DOE OSTI2020
Zr2Mn4P3 crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are three inequivalent Zr sites. In the first Zr site, Zr is bonded in a 8-coordinate geometry to two equivalent Mn and six P atoms. Both Zr–Mn bond lengths are 2.81 Å. There are two shorter (2.75 Å) and four longer (2.83 Å) Zr–P bond lengths. In the second Zr site, Zr is bonded in a 6-coordinate geometry to six equivalent P atoms. All Zr–P bond lengths are 2.79 Å. In the third Zr site, Zr is bonded in a 5-coordinate geometry to eight Mn and five P atoms. There are a spread of Zr–Mn bond distances ranging from 2.81–2.87 Å. There are one shorter (2.63 Å) and four longer (2.66 Å) Zr–P bond lengths. There are four inequivalent Mn sites. In the first Mn site, Mn is bonded to two equivalent Zr and four P atoms to form a mixture of distorted edge, corner, and face-sharing MnZr2P4 tetrahedra. There are two shorter (2.27 Å) and two longer (2.42 Å) Mn–P bond lengths. In the second Mn site, Mn is bonded to one Zr and four P atoms to form distorted MnZrP4 tetrahedra that share corners with seven MnZrP4 tetrahedra, edges with five MnZrP4 tetrahedra, and faces with two equivalent MnZr2P4 tetrahedra. There are a spread of Mn–P bond distances ranging from 2.31–2.37 Å. In the third Mn site, Mn is bonded to two equivalent Zr and four P atoms to form distorted MnZr2P4 tetrahedra that share corners with nine MnZr2P4 tetrahedra, edges with eight MnZrP4 tetrahedra, and faces with two MnZr2P4 tetrahedra. There are a spread of Mn–P bond distances ranging from 2.33–2.43 Å. In the fourth Mn site, Mn is bonded in a trigonal planar geometry to six equivalent Zr and three equivalent P atoms. All Mn–P bond lengths are 2.20 Å. There are three inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to three Zr and six Mn atoms. In the second P site, P is bonded in a 9-coordinate geometry to four equivalent Zr and five Mn atoms. In the third P site, P is bonded in a 9-coordinate geometry to four Zr and five Mn atoms.