Cs2CrO4Cl5 crystallizes in the triclinic P1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(4), one Cl(5), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form distorted CsCl8 hexagonal bipyramids that share corners with two equivalent Cs(1)Cl8 hexagonal bipyramids,  a cornercorner with one Cr(1)ClO3 tetrahedra, and edges with two equivalent Cs(1)Cl8 hexagonal bipyramids. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cl(3), one Cl(5), two equivalent Cl(2), and two equivalent Cl(4) atoms. Cr(1) is bonded to one O(1), one O(2), one O(4), and one Cl(4) atom to form CrClO3 tetrahedra that share  a cornercorner with one Cs(1)Cl8 hexagonal bipyramid. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cr(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cr(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Cl(1) and one Cl(5) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one Cr(1) atom. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one O(3) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Cl(3) atom. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one Cs(2), two equivalent Cs(1), and one Cl(2) atom. In the fourth Cl site, Cl(4) is bonded to one Cs(1), two equivalent Cs(2), and one Cr(1) atom to form distorted corner-sharing ClCs3Cr trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one O(3) atom.
Cs2CrO4Cl5 crystallizes in the triclinic P1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(4), one Cl(5), two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms to form distorted CsCl8 hexagonal bipyramids that share corners with two equivalent Cs(1)Cl8 hexagonal bipyramids,  a cornercorner with one Cr(1)ClO3 tetrahedra, and edges with two equivalent Cs(1)Cl8 hexagonal bipyramids. The Cs(1)-Cl(4) bond length is 3.61 Å. The Cs(1)-Cl(5) bond length is 3.75 Å. There is one shorter (3.79 Å) and one longer (3.84 Å) Cs(1)-Cl(1) bond length. There is one shorter (3.51 Å) and one longer (3.64 Å) Cs(1)-Cl(2) bond length. There is one shorter (3.43 Å) and one longer (3.60 Å) Cs(1)-Cl(3) bond length. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to one Cl(3), one Cl(5), two equivalent Cl(2), and two equivalent Cl(4) atoms. The Cs(2)-Cl(3) bond length is 3.47 Å. The Cs(2)-Cl(5) bond length is 3.76 Å. There is one shorter (3.61 Å) and one longer (3.86 Å) Cs(2)-Cl(2) bond length. There is one shorter (3.46 Å) and one longer (3.49 Å) Cs(2)-Cl(4) bond length. Cr(1) is bonded to one O(1), one O(2), one O(4), and one Cl(4) atom to form CrClO3 tetrahedra that share  a cornercorner with one Cs(1)Cl8 hexagonal bipyramid. The Cr(1)-O(1) bond length is 1.62 Å. The Cr(1)-O(2) bond length is 1.62 Å. The Cr(1)-O(4) bond length is 1.62 Å. The Cr(1)-Cl(4) bond length is 2.27 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to one Cr(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one Cr(1) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Cl(1) and one Cl(5) atom. The O(3)-Cl(1) bond length is 1.73 Å. The O(3)-Cl(5) bond length is 1.71 Å. In the fourth O site, O(4) is bonded in a single-bond geometry to one Cr(1) atom. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to two equivalent Cs(1) and one O(3) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Cl(3) atom. The Cl(2)-Cl(3) bond length is 2.64 Å. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one Cs(2), two equivalent Cs(1), and one Cl(2) atom. In the fourth Cl site, Cl(4) is bonded to one Cs(1), two equivalent Cs(2), and one Cr(1) atom to form distorted corner-sharing ClCs3Cr trigonal pyramids. In the fifth Cl site, Cl(5) is bonded in a 3-coordinate geometry to one Cs(1), one Cs(2), and one O(3) atom.