Ba3(OCl)2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent Cl(2), and three equivalent Cl(1) atoms. In the second Ba site, Ba(2) is bonded in a 4-coordinate geometry to four equivalent O(1), one Cl(1), and two equivalent Cl(2) atoms. In the third Ba site, Ba(3) is bonded in a distorted L-shaped geometry to two equivalent O(1), one Cl(1), and three equivalent Cl(2) atoms. O(1) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms to form a mixture of corner and edge-sharing OBa4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), and three equivalent Ba(1) atoms. In the second Cl site, Cl(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and three equivalent Ba(3) atoms.
Ba3(OCl)2 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 2-coordinate geometry to two equivalent O(1), two equivalent Cl(2), and three equivalent Cl(1) atoms. Both Ba(1)-O(1) bond lengths are 2.45 Å. There is one shorter (3.27 Å) and one longer (3.33 Å) Ba(1)-Cl(2) bond length. There is one shorter (3.62 Å) and two longer (3.71 Å) Ba(1)-Cl(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 4-coordinate geometry to four equivalent O(1), one Cl(1), and two equivalent Cl(2) atoms. There are two shorter (2.57 Å) and two longer (2.63 Å) Ba(2)-O(1) bond lengths. The Ba(2)-Cl(1) bond length is 3.57 Å. Both Ba(2)-Cl(2) bond lengths are 3.71 Å. In the third Ba site, Ba(3) is bonded in a distorted L-shaped geometry to two equivalent O(1), one Cl(1), and three equivalent Cl(2) atoms. Both Ba(3)-O(1) bond lengths are 2.39 Å. The Ba(3)-Cl(1) bond length is 3.40 Å. There is one shorter (3.45 Å) and two longer (3.90 Å) Ba(3)-Cl(2) bond lengths. O(1) is bonded to one Ba(1), one Ba(3), and two equivalent Ba(2) atoms to form a mixture of corner and edge-sharing OBa4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Ba(2), one Ba(3), and three equivalent Ba(1) atoms. In the second Cl site, Cl(2) is bonded in a 7-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and three equivalent Ba(3) atoms.