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 9-coordinate geometry to one O(10), one O(16), one O(3), one O(6), one O(7), one F(12), one F(6), one F(7), and one F(9) atom. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(14), one O(15), one O(5), one O(8), one F(10), one F(11), one F(12), one F(5), and one F(6) atom. Mg(1) is bonded to one O(4), one O(9), one F(10), one F(2), and one F(8) atom to form distorted MgO2F3 trigonal bipyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 42°. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(11), one O(15), one O(5), one F(1), and one F(3) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 35°. 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 P(5)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra,  a cornercorner with one P(3)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 35°. 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(1)O4F2 octahedra,  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, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 35°. In the fourth Fe site, Fe(4) is bonded to one O(10), one O(3), one O(4), and one F(1) atom to form distorted FeO3F tetrahedra that share  a cornercorner with one Fe(1)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, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 36°. 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(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-28°. 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(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-36°. 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)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 35-37°. 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(1)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-33°. 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 41-47°. 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(1)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-49°. There are sixteen 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 bent 150 degrees geometry to one Fe(2) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mg(1), 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 3-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 3-coordinate geometry to one K(1), one Fe(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one K(2), one Fe(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Mg(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted 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 2-coordinate geometry to one K(2), one Fe(3), and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one K(2), one Fe(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 bent 150 degrees geometry to one Fe(1) and one Fe(4) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Mg(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to 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 2-coordinate geometry to one K(1), 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 bent 150 degrees 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(2) and one P(6) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to one K(1), 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 9-coordinate geometry to one O(10), one O(16), one O(3), one O(6), one O(7), one F(12), one F(6), one F(7), and one F(9) atom. The K(1)-O(10) bond length is 3.20 Å. The K(1)-O(16) bond length is 3.21 Å. The K(1)-O(3) bond length is 2.98 Å. The K(1)-O(6) bond length is 2.84 Å. The K(1)-O(7) bond length is 2.89 Å. The K(1)-F(12) bond length is 3.05 Å. The K(1)-F(6) bond length is 3.20 Å. The K(1)-F(7) bond length is 2.87 Å. The K(1)-F(9) bond length is 2.86 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(14), one O(15), one O(5), one O(8), one F(10), one F(11), one F(12), one F(5), and one F(6) atom. The K(2)-O(14) bond length is 3.21 Å. The K(2)-O(15) bond length is 3.04 Å. The K(2)-O(5) bond length is 2.67 Å. The K(2)-O(8) bond length is 2.81 Å. The K(2)-F(10) bond length is 3.28 Å. The K(2)-F(11) bond length is 2.86 Å. The K(2)-F(12) bond length is 3.22 Å. The K(2)-F(5) bond length is 3.11 Å. The K(2)-F(6) bond length is 2.56 Å. Mg(1) is bonded to one O(4), one O(9), one F(10), one F(2), and one F(8) atom to form distorted MgO2F3 trigonal bipyramids that share  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 42°. The Mg(1)-O(4) bond length is 2.02 Å. The Mg(1)-O(9) bond length is 1.94 Å. The Mg(1)-F(10) bond length is 2.05 Å. The Mg(1)-F(2) bond length is 1.85 Å. The Mg(1)-F(8) bond length is 2.15 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(15), one O(5), one F(1), and one F(3) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra,  a cornercorner with one P(6)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 35°. The Fe(1)-O(1) bond length is 1.98 Å. The Fe(1)-O(11) bond length is 2.10 Å. The Fe(1)-O(15) bond length is 2.07 Å. The Fe(1)-O(5) bond length is 2.01 Å. The Fe(1)-F(1) bond length is 1.95 Å. The Fe(1)-F(3) bond length is 1.92 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 P(5)O2F2 tetrahedra,  a cornercorner with one P(1)O3F tetrahedra,  a cornercorner with one P(2)O3F tetrahedra,  a cornercorner with one P(3)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 35°. The Fe(2)-O(12) bond length is 2.03 Å. The Fe(2)-O(16) bond length is 2.03 Å. The Fe(2)-O(2) bond length is 2.00 Å. The Fe(2)-O(6) bond length is 2.02 Å. The Fe(2)-F(2) bond length is 2.02 Å. The Fe(2)-F(4) bond length is 1.91 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(1)O4F2 octahedra,  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, and  a cornercorner with one P(4)O3F tetrahedra. The corner-sharing octahedral tilt angles are 35°. The Fe(3)-O(13) bond length is 2.22 Å. The Fe(3)-O(14) bond length is 2.20 Å. The Fe(3)-O(7) bond length is 2.04 Å. The Fe(3)-O(8) bond length is 2.05 Å. The Fe(3)-F(3) bond length is 2.25 Å. The Fe(3)-F(4) bond length is 2.22 Å. In the fourth Fe site, Fe(4) is bonded to one O(10), one O(3), one O(4), and one F(1) atom to form distorted FeO3F tetrahedra that share  a cornercorner with one Fe(1)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, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 36°. The Fe(4)-O(10) bond length is 2.00 Å. The Fe(4)-O(3) bond length is 2.01 Å. The Fe(4)-O(4) bond length is 2.13 Å. The Fe(4)-F(1) bond length is 1.98 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(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-28°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(16) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.51 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(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one Fe(4)O3F tetrahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-36°. The P(2)-O(15) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-F(9) bond length is 1.59 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)O3F tetrahedra. The corner-sharing octahedral tilt angles range from 35-37°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(6) bond length is 1.52 Å. The P(3)-O(7) bond length is 1.51 Å. The P(3)-F(6) bond length is 1.63 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(1)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 27-33°. The P(4)-O(5) bond length is 1.52 Å. The P(4)-O(8) bond length is 1.51 Å. The P(4)-O(9) bond length is 1.52 Å. The P(4)-F(5) bond length is 1.62 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 41-47°. 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 1.59 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(1)O4F2 octahedra,  a cornercorner with one Fe(3)O4F2 octahedra, and  a cornercorner with one Mg(1)O2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 41-49°. The P(6)-O(11) bond length is 1.49 Å. The P(6)-O(13) bond length is 1.48 Å. The P(6)-F(11) bond length is 1.58 Å. The P(6)-F(8) bond length is 1.64 Å. There are sixteen 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 bent 150 degrees geometry to one Fe(2) and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(4), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mg(1), 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 3-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 3-coordinate geometry to one K(1), one Fe(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one K(2), one Fe(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Mg(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one K(1), one Fe(4), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted 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 2-coordinate geometry to one K(2), one Fe(3), and one P(5) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one K(2), one Fe(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 bent 150 degrees geometry to one Fe(1) and one Fe(4) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Mg(1) and one Fe(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to 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 2-coordinate geometry to one K(1), 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 bent 150 degrees 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(2) and one P(6) atom. In the twelfth F site, F(12) is bonded in a single-bond geometry to one K(1), one K(2), and one P(5) atom.