DOE OSTI2020
Mn3(OF2)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+2.67+ sites. In the first Mn+2.67+ site, Mn+2.67+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO2F4 octahedra. The corner-sharing octahedra tilt angles range from 41–58°. There is one shorter (1.89 Å) and one longer (1.92 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 2.05–2.26 Å. In the second Mn+2.67+ site, Mn+2.67+ is bonded to three O2- and three F1- atoms to form a mixture of edge and corner-sharing MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 42–52°. There are a spread of Mn–O bond distances ranging from 1.99–2.07 Å. There are a spread of Mn–F bond distances ranging from 2.10–2.20 Å. In the third Mn+2.67+ site, Mn+2.67+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with eight MnO2F4 octahedra and edges with two MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 41–58°. There is one shorter (1.97 Å) and one longer (1.99 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 2.13–2.18 Å. In the fourth Mn+2.67+ site, Mn+2.67+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO2F4 octahedra. The corner-sharing octahedra tilt angles range from 46–58°. There is one shorter (1.96 Å) and one longer (1.97 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 2.07–2.17 Å. In the fifth Mn+2.67+ site, Mn+2.67+ is bonded to one O2- and five F1- atoms to form MnOF5 octahedra that share corners with eight MnO3F3 octahedra and edges with two MnO2F4 octahedra. The corner-sharing octahedra tilt angles range from 42–56°. The Mn–O bond length is 1.97 Å. There are a spread of Mn–F bond distances ranging from 2.02–2.14 Å. In the sixth Mn+2.67+ site, Mn+2.67+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with eight MnO2F4 octahedra and edges with two MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 46–58°. There are one shorter (2.02 Å) and one longer (2.03 Å) Mn–O bond lengths. There are a spread of Mn–F bond distances ranging from 2.04–2.18 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. There are eight inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.67+ atoms. In the second F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the third F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the fourth F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.67+ atoms. In the fifth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the sixth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the seventh F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms. In the eighth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.67+ atoms.