DOE OSTI2020
Cu2OF2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are sixteen inequivalent Cu2+ sites. In the first Cu2+ site, Cu2+ is bonded to two O2- and three F1- atoms to form distorted CuO2F3 trigonal bipyramids that share corners with four CuO3F3 octahedra, an edgeedge with one CuO2F4 octahedra, and an edgeedge with one CuO2F4 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 41–62°. There is one shorter (1.94 Å) and one longer (1.96 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.98–2.35 Å. In the second Cu2+ site, Cu2+ is bonded to three O2- and three F1- atoms to form distorted CuO3F3 octahedra that share corners with two CuO2F4 octahedra, a cornercorner with one CuO2F3 trigonal bipyramid, and an edgeedge with one CuO2F4 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 29–50°. There are a spread of Cu–O bond distances ranging from 1.91–2.20 Å. There are a spread of Cu–F bond distances ranging from 2.03–2.49 Å. In the third Cu2+ site, Cu2+ is bonded to two O2- and four F1- atoms to form CuO2F4 octahedra that share a cornercorner with one CuO2F3 trigonal bipyramid, edges with two CuO2F4 octahedra, and an edgeedge with one CuO2F4 pentagonal pyramid. There is one shorter (1.99 Å) and one longer (2.00 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 2.11–2.18 Å. In the fourth Cu2+ site, Cu2+ is bonded to one O2- and five F1- atoms to form CuOF5 octahedra that share a cornercorner with one CuO2F4 octahedra, a cornercorner with one CuO2F4 pentagonal pyramid, a cornercorner with one CuO2F3 trigonal bipyramid, and an edgeedge with one CuO2F4 octahedra. The corner-sharing octahedral tilt angles are 43°. The Cu–O bond length is 1.91 Å. There are a spread of Cu–F bond distances ranging from 2.08–2.26 Å. In the fifth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to three O2- and three F1- atoms. There are a spread of Cu–O bond distances ranging from 1.89–1.99 Å. There are a spread of Cu–F bond distances ranging from 2.10–2.51 Å. In the sixth Cu2+ site, Cu2+ is bonded to two O2- and four F1- atoms to form distorted CuO2F4 pentagonal pyramids that share corners with two CuOF5 octahedra, edges with four CuO3F3 octahedra, and an edgeedge with one CuO2F3 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 38–54°. There is one shorter (1.97 Å) and one longer (2.00 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 2.09–2.24 Å. In the seventh Cu2+ site, Cu2+ is bonded to two O2- and four F1- atoms to form distorted CuO2F4 octahedra that share corners with three CuO3F3 octahedra, a cornercorner with one CuO2F3 trigonal bipyramid, edges with two CuO2F4 octahedra, and an edgeedge with one CuO2F4 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 43–64°. There is one shorter (1.96 Å) and one longer (1.99 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.98–2.36 Å. In the eighth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to three O2- and three F1- atoms. There are a spread of Cu–O bond distances ranging from 1.98–2.45 Å. There are a spread of Cu–F bond distances ranging from 1.91–2.18 Å. In the ninth Cu2+ site, Cu2+ is bonded in a 5-coordinate geometry to two O2- and three F1- atoms. There is one shorter (1.88 Å) and one longer (2.01 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 2.01–2.38 Å. In the tenth Cu2+ site, Cu2+ is bonded to two O2- and four F1- atoms to form distorted CuO2F4 octahedra that share corners with three CuO3F3 octahedra, edges with two CuO2F4 octahedra, and an edgeedge with one CuO2F4 pentagonal pyramid. The corner-sharing octahedra tilt angles range from 29–64°. There is one shorter (1.94 Å) and one longer (2.01 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.98–2.44 Å. In the eleventh Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Cu–O bond length is 1.92 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.45 Å. In the twelfth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There is one shorter (1.95 Å) and one longer (1.97 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.95–2.36 Å. In the thirteenth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There is one shorter (1.91 Å) and one longer (1.92 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 1.96–2.62 Å. In the fourteenth Cu2+ site, Cu2+ is bonded to two O2- and four F1- atoms to form CuO2F4 octahedra that share a cornercorner with one CuO2F4 