Cs3OCl crystallizes in the orthorhombic Pnma space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted single-bond geometry to one O(1) and four equivalent Cl(1) atoms. In the second Cs site, Cs(2) is bonded in a 3-coordinate geometry to three equivalent O(1) and two equivalent Cl(1) atoms. In the third Cs site, Cs(3) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent Cl(1) atoms. O(1) is bonded to one Cs(1), two equivalent Cs(3), and three equivalent Cs(2) atoms to form edge-sharing OCs6 octahedra. Cl(1) is bonded in a 9-coordinate geometry to two equivalent Cs(2), three equivalent Cs(3), and four equivalent Cs(1) atoms.
Cs3OCl crystallizes in the orthorhombic Pnma space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a distorted single-bond geometry to one O(1) and four equivalent Cl(1) atoms. The Cs(1)-O(1) bond length is 2.69 Å. There are two shorter (3.58 Å) and two longer (3.59 Å) Cs(1)-Cl(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 3-coordinate geometry to three equivalent O(1) and two equivalent Cl(1) atoms. All Cs(2)-O(1) bond lengths are 2.95 Å. There is one shorter (3.89 Å) and one longer (3.97 Å) Cs(2)-Cl(1) bond length. In the third Cs site, Cs(3) is bonded in a 5-coordinate geometry to two equivalent O(1) and three equivalent Cl(1) atoms. Both Cs(3)-O(1) bond lengths are 2.90 Å. There are two shorter (3.69 Å) and one longer (3.71 Å) Cs(3)-Cl(1) bond length. O(1) is bonded to one Cs(1), two equivalent Cs(3), and three equivalent Cs(2) atoms to form edge-sharing OCs6 octahedra. Cl(1) is bonded in a 9-coordinate geometry to two equivalent Cs(2), three equivalent Cs(3), and four equivalent Cs(1) atoms.