DOE OSTI2020
Co4Zn3(SbO6)2 is Spinel-derived structured and crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are five inequivalent Co2+ sites. In the first Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two SbO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.03–2.23 Å. In the second Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six ZnO4 tetrahedra, edges with three CoO6 octahedra, and edges with three SbO6 octahedra. There are a spread of Co–O bond distances ranging from 1.99–2.28 Å. In the third Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent SbO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.04–2.18 Å. In the fourth Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six ZnO4 tetrahedra, edges with three CoO6 octahedra, and edges with three SbO6 octahedra. There are a spread of Co–O bond distances ranging from 2.00–2.25 Å. In the fifth Co2+ site, Co2+ is bonded to six O2- atoms to form CoO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent SbO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Co–O bond distances ranging from 2.04–2.17 Å. There are three inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four SbO6 octahedra and corners with eight CoO6 octahedra. The corner-sharing octahedra tilt angles range from 50–63°. There are a spread of Zn–O bond distances ranging from 1.94–2.20 Å. In the second Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with five SbO6 octahedra and corners with seven CoO6 octahedra. The corner-sharing octahedra tilt angles range from 52–63°. There are a spread of Zn–O bond distances ranging from 1.97–2.13 Å. In the third Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three SbO6 octahedra and corners with nine CoO6 octahedra. The corner-sharing octahedra tilt angles range from 54–63°. There are a spread of Zn–O bond distances ranging from 1.93–2.08 Å. There are three inequivalent Sb5+ sites. In the first Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with six ZnO4 tetrahedra, edges with two equivalent SbO6 octahedra, and edges with four CoO6 octahedra. There are a spread of Sb–O bond distances ranging from 1.99–2.06 Å. In the second Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with six ZnO4 tetrahedra, an edgeedge with one SbO6 octahedra, and edges with five CoO6 octahedra. There are a spread of Sb–O bond distances ranging from 1.99–2.13 Å. In the third Sb5+ site, Sb5+ is bonded to six O2- atoms to form SbO6 octahedra that share corners with six ZnO4 tetrahedra and edges with six CoO6 octahedra. There are two shorter (2.01 Å) and four longer (2.02 Å) Sb–O bond lengths. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the second O2- site, O2- is bonded to two Co2+, one Zn2+, and one Sb5+ atom to form distorted corner-sharing OZnCo2Sb tetrahedra. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the fourth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the fifth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Co2+, one Zn2+, and two Sb5+ atoms. In the sixth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the seventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Co2+ and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the ninth O2- site, O2- is bonded to three Co2+ and one Zn2+ atom to form distorted OZnCo3 trigonal pyramids that share corners with two equivalent OZnCo2Sb tetrahedra and a cornercorner with one OZnCo3 trigonal pyramid. In the tenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Co2+, one Zn2+, and two Sb5+ atoms. In the twelfth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Co2+, one Zn2+, and one Sb5+ atom.