DOE OSTI2020
Mn6O5F7 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Mn+2.83+ sites. In the first Mn+2.83+ site, Mn+2.83+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with two equivalent MnO2F4 octahedra and corners with two equivalent MnOF4 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 36–45°. There are one shorter (1.92 Å) and one longer (2.14 Å) Mn–O bond lengths. There are a spread of Mn–F bond distances ranging from 1.95–2.27 Å. In the second Mn+2.83+ site, Mn+2.83+ is bonded to two O2- and four F1- atoms to form corner-sharing MnO2F4 octahedra. The corner-sharing octahedra tilt angles range from 36–59°. Both Mn–O bond lengths are 1.93 Å. There are a spread of Mn–F bond distances ranging from 1.99–2.18 Å. In the third Mn+2.83+ site, Mn+2.83+ is bonded to two O2- and four F1- atoms to form MnO2F4 octahedra that share corners with four MnO2F4 octahedra and edges with two equivalent MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 44–51°. There is one shorter (1.90 Å) and one longer (1.93 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 1.98–2.20 Å. In the fourth Mn+2.83+ site, Mn+2.83+ is bonded to two O2- and four F1- atoms to form corner-sharing MnO2F4 octahedra. The corner-sharing octahedra tilt angles range from 46–53°. There is one shorter (1.93 Å) and one longer (1.96 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 2.09–2.20 Å. In the fifth Mn+2.83+ site, Mn+2.83+ is bonded to three O2- and three F1- atoms to form MnO3F3 octahedra that share corners with two equivalent MnO2F4 octahedra, corners with two equivalent MnOF4 trigonal bipyramids, and edges with two equivalent MnO4F2 octahedra. The corner-sharing octahedra tilt angles range from 49–53°. There are a spread of Mn–O bond distances ranging from 1.92–2.05 Å. There are a spread of Mn–F bond distances ranging from 1.96–2.26 Å. In the sixth Mn+2.83+ site, Mn+2.83+ is bonded to one O2- and four F1- atoms to form distorted corner-sharing MnOF4 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 22–69°. The Mn–O bond length is 2.13 Å. There are a spread of Mn–F bond distances ranging from 2.04–2.18 Å. In the seventh Mn+2.83+ site, Mn+2.83+ is bonded in a 4-coordinate geometry to four O2- and two F1- atoms. There are a spread of Mn–O bond distances ranging from 1.90–1.96 Å. There are one shorter (2.56 Å) and one longer (2.59 Å) Mn–F bond lengths. In the eighth Mn+2.83+ site, Mn+2.83+ is bonded in a 5-coordinate geometry to three O2- and two F1- atoms. There are a spread of Mn–O bond distances ranging from 1.92–2.02 Å. There are one shorter (1.97 Å) and one longer (2.38 Å) Mn–F bond lengths. In the ninth Mn+2.83+ site, Mn+2.83+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share corners with two equivalent MnO2F4 octahedra, corners with two equivalent MnOF4 trigonal bipyramids, and edges with two equivalent MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 47–51°. There are a spread of Mn–O bond distances ranging from 1.93–2.08 Å. There are one shorter (2.01 Å) and one longer (2.06 Å) Mn–F bond lengths. In the tenth Mn+2.83+ site, Mn+2.83+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There are one shorter (2.00 Å) and one longer (2.03 Å) Mn–O bond lengths. There are a spread of Mn–F bond distances ranging from 2.03–2.45 Å. In the eleventh Mn+2.83+ site, Mn+2.83+ is bonded to three O2- and three F1- atoms to form a mixture of corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 46–59°. There are a spread of Mn–O bond distances ranging from 1.91–1.97 Å. There are a spread of Mn–F bond distances ranging from 2.09–2.31 Å. In the twelfth Mn+2.83+ site, Mn+2.83+ is bonded in a 6-coordinate geometry to three O2- and three F1- atoms. There are a spread of Mn–O bond distances ranging from 1.91–2.04 Å. There are a spread of Mn–F bond distances ranging from 2.00–2.49 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the second O2- site, O2- is bonded in a tetrahedral geometry to four Mn+2.83+ atoms. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the sixth O2- site, O2- is bonded in a distorted T-shaped geometry to three Mn+2.83+ atoms. In the seventh O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the eighth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the ninth O2- site, O2- is bonded in a trigonal planar geometry to three Mn+2.83+ atoms. In the tenth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. There are fourteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.83+ atoms. In the second F1- site, F1- is bonded in a distorted bent 150 degrees geometry to two Mn+2.83+ atoms. In the third F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.83+ atoms. In the fourth F1- site, F1- is bonded in a 2-coordinate geometry to three Mn+2.83+ atoms. In the fifth F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.83+ atoms. In the sixth F1- site, F1- is bonded in a distorted bent 150 degrees geometry to two Mn+2.83+ atoms. In the seventh F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the eighth F1- site, F1- is bonded in a distorted trigonal planar geometry to three Mn+2.83+ atoms. In the ninth F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.83+ atoms. In the tenth F1- site, F1- is bonded in a 2-coordinate geometry to three Mn+2.83+ atoms. In the eleventh F1- site, F1- is bonded in a water-like geometry to two Mn+2.83+ atoms. In the twelfth F1- site, F1- is bonded in a 2-coordinate geometry to three Mn+2.83+ atoms. In the thirteenth F1- site, F1- is bonded in a 3-coordinate geometry to three Mn+2.83+ atoms. In the fourteenth F1- site, F1- is bonded in a 2-coordinate geometry to three Mn+2.83+ atoms.