Cs3PO4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), and four equivalent O(1) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(3), and three equivalent O(1) atoms. P(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to two equivalent Cs(1), three equivalent Cs(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cs(1), four equivalent Cs(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(1), four equivalent Cs(2), and one P(1) atom.
Cs3PO4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), and four equivalent O(1) atoms. The Cs(1)-O(2) bond length is 2.94 Å. The Cs(1)-O(3) bond length is 3.00 Å. There are two shorter (3.14 Å) and two longer (3.21 Å) Cs(1)-O(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(3), and three equivalent O(1) atoms. There is one shorter (3.04 Å) and one longer (3.10 Å) Cs(2)-O(2) bond length. There is one shorter (3.02 Å) and one longer (3.23 Å) Cs(2)-O(3) bond length. There are a spread of Cs(2)-O(1) bond distances ranging from 3.14-3.42 Å. P(1) is bonded in a tetrahedral geometry to one O(2), one O(3), and two equivalent O(1) atoms. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.56 Å. Both P(1)-O(1) bond lengths are 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a single-bond geometry to two equivalent Cs(1), three equivalent Cs(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one Cs(1), four equivalent Cs(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Cs(1), four equivalent Cs(2), and one P(1) atom.