Ba3TiS5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(2) and six equivalent S(1) atoms. In the second Ba site, Ba(2) is bonded in a distorted q6 geometry to two equivalent S(2) and eight equivalent S(1) atoms. Ti(1) is bonded in a tetrahedral geometry to four equivalent S(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), and one Ti(1) atom. In the second S site, S(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form corner-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°.
Ba3TiS5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to two equivalent S(2) and six equivalent S(1) atoms. Both Ba(1)-S(2) bond lengths are 3.20 Å. There are two shorter (3.12 Å) and four longer (3.40 Å) Ba(1)-S(1) bond lengths. In the second Ba site, Ba(2) is bonded in a distorted q6 geometry to two equivalent S(2) and eight equivalent S(1) atoms. Both Ba(2)-S(2) bond lengths are 3.49 Å. All Ba(2)-S(1) bond lengths are 3.53 Å. Ti(1) is bonded in a tetrahedral geometry to four equivalent S(1) atoms. All Ti(1)-S(1) bond lengths are 2.24 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(2), three equivalent Ba(1), and one Ti(1) atom. In the second S site, S(2) is bonded to two equivalent Ba(2) and four equivalent Ba(1) atoms to form corner-sharing SBa6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°.