Mn3Fe9P4 crystallizes in the triclinic P1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 2-coordinate geometry to one Fe(6), one Fe(8), one P(1), and one P(3) atom. In the second Mn site, Mn(2) is bonded in a 2-coordinate geometry to one Fe(7), one Fe(8), one P(2), and one P(4) atom. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to one Fe(1), two equivalent Fe(8), one P(2), and one P(3) atom. There are nine inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 3-coordinate geometry to one Mn(3), one Fe(8), one P(1), and one P(4) atom. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(1) atoms. In the third Fe site, Fe(3) is bonded in a 4-coordinate geometry to one Fe(8), one P(3), one P(4), and two equivalent P(2) atoms. In the fourth Fe site, Fe(4) is bonded in a 4-coordinate geometry to one Fe(8), one P(1), one P(2), and two equivalent P(3) atoms. In the fifth Fe site, Fe(5) is bonded in a 4-coordinate geometry to one Fe(8), one P(1), one P(2), and two equivalent P(4) atoms. In the sixth Fe site, Fe(6) is bonded in a 4-coordinate geometry to one Mn(1), one P(1), one P(2), and one P(3) atom. In the seventh Fe site, Fe(7) is bonded in a 4-coordinate geometry to one Mn(2), one P(1), one P(2), and one P(4) atom. In the eighth Fe site, Fe(8) is bonded in a 13-coordinate geometry to one Mn(1), one Mn(2), two equivalent Mn(3), one Fe(1), one Fe(3), one Fe(4), one Fe(5), two equivalent Fe(9), one P(2), one P(3), and one P(4) atom. In the ninth Fe site, Fe(9) is bonded in a 3-coordinate geometry to two equivalent Fe(8), one P(1), one P(3), and one P(4) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Mn(1), one Fe(1), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(9), and two equivalent Fe(2) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Mn(2), one Mn(3), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(8), and two equivalent Fe(3) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Mn(1), one Mn(3), one Fe(2), one Fe(3), one Fe(6), one Fe(8), one Fe(9), and two equivalent Fe(4) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Mn(2), one Fe(1), one Fe(2), one Fe(3), one Fe(7), one Fe(8), one Fe(9), and two equivalent Fe(5) atoms.
Mn3Fe9P4 crystallizes in the triclinic P1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded in a 2-coordinate geometry to one Fe(6), one Fe(8), one P(1), and one P(3) atom. The Mn(1)-Fe(6) bond length is 2.52 Å. The Mn(1)-Fe(8) bond length is 2.75 Å. The Mn(1)-P(1) bond length is 2.30 Å. The Mn(1)-P(3) bond length is 2.35 Å. In the second Mn site, Mn(2) is bonded in a 2-coordinate geometry to one Fe(7), one Fe(8), one P(2), and one P(4) atom. The Mn(2)-Fe(7) bond length is 2.52 Å. The Mn(2)-Fe(8) bond length is 2.78 Å. The Mn(2)-P(2) bond length is 2.30 Å. The Mn(2)-P(4) bond length is 2.35 Å. In the third Mn site, Mn(3) is bonded in a 4-coordinate geometry to one Fe(1), two equivalent Fe(8), one P(2), and one P(3) atom. The Mn(3)-Fe(1) bond length is 2.39 Å. There is one shorter (2.52 Å) and one longer (2.63 Å) Mn(3)-Fe(8) bond length. The Mn(3)-P(2) bond length is 2.35 Å. The Mn(3)-P(3) bond length is 2.29 Å. There are nine inequivalent Fe sites. In the first Fe site, Fe(1) is bonded