K2MgFe4P6(O4F3)4 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(10), one O(16), one O(3), one O(6), one O(7), one F(11), one F(7), and one F(9) atom. In the second K site, K(2) is bonded in a 8-coordinate geometry to one O(15), one O(4), one O(5), one F(10), one F(11), one F(12), one F(5), and one F(6) atom. Mg(1) is bonded in a 5-coordinate geometry to one O(1), one O(15), one F(10), one F(3), and one F(8) atom. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(11), one O(5), one F(1), and one F(3) atom to form distorted FeO3F2 trigonal bipyramids that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. In the second Fe site, Fe(2) is bonded to one O(12), one O(16), one O(2), one O(6), one F(2), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra,  a cornercorner with one P(5)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 34-39°. In the third Fe site, Fe(3) is bonded to one O(13), one O(14), one O(7), one O(8), one F(3), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(5)O2F2 tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(3)O3F tetrahedra,  a cornercorner with one P(4)O3F tetrahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 34°. In the fourth Fe site, Fe(4) is bonded to one O(10), one O(3), one O(4), one O(9), 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 P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra,  a cornercorner with one P(3)O3F tetrahedra,  a cornercorner with one P(4)O3F tetrahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 39°. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(16), one O(3), and one F(10) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 32-33°. In the second P site, P(2) is bonded to one O(15), one O(2), one O(4), and one F(9) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra and  a cornercorner with one Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. In the third P site, P(3) is bonded to one O(10), one O(6), one O(7), and one F(6) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-44°. In the fourth P site, P(4) is bonded to one O(5), one O(8), one O(9), and one F(5) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-44°. In the fifth P site, P(5) is bonded to one O(12), one O(14), one F(12), and one F(7) atom to form PO2F2 tetrahedra that share  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 42-49°. In the sixth P site, P(6) is bonded to one O(11), one O(13), one F(11), and one F(8) atom to form PO2F2 tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 46°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Mg(1), one Fe(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one Fe(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one K(2), one Fe(4), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(2), one Fe(1), and one P(4) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one K(1), one Fe(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one P(4) atom. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one K(1), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(6) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Fe(3) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Fe(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a 2-coordinate geometry to one K(2), one Mg(1), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(2), and one P(1) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one Fe(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one Fe(4) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one Fe(1), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Fe(2) and one Fe(3) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one K(2) and one P(4) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one K(2) and one P(3) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one K(1) and one P(5) atom. In the eighth F site, F(8) is bonded in a distorted bent 120 degrees geometry to one Mg(1) and one P(6) atom. In the ninth F site, F(9) is bonded in a distorted single-bond geometry to one K(1) and one P(2) atom. In the tenth F site, F(10) is bonded in a distorted L-shaped geometry to one K(2), one Mg(1), and one P(1) atom. In the eleventh F site, F(11) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one P(6) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to one K(2) and one P(5) atom.
K2MgFe4P6(O4F3)4 crystallizes in the triclinic P1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one O(10), one O(16), one O(3), one O(6), one O(7), one F(11), one F(7), and one F(9) atom. The K(1)-O(10) bond length is 3.21 Å. The K(1)-O(16) bond length is 3.15 Å. The K(1)-O(3) bond length is 2.86 Å. The K(1)-O(6) bond length is 2.92 Å. The K(1)-O(7) bond length is 3.02 Å. The K(1)-F(11) bond length is 3.21 Å. The K(1)-F(7) bond length is 2.86 Å. The K(1)-F(9) bond length is 2.79 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to one O(15), one O(4), one O(5), one F(10), one F(11), one F(12), one F(5), and one F(6) atom. The K(2)-O(15) bond length is 2.89 Å. The K(2)-O(4) bond length is 2.98 Å. The K(2)-O(5) bond length is 2.77 Å. The K(2)-F(10) bond length is 3.10 Å. The K(2)-F(11) bond length is 2.94 Å. The K(2)-F(12) bond length is 3.17 Å. The K(2)-F(5) bond length is 3.18 Å. The K(2)-F(6) bond length is 2.96 Å. Mg(1) is bonded in a 5-coordinate geometry to one O(1), one O(15), one F(10), one F(3), and one F(8) atom. The Mg(1)-O(1) bond length is 2.10 Å. The Mg(1)-O(15) bond length is 1.99 Å. The Mg(1)-F(10) bond length is 2.08 Å. The Mg(1)-F(3) bond length is 1.87 Å. The Mg(1)-F(8) bond length is 2.06 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(11), one O(5), one F(1), and one F(3) atom to form distorted FeO3F2 trigonal bipyramids that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 39-46°. The Fe(1)-O(1) bond length is 2.15 Å. The Fe(1)-O(11) bond length is 2.07 Å. The Fe(1)-O(5) bond length is 2.02 Å. The Fe(1)-F(1) bond length is 2.04 Å. The Fe(1)-F(3) bond length is 2.26 Å. In the second