Cs2TiS3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 7-coordinate geometry to three equivalent S(2) and four equivalent S(1) atoms. Ti(1) is bonded to one S(2) and four equivalent S(1) atoms to form distorted edge-sharing TiS5 trigonal bipyramids. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing SCs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. In the second S site, S(2) is bonded in a distorted single-bond geometry to six equivalent Cs(1) and one Ti(1) atom.
Cs2TiS3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded in a 7-coordinate geometry to three equivalent S(2) and four equivalent S(1) atoms. There is one shorter (3.66 Å) and two longer (3.83 Å) Cs(1)-S(2) bond lengths. All Cs(1)-S(1) bond lengths are 3.52 Å. Ti(1) is bonded to one S(2) and four equivalent S(1) atoms to form distorted edge-sharing TiS5 trigonal bipyramids. The Ti(1)-S(2) bond length is 2.23 Å. All Ti(1)-S(1) bond lengths are 2.40 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing SCs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 34-48°. In the second S site, S(2) is bonded in a distorted single-bond geometry to six equivalent Cs(1) and one Ti(1) atom.