in a 3-coordinate geometry to one Mn(3), one Fe(8), one P(1), and one P(4) atom. The Fe(1)-Fe(8) bond length is 2.73 Å. The Fe(1)-P(1) bond length is 2.35 Å. The Fe(1)-P(4) bond length is 2.28 Å. In the second Fe site, Fe(2) is bonded in a 4-coordinate geometry to one P(3), one P(4), and two equivalent P(1) atoms. The Fe(2)-P(3) bond length is 2.31 Å. The Fe(2)-P(4) bond length is 2.30 Å. There is one shorter (2.28 Å) and one longer (2.31 Å) Fe(2)-P(1) bond length. In the third Fe site, Fe(3) is bonded in a 4-coordinate geometry to one Fe(8), one P(3), one P(4), and two equivalent P(2) atoms. The Fe(3)-Fe(8) bond length is 2.49 Å. The Fe(3)-P(3) bond length is 2.29 Å. The Fe(3)-P(4) bond length is 2.31 Å. There is one shorter (2.29 Å) and one longer (2.30 Å) Fe(3)-P(2) bond length. In the fourth Fe site, Fe(4) is bonded in a 4-coordinate geometry to one Fe(8), one P(1), one P(2), and two equivalent P(3) atoms. The Fe(4)-Fe(8) bond length is 2.62 Å. The Fe(4)-P(1) bond length is 2.31 Å. The Fe(4)-P(2) bond length is 2.30 Å. There is one shorter (2.27 Å) and one longer (2.31 Å) Fe(4)-P(3) bond length. In the fifth Fe site, Fe(5) is bonded in a 4-coordinate geometry to one Fe(8), one P(1), one P(2), and two equivalent P(4) atoms. The Fe(5)-Fe(8) bond length is 2.56 Å. The Fe(5)-P(1) bond length is 2.31 Å. The Fe(5)-P(2) bond length is 2.30 Å. There is one shorter (2.28 Å) and one longer (2.31 Å) Fe(5)-P(4) bond length. In the sixth Fe site, Fe(6) is bonded in a 4-coordinate geometry to one Mn(1), one P(1), one P(2), and one P(3) atom. The Fe(6)-P(1) bond length is 2.24 Å. The Fe(6)-P(2) bond length is 2.38 Å. The Fe(6)-P(3) bond length is 2.32 Å. In the seventh Fe site, Fe(7) is bonded in a 4-coordinate geometry to one Mn(2), one P(1), one P(2), and one P(4) atom. The Fe(7)-P(1) bond length is 2.38 Å. The Fe(7)-P(2) bond length is 2.25 Å. The Fe(7)-P(4) bond length is 2.32 Å. In the eighth Fe site, Fe(8) is bonded in a 13-coordinate geometry to one Mn(1), one Mn(2), two equivalent Mn(3), one Fe(1), one Fe(3), one Fe(4), one Fe(5), two equivalent Fe(9), one P(2), one P(3), and one P(4) atom. There is one shorter (2.68 Å) and one longer (2.69 Å) Fe(8)-Fe(9) bond length. The Fe(8)-P(2) bond length is 2.33 Å. The Fe(8)-P(3) bond length is 2.24 Å. The Fe(8)-P(4) bond length is 2.40 Å. In the ninth Fe site, Fe(9) is bonded in a 3-coordinate geometry to two equivalent Fe(8), one P(1), one P(3), and one P(4) atom. The Fe(9)-P(1) bond length is 2.32 Å. The Fe(9)-P(3) bond length is 2.41 Å. The Fe(9)-P(4) bond length is 2.25 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Mn(1), one Fe(1), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(9), and two equivalent Fe(2) atoms. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Mn(2), one Mn(3), one Fe(4), one Fe(5), one Fe(6), one Fe(7), one Fe(8), and two equivalent Fe(3) atoms. In the third P site, P(3) is bonded in a 9-coordinate geometry to one Mn(1), one Mn(3), one Fe(2), one Fe(3), one Fe(6), one Fe(8), one Fe(9), and two equivalent Fe(4) atoms. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one Mn(2), one Fe(1), one Fe(2), one Fe(3), one Fe(7), one Fe(8), one Fe(9), and two equivalent Fe(5) atoms.