S(2) atoms to form TiS6 octahedra that share  a cornercorner with one Ti(1)S6 octahedra, corners with two equivalent Cr(1)S6 octahedra, corners with two equivalent Cu(1)S5 square pyramids, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra,  an edgeedge with one Cu(1)S5 square pyramid, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 54-55°. The Ti(3)-S(16) bond length is 2.50 Å. The Ti(3)-S(6) bond length is 2.54 Å. Both Ti(3)-S(12) bond lengths are 2.42 Å. Both Ti(3)-S(2) bond lengths are 2.44 Å. In the fourth Ti site, Ti(4) is bonded to one S(13), one S(7), two equivalent S(3), and two equivalent S(9) atoms to form TiS6 octahedra that share  a cornercorner with one Cr(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra, edges with two equivalent Ti(4)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 55-56°. The Ti(4)-S(13) bond length is 2.51 Å. The Ti(4)-S(7) bond length is 2.56 Å. Both Ti(4)-S(3) bond lengths are 2.43 Å. Both Ti(4)-S(9) bond lengths are 2.43 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one S(5), one S(9), two equivalent S(13), and two equivalent S(6) atoms to form CrS6 octahedra that share  a cornercorner with one Ti(2)S6 octahedra, corners with two equivalent Ti(3)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, edges with two equivalent Ti(4)S6 octahedra, and edges with two equivalent Cr(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-54°. The Cr(1)-S(5) bond length is 2.47 Å. The Cr(1)-S(9) bond length is 2.42 Å. Both Cr(1)-S(13) bond lengths are 2.37 Å. Both Cr(1)-S(6) bond lengths are 2.44 Å. In the second Cr site, Cr(2) is bonded to one S(11), one S(7), two equivalent S(15), and two equivalent S(8) atoms to form CrS6 octahedra that share  a cornercorner with one Ti(4)S6 octahedra, corners with two equivalent Cr(4)S6 octahedra, corners with two equivalent Cu(1)S5 square pyramids, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  an edgeedge with one Cu(1)S5 square pyramid. The corner-sharing octahedral tilt angles range from 55-58°. The Cr(2)-S(11) bond length is 2.44 Å. The Cr(2)-S(7) bond length is 2.47 Å. Both Cr(2)-S(15) bond lengths are 2.42 Å. Both Cr(2)-S(8) bond lengths are 2.41 Å. In the third Cr site, Cr(3) is bonded to one S(12), one S(8), two equivalent S(16), and two equivalent S(7) atoms to form CrS6 octahedra that share  a cornercorner with one Cr(4)S6 octahedra, corners with two equivalent Ti(4)S6 octahedra, corners with two equivalent Cu(2)S5 square pyramids, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cr(2)S6 octahedra, edges with two equivalent Cr(3)S6 octahedra, and  an edgeedge with one Cu(2)S5 square pyramid. The corner-sharing octahedral tilt angles range from 54-56°. The Cr(3)-S(12) bond length is 2.48 Å. The Cr(3)-S(8) bond length is 2.46 Å. Both Cr(3)-S(16) bond lengths are 2.37 Å. Both Cr(3)-S(7) bond lengths are 2.43 Å. In the fourth Cr site, Cr(4) is bonded to one S(14), one S(8), two equivalent S(10), and two equivalent S(4) atoms to form CrS6 octahedra that share  a cornercorner with one Cr(3)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra, edges with two equivalent Ti(1)S6 octahedra, and edges with two equivalent Cr(4)S6 octahedra. The corner-sharing octahedral tilt angles range from 54-58°. The Cr(4)-S(14) bond length is 2.42 Å. The Cr(4)-S(8) bond length is 2.55 Å. Both Cr(4)-S(10) bond lengths are 2.40 Å. Both Cr(4)-S(4) bond lengths are 2.41 Å. There are four inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one S(1), two equivalent S(15), and two equivalent S(2) atoms to form distorted CuS5 square pyramids that share corners with two equivalent Ti(3)S6 octahedra, corners with two equivalent Cr(2)S6 octahedra,  an edgeedge with one Ti(3)S6 octahedra,  an edgeedge with one Cr(2)S6 octahedra, edges with two equivalent Ti(2)S6 octahedra, edges with two equivalent Cu(1)S5 square pyramids, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-13°. The Cu(1)-S(1) bond length is 2.48 Å. Both Cu(1)-S(15) bond lengths are 2.52 Å. Both Cu(1)-S(2) bond lengths are 2.43 Å. In the second Cu site, Cu(2) is bonded to one S(2), two equivalent S(1), and two equivalent S(16) atoms to form distorted CuS5 square pyramids that share corners with two equivalent Ti(2)S6 octahedra, corners with two equivalent Cr(3)S6 octahedra,  an edgeedge with one Ti(2)S6 octahedra,  an edgeedge with one Cr(3)S6 octahedra, edges with two equivalent Ti(3)S6 octahedra, edges with two equivalent Cu(1)S5 square pyramids, and edges with two equivalent Cu(2)S5 square pyramids. The corner-sharing octahedral tilt angles range from 9-13°. The Cu(2)-S(2) bond