DOE OSTI2020
Mn3(O2F)2 is zeta iron carbide-derived structured and crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are six inequivalent Mn+3.33+ sites. In the first Mn+3.33+ site, Mn+3.33+ is bonded to five O2- and one F1- atom to form MnO5F octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO4F2 octahedra. The corner-sharing octahedra tilt angles range from 49–52°. There are a spread of Mn–O bond distances ranging from 1.93–2.14 Å. The Mn–F bond length is 2.39 Å. In the second Mn+3.33+ site, Mn+3.33+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO5F octahedra. The corner-sharing octahedra tilt angles range from 45–52°. There are a spread of Mn–O bond distances ranging from 1.94–1.96 Å. There are one shorter (2.18 Å) and one longer (2.21 Å) Mn–F bond lengths. In the third Mn+3.33+ site, Mn+3.33+ is bonded to five O2- and one F1- atom to form MnO5F octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO5F octahedra. The corner-sharing octahedra tilt angles range from 38–52°. There are a spread of Mn–O bond distances ranging from 1.92–2.00 Å. The Mn–F bond length is 2.24 Å. In the fourth Mn+3.33+ site, Mn+3.33+ is bonded to three O2- and three F1- atoms to form MnO3F3 octahedra that share corners with eight MnO5F octahedra and edges with two MnO4F2 octahedra. The corner-sharing octahedra tilt angles range from 49–52°. There are a spread of Mn–O bond distances ranging from 1.89–2.02 Å. There are a spread of Mn–F bond distances ranging from 1.96–2.09 Å. In the fifth Mn+3.33+ site, Mn+3.33+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share corners with eight MnO5F octahedra and edges with two MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 38–52°. There are a spread of Mn–O bond distances ranging from 1.85–1.92 Å. There are one shorter (2.01 Å) and one longer (2.05 Å) Mn–F bond lengths. In the sixth Mn+3.33+ site, Mn+3.33+ is bonded to three O2- and three F1- atoms to form MnO3F3 octahedra that share corners with eight MnO5F octahedra and edges with two MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 50–52°. There are a spread of Mn–O bond distances ranging from 1.91–1.94 Å. There are a spread of Mn–F bond distances ranging from 1.97–2.16 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. There are four inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+3.33+ atoms. In the second F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+3.33+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+3.33+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+3.33+ atoms.