Ba3GaS4Br crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(2), one S(3), four equivalent S(1), and two equivalent Br(1) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to two equivalent S(2), two equivalent S(3), three equivalent S(1), and two equivalent Br(1) atoms. Ga(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(1), three equivalent Ba(2), and one Ga(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), four equivalent Ba(2), and one Ga(1) atom. In the third S site, S(3) is bonded to one Ba(1), four equivalent Ba(2), and one Ga(1) atom to form distorted SBa5Ga octahedra that share corners with four equivalent Br(1)Ba6 octahedra, edges with two equivalent S(3)Ba5Ga octahedra, and faces with two equivalent Br(1)Ba6 octahedra. The corner-sharing octahedral tilt angles range from 29-49°. Br(1) is bonded to two equivalent Ba(1) and four equivalent Ba(2) atoms to form distorted BrBa6 octahedra that share corners with four equivalent S(3)Ba5Ga octahedra, corners with six equivalent Br(1)Ba6 octahedra, and faces with two equivalent S(3)Ba5Ga octahedra. The corner-sharing octahedral tilt angles range from 29-49°.
Ba3GaS4Br crystallizes in the orthorhombic Pnma space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 8-coordinate geometry to one S(2), one S(3), four equivalent S(1), and two equivalent Br(1) atoms. The Ba(1)-S(2) bond length is 3.05 Å. The Ba(1)-S(3) bond length is 3.30 Å. There are two shorter (3.10 Å) and two longer (3.26 Å) Ba(1)-S(1) bond lengths. There is one shorter (3.31 Å) and one longer (3.70 Å) Ba(1)-Br(1) bond length. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to two equivalent S(2), two equivalent S(3), three equivalent S(1), and two equivalent Br(1) atoms. There is one shorter (3.30 Å) and one longer (3.59 Å) Ba(2)-S(2) bond length. There is one shorter (3.27 Å) and one longer (3.30 Å) Ba(2)-S(3) bond length. There are a spread of Ba(2)-S(1) bond distances ranging from 3.43-3.68 Å. There is one shorter (3.40 Å) and one longer (3.45 Å) Ba(2)-Br(1) bond length. Ga(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Ga(1)-S(2) bond length is 2.27 Å. The Ga(1)-S(3) bond length is 2.28 Å. Both Ga(1)-S(1) bond lengths are 2.24 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 6-coordinate geometry to two equivalent Ba(1), three equivalent Ba(2), and one Ga(1) atom. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Ba(1), four equivalent Ba(2), and one Ga(1) atom. In the third S site, S(3) is bonded to one Ba(1), four equivalent Ba(2), and one Ga(1) atom to form distorted SBa5Ga octahedra that share corners with four equivalent Br(1)Ba6 octahedra, edges with two equivalent S(3)Ba5Ga octahedra, and faces with two equivalent Br(1)Ba6 octahedra. The corner-sharing octahedral tilt angles range from 29-49°. Br(1) is bonded to two equivalent Ba(1) and four equivalent Ba(2) atoms to form distorted BrBa6 octahedra that share corners with four equivalent S(3)Ba5Ga octahedra, corners with six equivalent Br(1)Ba6 octahedra, and faces with two equivalent S(3)Ba5Ga octahedra. The corner-sharing octahedral tilt angles range from 29-49°.