Cs4PbO4 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 6-coordinate geometry to one O(3), two equivalent O(1), and three equivalent O(4) atoms. In the second Cs site, Cs(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted CsO4 trigonal pyramids that share corners with four equivalent Pb(1)O4 tetrahedra and  an edgeedge with one Cs(2)O4 trigonal pyramid. 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(3) atoms. In the fourth Cs site, Cs(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(4) atoms. Pb(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PbO4 tetrahedra that share corners with four equivalent Cs(2)O4 trigonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Pb(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Cs(4), two equivalent Cs(2), two equivalent Cs(3), and one Pb(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Pb(1) atom. In the fourth O site, O(4) is bonded to two equivalent Cs(4), three equivalent Cs(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OCs5Pb octahedra. The corner-sharing octahedral tilt angles range from 42-45°.
Cs4PbO4 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 6-coordinate geometry to one O(3), two equivalent O(1), and three equivalent O(4) atoms. The Cs(1)-O(3) bond length is 3.39 Å. There is one shorter (3.18 Å) and one longer (3.70 Å) Cs(1)-O(1) bond length. There are a spread of Cs(1)-O(4) bond distances ranging from 3.00-3.40 Å. In the second Cs site, Cs(2) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form distorted CsO4 trigonal pyramids that share corners with four equivalent Pb(1)O4 tetrahedra and  an edgeedge with one Cs(2)O4 trigonal pyramid. The Cs(2)-O(1) bond length is 2.95 Å. The Cs(2)-O(3) bond length is 2.89 Å. There is one shorter (2.86 Å) and one longer (2.96 Å) Cs(2)-O(2) 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(3) atoms. The Cs(3)-O(1) bond length is 3.07 Å. There is one shorter (3.11 Å) and one longer (3.16 Å) Cs(3)-O(2) bond length. Both Cs(3)-O(3) bond lengths are 3.16 Å. In the fourth Cs site, Cs(4) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(4) atoms. The Cs(4)-O(1) bond length is 2.86 Å. The Cs(4)-O(2) bond length is 3.49 Å. The Cs(4)-O(3) bond length is 3.11 Å. There is one shorter (2.83 Å) and one longer (3.08 Å) Cs(4)-O(4) bond length. Pb(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PbO4 tetrahedra that share corners with four equivalent Cs(2)O4 trigonal pyramids. The Pb(1)-O(1) bond length is 2.09 Å. The Pb(1)-O(2) bond length is 2.10 Å. The Pb(1)-O(3) bond length is 2.10 Å. The Pb(1)-O(4) bond length is 2.09 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Pb(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Cs(4), two equivalent Cs(2), two equivalent Cs(3), and one Pb(1) atom. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Cs(1), one Cs(2), one Cs(4), two equivalent Cs(3), and one Pb(1) atom. In the fourth O site, O(4) is bonded to two equivalent Cs(4), three equivalent Cs(1), and one Pb(1) atom to form a mixture of distorted corner and edge-sharing OCs5Pb octahedra. The corner-sharing octahedral tilt angles range from 42-45°.