DOE OSTI2020
Rb3Mo4FeO15 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are three inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Rb–O bond distances ranging from 2.88–3.56 Å. In the second Rb1+ site, Rb1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Rb–O bond distances ranging from 2.93–3.28 Å. In the third Rb1+ site, Rb1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Rb–O bond distances ranging from 2.92–3.44 Å. There are four inequivalent Mo6+ sites. In the first Mo6+ site, Mo6+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Mo–O bond distances ranging from 1.75–2.58 Å. In the second Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share a cornercorner with one FeO6 octahedra. The corner-sharing octahedral tilt angles are 62°. There are a spread of Mo–O bond distances ranging from 1.75–1.90 Å. In the third Mo6+ site, Mo6+ is bonded to four O2- atoms to form MoO4 tetrahedra that share corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 39–56°. There are a spread of Mo–O bond distances ranging from 1.76–1.83 Å. In the fourth Mo6+ site, Mo6+ is bonded to four O2- atoms to form distorted MoO4 tetrahedra that share corners with two FeO6 octahedra. The corner-sharing octahedra tilt angles range from 32–54°. There are a spread of Mo–O bond distances ranging from 1.74–1.92 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with four MoO4 tetrahedra. There are four shorter (2.03 Å) and two longer (2.07 Å) Fe–O bond lengths. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with six MoO4 tetrahedra. There are a spread of Fe–O bond distances ranging from 2.01–2.07 Å. There are fifteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to three Rb1+ and one Mo6+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to three Rb1+ and one Mo6+ atom. In the third O2- site, O2- is bonded in a distorted water-like geometry to two Rb1+, one Mo6+, and one Fe3+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to two Mo6+ atoms. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to two Mo6+ and one Fe3+ atom. In the sixth O2- site, O2- is bonded in a distorted single-bond geometry to one Rb1+ and two Mo6+ atoms. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to three Rb1+ and one Mo6+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to three Rb1+ and one Mo6+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+, one Mo6+, and one Fe3+ atom. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to two Rb1+ and one Mo6+ atom. In the eleventh O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Rb1+, one Mo6+, and one Fe3+ atom. In the twelfth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Rb1+, one Mo6+, and one Fe3+ atom. In the thirteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Rb1+ and one Mo6+ atom. In the fourteenth O2- site, O2- is bonded in a distorted single-bond geometry to two Rb1+ and one Mo6+ atom. In the fifteenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Rb1+, one Mo6+, and one Fe3+ atom.