DOE OSTI2020
Fe4W2N crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are five inequivalent W sites. In the first W site, W is bonded in a 2-coordinate geometry to six Fe and two N atoms. There are a spread of W–Fe bond distances ranging from 2.63–2.77 Å. There are one shorter (2.06 Å) and one longer (2.11 Å) W–N bond lengths. In the second W site, W is bonded in a 2-coordinate geometry to six Fe and two N atoms. There are a spread of W–Fe bond distances ranging from 2.64–2.74 Å. There are one shorter (2.11 Å) and one longer (2.21 Å) W–N bond lengths. In the third W site, W is bonded in a 2-coordinate geometry to six Fe and two N atoms. There are a spread of W–Fe bond distances ranging from 2.61–2.75 Å. There are one shorter (2.11 Å) and one longer (2.17 Å) W–N bond lengths. In the fourth W site, W is bonded in a 2-coordinate geometry to six Fe and two equivalent N atoms. There are a spread of W–Fe bond distances ranging from 2.59–2.80 Å. Both W–N bond lengths are 2.14 Å. In the fifth W site, W is bonded in a 2-coordinate geometry to six Fe and two N atoms. There are a spread of W–Fe bond distances ranging from 2.65–2.76 Å. There are one shorter (2.08 Å) and one longer (2.12 Å) W–N bond lengths. There are twelve inequivalent Fe sites. In the first Fe site, Fe is bonded to five W and seven Fe atoms to form distorted FeFe7W5 cuboctahedra that share edges with six NFe2W4 octahedra and faces with six FeFe8W4 cuboctahedra. There are a spread of Fe–Fe bond distances ranging from 2.31–2.69 Å. In the second Fe site, Fe is bonded to four W and eight Fe atoms to form distorted FeFe8W4 cuboctahedra that share edges with six NFe3W3 octahedra and faces with six FeFe7W5 cuboctahedra. There are a spread of Fe–Fe bond distances ranging from 2.30–2.72 Å. In the third Fe site, Fe is bonded to three W and nine Fe atoms to form distorted FeFe9W3 cuboctahedra that share edges with six NFe3W3 octahedra and faces with six FeFe7W5 cuboctahedra. There are a spread of Fe–Fe bond distances ranging from 2.29–2.72 Å. In the fourth Fe site, Fe is bonded in a 12-coordinate geometry to three W and nine Fe atoms. There are a spread of Fe–Fe bond distances ranging from 2.43–2.78 Å. In the fifth Fe site, Fe is bonded in a 12-coordinate geometry to four W and eight Fe atoms. There are a spread of Fe–Fe bond distances ranging from 2.47–2.70 Å. In the sixth Fe site, Fe is bonded in a 12-coordinate geometry to five W and seven Fe atoms. The Fe–Fe bond length is 2.71 Å. In the seventh Fe site, Fe is bonded in a 12-coordinate geometry to five W and seven Fe atoms. There are a spread of Fe–Fe bond distances ranging from 2.43–2.65 Å. In the eighth Fe site, Fe is bonded in a 12-coordinate geometry to four W and eight Fe atoms. There are a spread of Fe–Fe bond distances ranging from 2.44–2.65 Å. In the ninth Fe site, Fe is bonded in a 12-coordinate geometry to three W and nine Fe atoms. There are one shorter (2.62 Å) and two longer (2.65 Å) Fe–Fe bond lengths. In the tenth Fe site, Fe is bonded in a distorted bent 120 degrees geometry to six Fe and two N atoms. There are one shorter (1.98 Å) and one longer (2.08 Å) Fe–N bond lengths. In the eleventh Fe site, Fe is bonded in a distorted bent 120 degrees geometry to six Fe and two N atoms. There are one shorter (2.02 Å) and one longer (2.07 Å) Fe–N bond lengths. In the twelfth Fe site, Fe is bonded in a distorted bent 120 degrees geometry to six Fe and two equivalent N atoms. Both Fe–N bond lengths are 2.06 Å. There are three inequivalent N sites. In the first N site, N is bonded to three W and three Fe atoms to form NFe3W3 octahedra that share corners with six NFe2W4 octahedra and edges with six FeFe8W4 cuboctahedra. The corner-sharing octahedra tilt angles range from 44–49°. In the second N site, N is bonded to four W and two Fe atoms to form NFe2W4 octahedra that share corners with six NFe3W3 octahedra and edges with six FeFe7W5 cuboctahedra. The corner-sharing octahedra tilt angles range from 44–49°. In the third N site, N is bonded to five W and one Fe atom to form NFeW5 octahedra that share corners with six NFe3W3 octahedra and edges with six FeFe7W5 cuboctahedra. The corner-sharing octahedra tilt angles range from 44–47°.