K3PO3F2 crystallizes in the orthorhombic Fmm2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent O(1), four equivalent O(2), and two equivalent F(1) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to four equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. In the fourth K site, K(4) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. P(1) is bonded in a tetrahedral geometry to one O(1), two equivalent O(2), and one F(2) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(3), two equivalent K(4), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), two equivalent K(4), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(3), two equivalent K(4), and one P(1) atom. In the second F site, F(1) is bonded to one K(1), one K(2), two equivalent K(3), and two equivalent K(4) atoms to form corner-sharing FK6 octahedra. The corner-sharing octahedral tilt angles range from 2-29°.
K3PO3F2 crystallizes in the orthorhombic Fmm2 space group. There are four inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to two equivalent O(1), four equivalent O(2), and two equivalent F(1) atoms. Both K(1)-O(1) bond lengths are 2.68 Å. All K(1)-O(2) bond lengths are 3.02 Å. Both K(1)-F(1) bond lengths are 2.78 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to four equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. All K(2)-O(2) bond lengths are 3.02 Å. Both K(2)-F(1) bond lengths are 2.66 Å. Both K(2)-F(2) bond lengths are 2.74 Å. In the third K site, K(3) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. Both K(3)-O(1) bond lengths are 3.04 Å. Both K(3)-O(2) bond lengths are 2.70 Å. There is one shorter (2.64 Å) and one longer (2.66 Å) K(3)-F(1) bond length. Both K(3)-F(2) bond lengths are 3.12 Å. In the fourth K site, K(4) is bonded in a 10-coordinate geometry to two equivalent O(1), four equivalent O(2), two equivalent F(1), and two equivalent F(2) atoms. Both K(4)-O(1) bond lengths are 3.12 Å. There are two shorter (3.06 Å) and two longer (3.08 Å) K(4)-O(2) bond lengths. Both K(4)-F(1) bond lengths are 2.79 Å. Both K(4)-F(2) bond lengths are 3.11 Å. P(1) is bonded in a tetrahedral geometry to one O(1), two equivalent O(2), and one F(2) atom. The P(1)-O(1) bond length is 1.52 Å. Both P(1)-O(2) bond lengths are 1.52 Å. The P(1)-F(2) bond length is 1.69 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one K(1), two equivalent K(3), two equivalent K(4), and one P(1) atom. In the second O site, O(2) is bonded in a distorted single-bond geometry to one K(1), one K(2), one K(3), two equivalent K(4), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(2) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(3), two equivalent K(4), and one P(1) atom. In the second F site, F(1) is bonded to one K(1), one K(2), two equivalent K(3), and two equivalent K(4) atoms to form corner-sharing FK6 octahedra. The corner-sharing octahedral tilt angles range from 2-29°.