MnP4 is Sylvanite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one P(12), one P(3), one P(6), one P(9), and two equivalent P(4) atoms to form edge-sharing MnP6 octahedra. In the second Mn site, Mn(2) is bonded to one P(11), one P(5), one P(7), one P(8), and two equivalent P(10) atoms to form edge-sharing MnP6 octahedra. In the third Mn site, Mn(3) is bonded to one P(1), one P(2), one P(5), one P(6), one P(8), and one P(9) atom to form edge-sharing MnP6 octahedra. There are twelve inequivalent P sites. In the first P site, P(1) is bonded in a distorted single-bond geometry to one Mn(3), one P(12), one P(2), and one P(8) atom. In the second P site, P(2) is bonded in a distorted single-bond geometry to one Mn(3), one P(1), one P(7), and one P(9) atom. In the third P site, P(3) is bonded in a distorted single-bond geometry to one Mn(1), one P(12), one P(3), and one P(6) atom. In the fourth P site, P(4) is bonded in a 4-coordinate geometry to two equivalent Mn(1), one P(12), and one P(6) atom. In the fifth P site, P(5) is bonded in a 4-coordinate geometry to one Mn(2), one Mn(3), one P(10), and one P(11) atom. In the sixth P site, P(6) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(3), one P(3), and one P(4) atom. In the seventh P site, P(7) is bonded in a distorted single-bond geometry to one Mn(2), one P(10), one P(11), and one P(2) atom. In the eighth P site, P(8) is bonded in a 4-coordinate geometry to one Mn(2), one Mn(3), one P(1), and one P(9) atom. In the ninth P site, P(9) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(3), one P(2), and one P(8) atom. In the tenth P site, P(10) is bonded in a 4-coordinate geometry to two equivalent Mn(2), one P(5), and one P(7) atom. In the eleventh P site, P(11) is bonded in a distorted single-bond geometry to one Mn(2), one P(11), one P(5), and one P(7) atom. In the twelfth P site, P(12) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(3), and one P(4) atom.
MnP4 is Sylvanite-derived structured and crystallizes in the triclinic P-1 space group. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one P(12), one P(3), one P(6), one P(9), and two equivalent P(4) atoms to form edge-sharing MnP6 octahedra. The Mn(1)-P(12) bond length is 2.24 Å. The Mn(1)-P(3) bond length is 2.24 Å. The Mn(1)-P(6) bond length is 2.21 Å. The Mn(1)-P(9) bond length is 2.26 Å. There is one shorter (2.32 Å) and one longer (2.34 Å) Mn(1)-P(4) bond length. In the second Mn site, Mn(2) is bonded to one P(11), one P(5), one P(7), one P(8), and two equivalent P(10) atoms to form edge-sharing MnP6 octahedra. The Mn(2)-P(11) bond length is 2.22 Å. The Mn(2)-P(5) bond length is 2.33 Å. The Mn(2)-P(7) bond length is 2.23 Å. The Mn(2)-P(8) bond length is 2.37 Å. There is one shorter (2.21 Å) and one longer (2.22 Å) Mn(2)-P(10) bond length. In the third Mn site, Mn(3) is bonded to one P(1), one P(2), one P(5), one P(6), one P(8), and one P(9) atom to form edge-sharing MnP6 octahedra. The Mn(3)-P(1) bond length is 2.20 Å. The Mn(3)-P(2) bond length is 2.26 Å. The Mn(3)-P(5) bond length is 2.33 Å. The Mn(3)-P(6) bond length is 2.21 Å. The Mn(3)-P(8) bond length is 2.30 Å. The Mn(3)-P(9) bond length is 2.23 Å. There are twelve inequivalent P sites. In the first P site, P(1) is bonded in a distorted single-bond geometry to one Mn(3), one P(12), one P(2), and one P(8) atom. The P(1)-P(12) bond length is 2.22 Å. The P(1)-P(2) bond length is 2.19 Å. The P(1)-P(8) bond length is 2.23 Å. In the second P site, P(2) is bonded in a distorted single-bond geometry to one Mn(3), one P(1), one P(7), and one P(9) atom. The P(2)-P(7) bond length is 2.24 Å. The P(2)-P(9) bond length is 2.24 Å. In the third P site, P(3) is bonded in a distorted single-bond geometry to one Mn(1), one P(12), one P(3), and one P(6) atom. The P(3)-P(12) bond length is 2.25 Å. The P(3)-P(3) bond length is 2.24 Å. The P(3)-P(6) bond length is 2.17 Å. In the fourth P site, P(4) is bonded in a 4-coordinate geometry to two equivalent Mn(1), one P(12), and one P(6) atom. The P(4)-P(12) bond length is 2.23 Å. The P(4)-P(6) bond length is 2.24 Å. In the fifth P site, P(5) is bonded in a 4-coordinate geometry to one Mn(2), one Mn(3), one P(10), and one P(11) atom. The P(5)-P(10) bond length is 2.23 Å. The P(5)-P(11) bond length is 2.23 Å. In the sixth P site, P(6) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(3), one P(3), and one P(4) atom. In the seventh P site, P(7) is bonded in a distorted single-bond geometry to one Mn(2), one P(10), one P(11), and one P(2) atom. The P(7)-P(10) bond length is 2.18 Å. The P(7)-P(11) bond length is 2.25 Å. In the eighth P site, P(8) is bonded in a 4-coordinate geometry to one Mn(2), one Mn(3), one P(1), and one P(9) atom. The P(8)-P(9) bond length is 2.22 Å. In the ninth P site, P(9) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(3), one P(2), and one P(8) atom. In the tenth P site, P(10) is bonded in a 4-coordinate geometry to two equivalent Mn(2), one P(5), and one P(7) atom. In the eleventh P site, P(11) is bonded in a distorted single-bond geometry to one Mn(2), one P(11), one P(5), and one P(7) atom. The P(11)-P(11) bond length is 2.26 Å. In the twelfth P site, P(12) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(3), and one P(4) atom.