Cs2TmOCl5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(4), and three equivalent Cl(3) atoms. Tm(1) is bonded in a distorted octahedral geometry to one O(1), one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. O(1) is bonded in a single-bond geometry to one Tm(1) and one Cl(2) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tm(1) atom. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Tm(1), and one O(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one Tm(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tm(1) atom.
Cs2TmOCl5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(4), and three equivalent Cl(3) atoms. There is one shorter (3.61 Å) and one longer (3.78 Å) Cs(1)-Cl(1) bond length. There is one shorter (3.56 Å) and one longer (4.13 Å) Cs(1)-Cl(2) bond length. There is one shorter (3.65 Å) and one longer (3.96 Å) Cs(1)-Cl(4) bond length. There are a spread of Cs(1)-Cl(3) bond distances ranging from 3.67-3.93 Å. Tm(1) is bonded in a distorted octahedral geometry to one O(1), one Cl(1), one Cl(2), one Cl(4), and two equivalent Cl(3) atoms. The Tm(1)-O(1) bond length is 2.24 Å. The Tm(1)-Cl(1) bond length is 2.57 Å. The Tm(1)-Cl(2) bond length is 2.73 Å. The Tm(1)-Cl(4) bond length is 2.57 Å. Both Tm(1)-Cl(3) bond lengths are 2.58 Å. O(1) is bonded in a single-bond geometry to one Tm(1) and one Cl(2) atom. The O(1)-Cl(2) bond length is 2.42 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tm(1) atom. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to four equivalent Cs(1), one Tm(1), and one O(1) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to three equivalent Cs(1) and one Tm(1) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Tm(1) atom.