DOE OSTI2020
KMnP(OF)3 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. K1+ is bonded in a 10-coordinate geometry to four O2- and six F1- atoms. There are a spread of K–O bond distances ranging from 2.87–3.10 Å. There are a spread of K–F bond distances ranging from 2.68–3.10 Å. There are two inequivalent Mn3+ sites. In the first Mn3+ site, Mn3+ is bonded to four O2- and two equivalent F1- atoms to form MnO4F2 octahedra that share corners with two equivalent MnO2F4 octahedra and corners with four equivalent PO3F tetrahedra. The corner-sharing octahedral tilt angles are 47°. There are two shorter (1.96 Å) and two longer (2.26 Å) Mn–O bond lengths. Both Mn–F bond lengths are 1.89 Å. In the second Mn3+ site, Mn3+ is bonded to two equivalent O2- and four F1- atoms to form MnO2F4 octahedra that share corners with two equivalent MnO4F2 octahedra and corners with two equivalent PO3F tetrahedra. The corner-sharing octahedral tilt angles are 47°. Both Mn–O bond lengths are 1.97 Å. There are two shorter (1.86 Å) and two longer (2.22 Å) Mn–F bond lengths. P5+ is bonded to three O2- and one F1- atom to form PO3F tetrahedra that share corners with three MnO4F2 octahedra. The corner-sharing octahedra tilt angles range from 40–53°. There are a spread of P–O bond distances ranging from 1.52–1.54 Å. The P–F bond length is 1.61 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to two equivalent K1+, one Mn3+, and one P5+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one K1+, one Mn3+, and one P5+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one K1+, one Mn3+, and one P5+ atom. There are three inequivalent F1- sites. In the first F1- site, F1- is bonded in a single-bond geometry to three equivalent K1+ and one P5+ atom. In the second F1- site, F1- is bonded in a 3-coordinate geometry to one K1+ and two Mn3+ atoms. In the third F1- site, F1- is bonded in a distorted single-bond geometry to two equivalent K1+ and one Mn3+ atom.