CsBaVS4 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 10-coordinate geometry to one S(3), three equivalent S(2), and six equivalent S(1) atoms. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(2), three equivalent S(3), and four equivalent S(1) atoms. V(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 distorted single-bond geometry to three equivalent Cs(1), two equivalent Ba(1), and one V(1) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to three equivalent Cs(1), two equivalent Ba(1), and one V(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Cs(1), three equivalent Ba(1), and one V(1) atom.
CsBaVS4 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 10-coordinate geometry to one S(3), three equivalent S(2), and six equivalent S(1) atoms. The Cs(1)-S(3) bond length is 3.55 Å. There are two shorter (3.57 Å) and one longer (3.83 Å) Cs(1)-S(2) bond length. There are a spread of Cs(1)-S(1) bond distances ranging from 3.74-3.96 Å. Ba(1) is bonded in a 9-coordinate geometry to two equivalent S(2), three equivalent S(3), and four equivalent S(1) atoms. There is one shorter (3.22 Å) and one longer (3.72 Å) Ba(1)-S(2) bond length. There is one shorter (3.19 Å) and two longer (3.60 Å) Ba(1)-S(3) bond lengths. There are two shorter (3.26 Å) and two longer (3.40 Å) Ba(1)-S(1) bond lengths. V(1) is bonded in a tetrahedral geometry to one S(2), one S(3), and two equivalent S(1) atoms. The V(1)-S(2) bond length is 2.16 Å. The V(1)-S(3) bond length is 2.16 Å. Both V(1)-S(1) bond lengths are 2.15 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted single-bond geometry to three equivalent Cs(1), two equivalent Ba(1), and one V(1) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to three equivalent Cs(1), two equivalent Ba(1), and one V(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Cs(1), three equivalent Ba(1), and one V(1) atom.