U2TiS5 crystallizes in the orthorhombic Pnma space group. U(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. Ti(1) is bonded to one S(2), one S(3), one S(4), and four equivalent S(1) atoms to form distorted edge-sharing TiS7 pentagonal bipyramids. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent U(1) and two equivalent Ti(1) atoms to form distorted SU2Ti2 trigonal pyramids that share corners with four equivalent S(3)U4Ti square pyramids, corners with two equivalent S(2)U4Ti trigonal bipyramids, corners with two equivalent S(4)U4Ti trigonal bipyramids, corners with six equivalent S(1)U2Ti2 trigonal pyramids,  an edgeedge with one S(3)U4Ti square pyramid, edges with two equivalent S(2)U4Ti trigonal bipyramids, edges with two equivalent S(4)U4Ti trigonal bipyramids, and  an edgeedge with one S(1)U2Ti2 trigonal pyramid. In the second S site, S(2) is bonded to four equivalent U(1) and one Ti(1) atom to form distorted SU4Ti trigonal bipyramids that share corners with five equivalent S(3)U4Ti square pyramids,  a cornercorner with one S(4)U4Ti trigonal bipyramid, corners with four equivalent S(2)U4Ti trigonal bipyramids, corners with four equivalent S(1)U2Ti2 trigonal pyramids, edges with two equivalent S(3)U4Ti square pyramids, edges with four equivalent S(4)U4Ti trigonal bipyramids, and edges with four equivalent S(1)U2Ti2 trigonal pyramids. In the third S site, S(3) is bonded to four equivalent U(1) and one Ti(1) atom to form SU4Ti square pyramids that share corners with four equivalent S(4)U4Ti trigonal bipyramids, corners with five equivalent S(2)U4Ti trigonal bipyramids, corners with eight equivalent S(1)U2Ti2 trigonal pyramids, edges with two equivalent S(3)U4Ti square pyramids,  an edgeedge with one S(4)U4Ti trigonal bipyramid, edges with two equivalent S(2)U4Ti trigonal bipyramids, edges with two equivalent S(1)U2Ti2 trigonal pyramids, and  a faceface with one S(4)U4Ti trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent U(1) and one Ti(1) atom to form distorted SU4Ti trigonal bipyramids that share corners with four equivalent S(3)U4Ti square pyramids,  a cornercorner with one S(2)U4Ti trigonal bipyramid, corners with four equivalent S(4)U4Ti trigonal bipyramids, corners with four equivalent S(1)U2Ti2 trigonal pyramids,  an edgeedge with one S(3)U4Ti square pyramid, edges with four equivalent S(2)U4Ti trigonal bipyramids, edges with four equivalent S(1)U2Ti2 trigonal pyramids, and  a faceface with one S(3)U4Ti square pyramid.
U2TiS5 crystallizes in the orthorhombic Pnma space group. U(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), two equivalent S(3), and two equivalent S(4) atoms. There is one shorter (2.80 Å) and one longer (2.83 Å) U(1)-S(1) bond length. There is one shorter (2.81 Å) and one longer (2.93 Å) U(1)-S(2) bond length. There is one shorter (2.80 Å) and one longer (2.81 Å) U(1)-S(3) bond length. There is one shorter (2.77 Å) and one longer (2.81 Å) U(1)-S(4) bond length. Ti(1) is bonded to one S(2), one S(3), one S(4), and four equivalent S(1) atoms to form distorted edge-sharing TiS7 pentagonal bipyramids. The Ti(1)-S(2) bond length is 2.61 Å. The Ti(1)-S(3) bond length is 2.66 Å. The Ti(1)-S(4) bond length is 2.47 Å. There are two shorter (2.45 Å) and two longer (2.60 Å) Ti(1)-S(1) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded to two equivalent U(1) and two equivalent Ti(1) atoms to form distorted SU2Ti2 trigonal pyramids that share corners with four equivalent S(3)U4Ti square pyramids, corners with two equivalent S(2)U4Ti trigonal bipyramids, corners with two equivalent S(4)U4Ti trigonal bipyramids, corners with six equivalent S(1)U2Ti2 trigonal pyramids,  an edgeedge with one S(3)U4Ti square pyramid, edges with two equivalent S(2)U4Ti trigonal bipyramids, edges with two equivalent S(4)U4Ti trigonal bipyramids, and  an edgeedge with one S(1)U2Ti2 trigonal pyramid. In the second S site, S(2) is bonded to four equivalent U(1) and one Ti(1) atom to form distorted SU4Ti trigonal bipyramids that share corners with five equivalent S(3)U4Ti square pyramids,  a cornercorner with one S(4)U4Ti trigonal bipyramid, corners with four equivalent S(2)U4Ti trigonal bipyramids, corners with four equivalent S(1)U2Ti2 trigonal pyramids, edges with two equivalent S(3)U4Ti square pyramids, edges with four equivalent S(4)U4Ti trigonal bipyramids, and edges with four equivalent S(1)U2Ti2 trigonal pyramids. In the third S site, S(3) is bonded to four equivalent U(1) and one Ti(1) atom to form SU4Ti square pyramids that share corners with four equivalent S(4)U4Ti trigonal bipyramids, corners with five equivalent S(2)U4Ti trigonal bipyramids, corners with eight equivalent S(1)U2Ti2 trigonal pyramids, edges with two equivalent S(3)U4Ti square pyramids,  an edgeedge with one S(4)U4Ti trigonal bipyramid, edges with two equivalent S(2)U4Ti trigonal bipyramids, edges with two equivalent S(1)U2Ti2 trigonal pyramids, and  a faceface with one S(4)U4Ti trigonal bipyramid. In the fourth S site, S(4) is bonded to four equivalent U(1) and one Ti(1) atom to form distorted SU4Ti trigonal bipyramids that share corners with four equivalent S(3)U4Ti square pyramids,  a cornercorner with one S(2)U4Ti trigonal bipyramid, corners with four equivalent S(4)U4Ti trigonal bipyramids, corners with four equivalent S(1)U2Ti2 trigonal pyramids,  an edgeedge with one S(3)U4Ti square pyramid, edges with four equivalent S(2)U4Ti trigonal bipyramids, edges with four equivalent S(1)U2Ti2 trigonal pyramids, and  a faceface with one S(3)U4Ti square pyramid.