KFe2P3(O4F3)2 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 11-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(8), one F(4), one F(5), two equivalent F(3), and two equivalent F(6) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), one O(6), one O(8), one F(1), and one F(2) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one P(3)O2F2 tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and corners with two equivalent P(1)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 33-39°. In the second Fe site, Fe(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(3)O2F2 tetrahedra, and corners with two equivalent P(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 33°. In the third Fe site, Fe(3) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(1)O3F tetrahedra, and corners with two equivalent P(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 39°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(8), and one F(5) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra and corners with two equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 33-44°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one F(3) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra, and  a cornercorner with one Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-46°. In the third P site, P(3) is bonded to one O(6), one O(7), one F(4), and one F(6) atom to form PO2F2 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-46°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Fe(3), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one Fe(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one K(1), one Fe(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one K(1), one Fe(1), and one P(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a single-bond geometry to two equivalent K(1) and one P(2) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to one K(1) and one P(3) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one K(1) and one P(1) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to two equivalent K(1) and one P(3) atom.
KFe2P3(O4F3)2 crystallizes in the triclinic P-1 space group. K(1) is bonded in a 11-coordinate geometry to one O(2), one O(3), one O(4), one O(5), one O(8), one F(4), one F(5), two equivalent F(3), and two equivalent F(6) atoms. The K(1)-O(2) bond length is 2.73 Å. The K(1)-O(3) bond length is 2.80 Å. The K(1)-O(4) bond length is 3.03 Å. The K(1)-O(5) bond length is 3.07 Å. The K(1)-O(8) bond length is 3.21 Å. The K(1)-F(4) bond length is 2.98 Å. The K(1)-F(5) bond length is 2.68 Å. There is one shorter (2.91 Å) and one longer (3.08 Å) K(1)-F(3) bond length. There is one shorter (2.99 Å) and one longer (3.05 Å) K(1)-F(6) bond length. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), one O(6), one O(8), one F(1), and one F(2) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one P(3)O2F2 tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and corners with two equivalent P(1)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 33-39°. The Fe(1)-O(1) bond length is 1.93 Å. The Fe(1)-O(3) bond length is 2.00 Å. The Fe(1)-O(6) bond length is 2.04 Å. The Fe(1)-O(8) bond length is 1.95 Å. The Fe(1)-F(1) bond length is 1.96 Å. The Fe(1)-F(2) bond length is 1.99 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(4), two equivalent O(7), and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(3)O2F2 tetrahedra, and corners with two equivalent P(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 33°. Both Fe(2)-O(4) bond lengths are 1.97 Å. Both Fe(2)-O(7) bond lengths are 2.02 Å. Both Fe(2)-F(2) bond lengths are 1.95 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(1)O3F tetrahedra, and corners with two equivalent P(2)O3F tetrahedra. The corner-sharing octahedral tilt angles are 39°. Both Fe(3)-O(2) bond lengths are 1.96 Å. Both Fe(3)-O(5) bond lengths are 2.02 Å. Both Fe(3)-F(1) bond lengths are 1.97 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(8), and one F(5) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra and corners with two equivalent Fe(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 33-44°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(8) bond length is 1.51 Å. The P(1)-F(5) bond length is 1.58 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(5), and one F(3) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra, and  a cornercorner with one Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-46°. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.51 Å. The P(2)-F(3) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(6), one O(7), one F(4), and one F(6) atom to form PO2F2 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and  a cornercorner with one Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-46°. The P(3)-O(6) bond length is 1.47 Å. The P(3)-O(7) bond length is 1.49 Å. The P(3)-F(4) bond length is 1.54 Å. The P(3)-F(6) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Fe(3), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one Fe(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one K(1), one Fe(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Fe(2) and one P(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one K(1), one Fe(1), and one P(1) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(3) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a single-bond geometry to two equivalent K(1) and one P(2) atom. In the fourth F site, F(4) is bonded in a single-bond geometry to one K(1) and one P(3) atom. In the fifth F site, F(5) is bonded in a distorted single-bond geometry to one K(1) and one P(1) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to two equivalent K(1) and one P(3) atom.