Fe site, Fe(2) is bonded to one O(12), one O(16), one O(2), one O(6), one F(2), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra,  a cornercorner with one P(5)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(3)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 34-39°. The Fe(2)-O(12) bond length is 2.04 Å. The Fe(2)-O(16) bond length is 2.06 Å. The Fe(2)-O(2) bond length is 1.99 Å. The Fe(2)-O(6) bond length is 2.00 Å. The Fe(2)-F(2) bond length is 2.03 Å. The Fe(2)-F(4) bond length is 1.92 Å. In the third Fe site, Fe(3) is bonded to one O(13), one O(14), one O(7), one O(8), one F(3), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(5)O2F2 tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(3)O3F tetrahedra,  a cornercorner with one P(4)O3F tetrahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 34°. The Fe(3)-O(13) bond length is 2.19 Å. The Fe(3)-O(14) bond length is 2.18 Å. The Fe(3)-O(7) bond length is 2.04 Å. The Fe(3)-O(8) bond length is 2.10 Å. The Fe(3)-F(3) bond length is 2.22 Å. The Fe(3)-F(4) bond length is 2.08 Å. In the fourth Fe site, Fe(4) is bonded to one O(10), one O(3), one O(4), one O(9), 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 P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra,  a cornercorner with one P(3)O3F tetrahedra,  a cornercorner with one P(4)O3F tetrahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 39°. The Fe(4)-O(10) bond length is 2.01 Å. The Fe(4)-O(3) bond length is 2.07 Å. The Fe(4)-O(4) bond length is 2.01 Å. The Fe(4)-O(9) bond length is 2.02 Å. The Fe(4)-F(1) bond length is 1.96 Å. The Fe(4)-F(2) bond length is 2.00 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(16), one O(3), and one F(10) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 32-33°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(16) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-F(10) bond length is 1.72 Å. In the second P site, P(2) is bonded to one O(15), one O(2), one O(4), and one F(9) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra and  a cornercorner with one Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. The P(2)-O(15) bond length is 1.54 Å. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.52 Å. The P(2)-F(9) bond length is 1.60 Å. In the third P site, P(3) is bonded to one O(10), one O(6), one O(7), and one F(6) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Fe(4)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 34-44°. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(6) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.51 Å. The P(3)-F(6) bond length is 1.61 Å. In the fourth P site, P(4) is bonded to one O(5), one O(8), one O(9), and one F(5) atom to form PO3F tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O4F2 octahedra, and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 42-44°. The P(4)-O(5) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.52 Å. The P(4)-O(9) bond length is 1.53 Å. The P(4)-F(5) bond length is 1.61 Å. In the fifth P site, P(5) is bonded to one O(12), one O(14), one F(12), and one F(7) atom to form PO2F2 tetrahedra that share  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 42-49°. The P(5)-O(12) bond length is 1.49 Å. The P(5)-O(14) bond length is 1.49 Å. The P(5)-F(12) bond length is 1.58 Å. The P(5)-F(7) bond length is 1.57 Å. In the sixth P site, P(6) is bonded to one O(11), one O(13), one F(11), and one F(8) atom to form PO2F2 tetrahedra that share  a cornercorner with one Fe(3)O4F2 octahedra and  a cornercorner with one Fe(1)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles are 46°. The P(6)-O(11) bond length is 1.48 Å. The P(6)-O(13) bond length is 1.48 Å. The P(6)-F(11) bond length is 1.59 Å. The P(6)-F(8) bond length is 1.65 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Mg(1), one Fe(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one K(1), one Fe(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one K(2), one Fe(4), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one K(2), one Fe(1), and one P(4) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one K(1), one Fe(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Fe(3) and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Fe(4) and one P(4) atom. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one K(1), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(6) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one Fe(2) and one P(5) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 120 degrees geometry to one Fe(3) and one P(6) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 120 degrees geometry to one Fe(3) and one P(5) atom. In the fifteenth O site, O(15) is bonded in a 2-coordinate geometry to one K(2), one Mg(1), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(2), and one P(1) atom. There are twelve inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 120 degrees geometry to one Fe(1) and one Fe(4) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one Fe(2) and one Fe(4) atom. In the third F site, F(3) is bonded in a 3-coordinate geometry to one Mg(1), one Fe(1), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one Fe(2) and one Fe(3) atom. In the fifth F site, F(5) is bonded in a single-bond geometry to one K(2) and one P(4) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one K(2) and one P(3) atom. In the seventh F site, F(7) is bonded in a distorted single-bond geometry to one K(1) and one P(5) atom. In the eighth F site, F(8) is bonded in a distorted bent 120 degrees geometry to one Mg(1) and one P(6) atom. In the ninth F site, F(9) is bonded in a distorted single-bond geometry to one K(1) and one P(2) atom. In the tenth F site, F(10) is bonded in a distorted L-shaped geometry to one K(2), one Mg(1), and one P(1) atom. In the eleventh F site, F(11) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one P(6) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to one K(2) and one P(5) atom.