length is 2.49 Å. Both Cu(2)-S(1) bond lengths are 2.44 Å. Both Cu(2)-S(16) bond lengths are 2.51 Å. In the third Cu site, Cu(3) is bonded in a 7-coordinate geometry to one S(3), two equivalent S(11), two equivalent S(13), and two equivalent S(4) atoms. The Cu(3)-S(3) bond length is 2.43 Å. Both Cu(3)-S(11) bond lengths are 2.95 Å. Both Cu(3)-S(13) bond lengths are 2.63 Å. Both Cu(3)-S(4) bond lengths are 2.43 Å. In the fourth Cu site, Cu(4) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(12), two equivalent S(14), and two equivalent S(3) atoms. The Cu(4)-S(4) bond length is 2.38 Å. Both Cu(4)-S(12) bond lengths are 2.97 Å. Both Cu(4)-S(14) bond lengths are 2.61 Å. Both Cu(4)-S(3) bond lengths are 2.43 Å. There are sixteen inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ti(2), one Cu(1), and two equivalent Cu(2) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(16)TiCr2Cu2 square pyramids,  an edgeedge with one S(16)TiCr2Cu2 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(15)TiCr2Cu2 square pyramids. In the second S site, S(2) is bonded to two equivalent Ti(3), one Cu(2), and two equivalent Cu(1) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(15)TiCr2Cu2 square pyramids,  an edgeedge with one S(15)TiCr2Cu2 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(16)TiCr2Cu2 square pyramids. In the third S site, S(3) is bonded to two equivalent Ti(4), one Cu(3), and two equivalent Cu(4) atoms to form STi2Cu3 square pyramids that share corners with two equivalent S(14)Ti2CrCu2 square pyramids,  an edgeedge with one S(14)Ti2CrCu2 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, edges with two equivalent S(3)Ti2Cu3 square pyramids, and edges with two equivalent S(13)TiCr2Cu2 square pyramids. In the fourth S site, S(4) is bonded to two equivalent Cr(4), one Cu(4), and two equivalent Cu(3) atoms to form SCr2Cu3 square pyramids that share corners with two equivalent S(13)TiCr2Cu2 square pyramids,  an edgeedge with one S(13)TiCr2Cu2 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, edges with two equivalent S(14)Ti2CrCu2 square pyramids, and edges with two equivalent S(3)Ti2Cu3 square pyramids. In the fifth S site, S(5) is bonded in a rectangular see-saw-like geometry to one Ti(2), two equivalent Ti(1), and one Cr(1) atom. In the sixth S site, S(6) is bonded in a rectangular see-saw-like geometry to one Ti(1), one Ti(3), and two equivalent Cr(1) atoms. In the seventh S site, S(7) is bonded in a rectangular see-saw-like geometry to one Ti(4), one Cr(2), and two equivalent Cr(3) atoms. In the eighth S site, S(8) is bonded in a rectangular see-saw-like geometry to one Cr(3), one Cr(4), and two equivalent Cr(2) atoms. In the ninth S site, S(9) is bonded in a 3-coordinate geometry to two equivalent Ti(4) and one Cr(1) atom. In the tenth S site, S(10) is bonded in a 3-coordinate geometry to one Ti(1) and two equivalent Cr(4) atoms. In the eleventh S site, S(11) is bonded in a 5-coordinate geometry to two equivalent Ti(2), one Cr(2), and two equivalent Cu(3) atoms. In the twelfth S site, S(12) is bonded in a 5-coordinate geometry to two equivalent Ti(3), one Cr(3), and two equivalent Cu(4) atoms. In the thirteenth S site, S(13) is bonded to one Ti(4), two equivalent Cr(1), and two equivalent Cu(3) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(4)Cr2Cu3 square pyramids,  an edgeedge with one S(4)Cr2Cu3 square pyramid, edges with two equivalent S(3)Ti2Cu3 square pyramids, and edges with two equivalent S(13)TiCr2Cu2 square pyramids. In the fourteenth S site, S(14) is bonded to two equivalent Ti(1), one Cr(4), and two equivalent Cu(4) atoms to form STi2CrCu2 square pyramids that share corners with two equivalent S(3)Ti2Cu3 square pyramids,  an edgeedge with one S(3)Ti2Cu3 square pyramid, edges with two equivalent S(4)Cr2Cu3 square pyramids, and edges with two equivalent S(14)Ti2CrCu2 square pyramids. In the fifteenth S site, S(15) is bonded to one Ti(2), two equivalent Cr(2), and two equivalent Cu(1) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(2)Ti2Cu3 square pyramids,  an edgeedge with one S(2)Ti2Cu3 square pyramid, edges with two equivalent S(1)Ti2Cu3 square pyramids, and edges with two equivalent S(15)TiCr2Cu2 square pyramids. In the sixteenth S site, S(16) is bonded to one Ti(3), two equivalent Cr(3), and two equivalent Cu(2) atoms to form STiCr2Cu2 square pyramids that share corners with two equivalent S(1)Ti2Cu3 square pyramids,  an edgeedge with one S(1)Ti2Cu3 square pyramid, edges with two equivalent S(2)Ti2Cu3 square pyramids, and edges with two equivalent S(16)TiCr2Cu2 square pyramids.