Cs4ZrO4 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. In the third Cs site, Cs(3) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. In the fourth Cs site, Cs(4) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted CsO4 tetrahedra that share corners with four equivalent Zr(1)O4 tetrahedra and edges with two equivalent Cs(4)O4 tetrahedra. Zr(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form ZrO4 tetrahedra that share corners with four equivalent Cs(4)O4 tetrahedra. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Zr(1) atom to form distorted edge-sharing OCs5Zr octahedra. In the second O site, O(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), and one Zr(1) atom. In the third O site, O(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Zr(1) atom. In the fourth O site, O(3) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(4), and one Zr(1) atom.
Cs4ZrO4 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. The Cs(1)-O(1) bond length is 3.39 Å. The Cs(1)-O(2) bond length is 3.06 Å. The Cs(1)-O(4) bond length is 3.14 Å. There is one shorter (2.94 Å) and one longer (3.33 Å) Cs(1)-O(3) bond length. In the second Cs site, Cs(2) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. The Cs(2)-O(1) bond length is 3.07 Å. There is one shorter (3.18 Å) and one longer (3.22 Å) Cs(2)-O(2) bond length. There is one shorter (3.03 Å) and one longer (3.17 Å) Cs(2)-O(4) bond length. In the third Cs site, Cs(3) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(2), and two equivalent O(4) atoms. The Cs(3)-O(1) bond length is 3.11 Å. There is one shorter (2.99 Å) and one longer (3.47 Å) Cs(3)-O(2) bond length. There is one shorter (2.90 Å) and one longer (3.01 Å) Cs(3)-O(4) bond length. In the fourth Cs site, Cs(4) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form distorted CsO4 tetrahedra that share corners with four equivalent Zr(1)O4 tetrahedra and edges with two equivalent Cs(4)O4 tetrahedra. There is one shorter (2.94 Å) and one longer (2.99 Å) Cs(4)-O(1) bond length. There is one shorter (2.96 Å) and one longer (3.03 Å) Cs(4)-O(3) bond length. Zr(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form ZrO4 tetrahedra that share corners with four equivalent Cs(4)O4 tetrahedra. The Zr(1)-O(1) bond length is 1.99 Å. The Zr(1)-O(2) bond length is 1.99 Å. The Zr(1)-O(3) bond length is 1.98 Å. The Zr(1)-O(4) bond length is 1.98 Å. There are four inequivalent O sites. In the first O site, O(4) is bonded to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Zr(1) atom to form distorted edge-sharing OCs5Zr octahedra. In the second O site, O(1) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(3), two equivalent Cs(4), and one Zr(1) atom. In the third O site, O(2) is bonded in a 6-coordinate geometry to one Cs(1), two equivalent Cs(2), two equivalent Cs(3), and one Zr(1) atom. In the fourth O site, O(3) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(4), and one Zr(1) atom.