Rb2PO3F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to three equivalent O(1), four equivalent O(2), and one F(1) atom. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to two equivalent O(1), four equivalent O(2), and one F(1) atom. P(1) is bonded in a tetrahedral geometry to one O(1), two equivalent O(2), and one F(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Rb(2), three equivalent Rb(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one P(1) atom. F(1) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(1) atom.
Rb2PO3F crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to three equivalent O(1), four equivalent O(2), and one F(1) atom. There are two shorter (3.08 Å) and one longer (3.13 Å) Rb(1)-O(1) bond length. There are two shorter (3.10 Å) and two longer (3.13 Å) Rb(1)-O(2) bond lengths. The Rb(1)-F(1) bond length is 2.86 Å. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to two equivalent O(1), four equivalent O(2), and one F(1) atom. There is one shorter (2.91 Å) and one longer (2.98 Å) Rb(2)-O(1) bond length. There are two shorter (2.83 Å) and two longer (2.89 Å) Rb(2)-O(2) bond lengths. The Rb(2)-F(1) bond length is 2.94 Å. P(1) is bonded in a tetrahedral geometry to one O(1), two equivalent O(2), and one F(1) atom. The P(1)-O(1) bond length is 1.51 Å. Both P(1)-O(2) bond lengths are 1.50 Å. The P(1)-F(1) bond length is 1.65 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to two equivalent Rb(2), three equivalent Rb(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one P(1) atom. F(1) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one P(1) atom.