Ba2S3 crystallizes in the tetragonal I4_1md space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent S(2) and six equivalent S(1) atoms. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to two equivalent S(1) and three equivalent S(2) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(2), three equivalent Ba(1), and one S(1) atom. In the second S site, S(2) is bonded to three equivalent Ba(1) and three equivalent Ba(2) atoms to form a mixture of distorted corner and edge-sharing SBa6 pentagonal pyramids.
Ba2S3 crystallizes in the tetragonal I4_1md space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to three equivalent S(2) and six equivalent S(1) atoms. There are two shorter (3.13 Å) and one longer (3.32 Å) Ba(1)-S(2) bond length. There are two shorter (3.21 Å) and four longer (3.38 Å) Ba(1)-S(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 5-coordinate geometry to two equivalent S(1) and three equivalent S(2) atoms. Both Ba(2)-S(1) bond lengths are 3.23 Å. There are two shorter (3.15 Å) and one longer (3.22 Å) Ba(2)-S(2) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to one Ba(2), three equivalent Ba(1), and one S(1) atom. The S(1)-S(1) bond length is 2.11 Å. In the second S site, S(2) is bonded to three equivalent Ba(1) and three equivalent Ba(2) atoms to form a mixture of distorted corner and edge-sharing SBa6 pentagonal pyramids.