octahedra, a cornercorner with one CuO2F4 pentagonal pyramid, an edgeedge with one CuO2F4 octahedra, and an edgeedge with one CuO2F3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 57°. There is one shorter (1.92 Å) and one longer (1.99 Å) Cu–O bond length. There are a spread of Cu–F bond distances ranging from 2.00–2.26 Å. In the fifteenth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to one O2- and five F1- atoms. The Cu–O bond length is 1.90 Å. There are a spread of Cu–F bond distances ranging from 1.95–2.51 Å. In the sixteenth Cu2+ site, Cu2+ is bonded in a 6-coordinate geometry to two O2- and four F1- atoms. There are one shorter (1.90 Å) and one longer (2.56 Å) Cu–O bond lengths. There are a spread of Cu–F bond distances ranging from 2.01–2.21 Å. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded to four Cu2+ atoms to form OCu4 tetrahedra that share corners with four OCu4 tetrahedra, corners with two FCu4 trigonal pyramids, and an edgeedge with one FCu4 trigonal pyramid. In the second O2- site, O2- is bonded in a 3-coordinate geometry to four Cu2+ atoms. In the third O2- site, O2- is bonded to four Cu2+ atoms to form distorted OCu4 tetrahedra that share a cornercorner with one OCu4 tetrahedra, corners with three FCu4 trigonal pyramids, an edgeedge with one OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid. In the fourth O2- site, O2- is bonded to four Cu2+ atoms to form OCu4 tetrahedra that share a cornercorner with one OCu4 tetrahedra, corners with two FCu4 trigonal pyramids, an edgeedge with one OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid. In the fifth O2- site, O2- is bonded to four Cu2+ atoms to form distorted OCu4 tetrahedra that share a cornercorner with one OCu4 tetrahedra, corners with two FCu4 trigonal pyramids, an edgeedge with one OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid. In the sixth O2- site, O2- is bonded to four Cu2+ atoms to form distorted OCu4 tetrahedra that share a cornercorner with one OCu4 tetrahedra, corners with two FCu4 trigonal pyramids, and an edgeedge with one FCu4 trigonal pyramid. In the seventh O2- site, O2- is bonded to four Cu2+ atoms to form distorted OCu4 tetrahedra that share corners with two OCu4 tetrahedra, corners with two FCu4 trigonal pyramids, an edgeedge with one OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to four Cu2+ atoms. There are sixteen inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the second F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the third F1- site, F1- is bonded in a 4-coordinate geometry to four Cu2+ atoms. In the fourth F1- site, F1- is bonded to four Cu2+ atoms to form distorted FCu4 trigonal pyramids that share corners with two OCu4 tetrahedra, a cornercorner with one FCu4 trigonal pyramid, edges with three OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid. In the fifth F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the sixth F1- site, F1- is bonded in a 4-coordinate geometry to four Cu2+ atoms. In the seventh F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the eighth F1- site, F1- is bonded to four Cu2+ atoms to form distorted FCu4 trigonal pyramids that share corners with four OCu4 tetrahedra, corners with three FCu4 trigonal pyramids, and an edgeedge with one OCu4 tetrahedra. In the ninth F1- site, F1- is bonded in a 2-coordinate geometry to four Cu2+ atoms. In the tenth F1- site, F1- is bonded in a 4-coordinate geometry to four Cu2+ atoms. In the eleventh F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the twelfth F1- site, F1- is bonded in a distorted trigonal non-coplanar geometry to three Cu2+ atoms. In the thirteenth F1- site, F1- is bonded in a 3-coordinate geometry to three Cu2+ atoms. In the fourteenth F1- site, F1- is bonded to four Cu2+ atoms to form distorted FCu4 trigonal pyramids that share corners with five OCu4 tetrahedra, a cornercorner with one FCu4 trigonal pyramid, an edgeedge with one OCu4 tetrahedra, and edges with two FCu4 trigonal pyramids. In the fifteenth F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to four Cu2+ atoms. In the sixteenth F1- site, F1- is bonded to four Cu2+ atoms to form distorted FCu4 trigonal pyramids that share corners with two OCu4 tetrahedra, a cornercorner with one FCu4 trigonal pyramid, an edgeedge with one OCu4 tetrahedra, and an edgeedge with one FCu4 trigonal pyramid.