DOE OSTI2020
BaZnRu5O11 crystallizes in the hexagonal P6_3/m space group. The structure is three-dimensional. there are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with six equivalent BaO12 cuboctahedra, edges with six equivalent RuO6 octahedra, edges with three equivalent ZnO5 trigonal bipyramids, and faces with six equivalent RuO6 octahedra. There are nine shorter (2.94 Å) and three longer (2.97 Å) Ba–O bond lengths. In the second Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form distorted BaO12 cuboctahedra that share corners with six BaO12 cuboctahedra, edges with six RuO6 octahedra, edges with three ZnO5 trigonal bipyramids, and faces with six RuO6 octahedra. There are a spread of Ba–O bond distances ranging from 2.80–3.19 Å. There are four inequivalent Ru+3.60+ sites. In the first Ru+3.60+ site, Ru+3.60+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with six RuO6 octahedra, corners with three ZnO5 trigonal bipyramids, faces with three BaO12 cuboctahedra, and a faceface with one RuO6 octahedra. The corner-sharing octahedra tilt angles range from 46–56°. There are a spread of Ru–O bond distances ranging from 1.99–2.07 Å. In the second Ru+3.60+ site, Ru+3.60+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with four equivalent RuO6 octahedra, corners with two ZnO5 trigonal bipyramids, edges with two BaO12 cuboctahedra, and edges with four RuO6 octahedra. The corner-sharing octahedra tilt angles range from 46–56°. There are a spread of Ru–O bond distances ranging from 2.02–2.07 Å. In the third Ru+3.60+ site, Ru+3.60+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with six equivalent RuO6 octahedra, corners with three equivalent ZnO5 trigonal bipyramids, faces with three equivalent BaO12 cuboctahedra, and a faceface with one RuO6 octahedra. The corner-sharing octahedra tilt angles range from 50–53°. There are three shorter (2.04 Å) and three longer (2.05 Å) Ru–O bond lengths. In the fourth Ru+3.60+ site, Ru+3.60+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with four RuO6 octahedra, corners with two equivalent ZnO5 trigonal bipyramids, edges with two equivalent BaO12 cuboctahedra, and edges with four RuO6 octahedra. The corner-sharing octahedra tilt angles range from 49–54°. There are a spread of Ru–O bond distances ranging from 2.02–2.07 Å. There are two inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to five O2- atoms to form ZnO5 trigonal bipyramids that share corners with twelve RuO6 octahedra and edges with three equivalent BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 43–61°. There are three shorter (1.92 Å) and two longer (2.49 Å) Zn–O bond lengths. In the second Zn2+ site, Zn2+ is bonded to five O2- atoms to form ZnO5 trigonal bipyramids that share corners with twelve RuO6 octahedra and edges with three BaO12 cuboctahedra. The corner-sharing octahedra tilt angles range from 42–59°. There are a spread of Zn–O bond distances ranging from 1.91–2.34 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded to three equivalent Ru+3.60+ and one Zn2+ atom to form distorted corner-sharing OZnRu3 tetrahedra. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+ and three Ru+3.60+ atoms. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Ru+3.60+ and one Zn2+ atom. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent Ba2+, two equivalent Ru+3.60+, and one Zn2+ atom. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent Ba2+, two equivalent Ru+3.60+, and one Zn2+ atom. In the sixth O2- site, O2- is bonded in a 4-coordinate geometry to one Ba2+ and three Ru+3.60+ atoms. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to two Ba2+, two equivalent Ru+3.60+, and one Zn2+ atom. In the eighth O2- site, O2- is bonded in a 4-coordinate geometry to one Ba2+ and three Ru+3.60+ atoms. In the ninth O2- site, O2- is bonded in a 5-coordinate geometry to two Ba2+, two equivalent Ru+3.60+, and one Zn2+ atom. In the tenth O2- site, O2- is bonded in a 3-coordinate geometry to one Ba2+ and three Ru+3.60+ atoms.