MnP4 is Sylvanite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent P(2), two equivalent P(3), and two equivalent P(4) atoms to form edge-sharing MnP6 octahedra. In the second Mn site, Mn(2) is bonded to one P(2), one P(4), one P(5), one P(6), and two equivalent P(1) atoms to form a mixture of edge and corner-sharing MnP6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to two equivalent Mn(2), one P(3), and one P(6) atom. In the second P site, P(2) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one P(4), and one P(5) atom. In the third P site, P(3) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(5), and one P(6) atom. In the fourth P site, P(4) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one P(2), and one P(6) atom. In the fifth P site, P(5) is bonded in a distorted single-bond geometry to one Mn(2), one P(2), one P(3), and one P(5) atom. In the sixth P site, P(6) is bonded in a distorted single-bond geometry to one Mn(2), one P(1), one P(3), and one P(4) atom.
MnP4 is Sylvanite-derived structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent P(2), two equivalent P(3), and two equivalent P(4) atoms to form edge-sharing MnP6 octahedra. Both Mn(1)-P(2) bond lengths are 2.31 Å. Both Mn(1)-P(3) bond lengths are 2.30 Å. Both Mn(1)-P(4) bond lengths are 2.32 Å. In the second Mn site, Mn(2) is bonded to one P(2), one P(4), one P(5), one P(6), and two equivalent P(1) atoms to form a mixture of edge and corner-sharing MnP6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Mn(2)-P(2) bond length is 2.28 Å. The Mn(2)-P(4) bond length is 2.25 Å. The Mn(2)-P(5) bond length is 2.19 Å. The Mn(2)-P(6) bond length is 2.30 Å. There is one shorter (2.33 Å) and one longer (2.39 Å) Mn(2)-P(1) bond length. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 4-coordinate geometry to two equivalent Mn(2), one P(3), and one P(6) atom. The P(1)-P(3) bond length is 2.24 Å. The P(1)-P(6) bond length is 2.27 Å. In the second P site, P(2) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one P(4), and one P(5) atom. The P(2)-P(4) bond length is 2.19 Å. The P(2)-P(5) bond length is 2.21 Å. In the third P site, P(3) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(5), and one P(6) atom. The P(3)-P(5) bond length is 2.26 Å. The P(3)-P(6) bond length is 2.30 Å. In the fourth P site, P(4) is bonded in a 4-coordinate geometry to one Mn(1), one Mn(2), one P(2), and one P(6) atom. The P(4)-P(6) bond length is 2.18 Å. In the fifth P site, P(5) is bonded in a distorted single-bond geometry to one Mn(2), one P(2), one P(3), and one P(5) atom. The P(5)-P(5) bond length is 2.29 Å. In the sixth P site, P(6) is bonded in a distorted single-bond geometry to one Mn(2), one P(1), one P(3), and one P(4) atom.