Materials Data on NaCu4P2ClO9 by Materials Project
NaCu4P2O9Cl crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Na1+ is bonded in a 6-coordinate geometry to four O2- and two equivalent Cl1- atoms. There are a spread of Na–O bond distances ranging from 2.27–2.47 Å. There are one shorter (2.75 Å) and one longer (2.86 Å) Na–Cl bond lengths. There are five inequivalent Cu2+ sites. In the first Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with two equivalent CuO6 octahedra, corners with four PO4 tetrahedra, and edges with four CuClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 59°. There are a spread of Cu–O bond distances ranging from 1.86–2.34 Å. In the second Cu2+ site, Cu2+ is bonded to six O2- atoms to form distorted CuO6 octahedra that share corners with two equivalent CuO6 octahedra, corners with four PO4 tetrahedra, and edges with four CuClO4 trigonal bipyramids. The corner-sharing octahedral tilt angles are 59°. There are a spread of Cu–O bond distances ranging from 1.86–2.45 Å. In the third Cu2+ site, Cu2+ is bonded to four O2- and one Cl1- atom to form distorted CuClO4 trigonal bipyramids that share corners with three equivalent PO4 tetrahedra, edges with two CuO6 octahedra, and an edgeedge with one CuClO4 trigonal bipyramid. There are a spread of Cu–O bond distances ranging from 1.94–2.08 Å. The Cu–Cl bond length is 2.47 Å. In the fourth Cu2+ site, Cu2+ is bonded to four O2- and one Cl1- atom to form distorted CuClO4 trigonal bipyramids that share corners with three equivalent PO4 tetrahedra, edges with two CuO6 octahedra, and an edgeedge with one CuClO4 trigonal bipyramid. There are a spread of Cu–O bond distances ranging from 1.94–2.09 Å. The Cu–Cl bond length is 2.45 Å. In the fifth Cu2+ site, Cu2+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Cu–O bond distances ranging from 1.93–2.08 Å. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two CuO6 octahedra and corners with three equivalent CuClO4 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 43–52°. There are a spread of P–O bond distances ranging from 1.54–1.60 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two CuO6 octahedra and corners with three equivalent CuClO4 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 41–52°. There are a spread of P–O bond distances ranging from 1.53–1.60 Å. There are nine inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to two Cu2+ and one P5+ atom. In the second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Na1+, one Cu2+, and one P5+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to two Cu2+ and one P5+ atom. In the fourth O2- site, O2- is bonded to four Cu2+ atoms to form corner-sharing OCu4 tetrahedra. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, two Cu2+, and one P5+ atom. In the sixth O2- site, O2- is bonded to one Na1+, two Cu2+, and one P5+ atom to form distorted corner-sharing ONaCu2P tetrahedra. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Cu2+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to two Cu2+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a 1-coordinate geometry to two Cu2+ and one P5+ atom. Cl1- is bonded in a 5-coordinate geometry to two equivalent Na1+ and two Cu2+ atoms.