DOE OSTI2020
ZnSn2O4 is Spinel-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are six inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with three ZnO6 octahedra and corners with nine SnO6 octahedra. The corner-sharing octahedra tilt angles range from 53–62°. There are a spread of Zn–O bond distances ranging from 1.99–2.54 Å. In the second Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with six SnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four SnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.24–2.35 Å. In the third Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with three SnO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five SnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.03–2.37 Å. In the fourth Zn2+ site, Zn2+ is bonded to six O2- atoms to form distorted ZnO6 octahedra that share corners with six SnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four SnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.21–2.31 Å. In the fifth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share corners with six SnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four equivalent SnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.11–2.26 Å. In the sixth Zn2+ site, Zn2+ is bonded to six O2- atoms to form ZnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with three SnO4 tetrahedra, an edgeedge with one ZnO6 octahedra, and edges with five SnO6 octahedra. There are a spread of Zn–O bond distances ranging from 2.12–2.46 Å. There are nine inequivalent Sn3+ sites. In the first Sn3+ site, Sn3+ is bonded to six O2- atoms to form SnO6 octahedra that share corners with two equivalent ZnO4 tetrahedra, corners with three SnO4 tetrahedra, edges with three ZnO6 octahedra, and edges with three SnO6 octahedra. There are a spread of Sn–O bond distances ranging from 2.08–2.21 Å. In the second Sn3+ site, Sn3+ is bonded to four O2- atoms to form SnO4 tetrahedra that share corners with six ZnO6 octahedra and corners with six SnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–70°. There are a spread of Sn–O bond distances ranging from 2.19–2.68 Å. In the third Sn3+ site, Sn3+ is bonded to six O2- atoms to form distorted SnO6 octahedra that share corners with three equivalent ZnO4 tetrahedra, edges with two ZnO6 octahedra, and edges with four SnO6 octahedra. There are a spread of Sn–O bond distances ranging from 2.32–2.68 Å. In the fourth Sn3+ site, Sn3+ is bonded to six O2- atoms to form SnO6 octahedra that share corners with six SnO4 tetrahedra, edges with two equivalent SnO6 octahedra, and edges with four ZnO6 octahedra. There are a spread of Sn–O bond distances ranging from 2.10–2.15 Å. In the fifth Sn3+ site, Sn3+ is bonded to four O2- atoms to form SnO4 tetrahedra that share corners with six ZnO6 octahedra and corners with six SnO6 octahedra. The corner-sharing octahedra tilt angles range from 58–68°. There are a spread of Sn–O bond distances ranging from 2.21–2.59 Å. In the sixth Sn3+ site, Sn3+ is bonded to six O2- atoms to form SnO6 octahedra that share a cornercorner with one ZnO4 tetrahedra, corners with three SnO4 tetrahedra, edges with three ZnO6 octahedra, and edges with three SnO6 octahedra. There are a spread of Sn–O bond distances ranging from 2.08–2.15 Å. In the seventh Sn3+ site, Sn3+ is bonded to four O2- atoms to form SnO4 tetrahedra that share corners with six ZnO6 octahedra and corners with six SnO6 octahedra. The corner-sharing octahedra tilt angles range from 55–71°. There are a spread of Sn–O bond distances ranging from 2.19–2.53 Å. In the eighth Sn3+ site, Sn3+ is bonded to four O2- atoms to form SnO4 tetrahedra that share corners with six ZnO6 octahedra and corners with six SnO6 octahedra. The corner-sharing octahedra tilt angles range from 56–71°. There are a spread of Sn–O bond distances ranging from 2.21–2.48 Å. In the ninth Sn3+ site, Sn3+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Sn–O bond distances ranging from 2.14–2.76 Å. There are eighteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Zn2+ and two Sn3+ atoms. In the second O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form distorted corner-sharing OZnSn3 tetrahedra. In the third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Zn2+ and three Sn3+ atoms. In the fourth O2- site, O2- is bonded to two Zn2+ and two Sn3+ atoms to form distorted OZn2Sn2 tetrahedra that share corners with twelve OZnSn3 tetrahedra and edges with three OZn2Sn2 tetrahedra. In the fifth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form distorted OZnSn3 tetrahedra that share corners with eight OZnSn3 tetrahedra and edges with two equivalent OZn2Sn2 tetrahedra. In the sixth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form a mixture of distorted edge and corner-sharing OZnSn3 tetrahedra. In the seventh O2- site, O2- is bonded to two Zn2+ and two Sn3+ atoms to form a mixture of distorted edge and corner-sharing OZn2Sn2 tetrahedra. In the eighth O2- site, O2- is bonded in a 4-coordinate geometry to one Zn2+ and three Sn3+ atoms. In the ninth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form distorted OZnSn3 tetrahedra that share corners with twelve OZnSn3 tetrahedra and edges with three OZn2Sn2 tetrahedra. In the tenth O2- site, O2- is bonded to two Zn2+ and two Sn3+ atoms to form distorted OZn2Sn2 tetrahedra that share corners with eight OZnSn3 tetrahedra, a cornercorner with one OSn4 trigonal pyramid, and edges with two OZn2Sn2 tetrahedra. In the eleventh O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form a mixture of distorted edge and corner-sharing OZnSn3 tetrahedra. In the twelfth O2- site, O2- is bonded to two Zn2+ and two Sn3+ atoms to form distorted OZn2Sn2 tetrahedra that share corners with twelve OZn2Sn2 tetrahedra and edges with three OZnSn3 tetrahedra. In the thirteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to two Zn2+ and two equivalent Sn3+ atoms. In the fourteenth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form distorted OZnSn3 tetrahedra that share corners with twelve OZn2Sn2 tetrahedra and edges with three OZnSn3 tetrahedra. In the fifteenth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form OZnSn3 tetrahedra that share corners with eight OZnSn3 tetrahedra, corners with two equivalent OSn4 trigonal pyramids, and edges with two equivalent OZn2Sn2 tetrahedra. In the sixteenth O2- site, O2- is bonded to four Sn3+ atoms to form distorted OSn4 trigonal pyramids that share corners with four OZn2Sn2 tetrahedra and an edgeedge with one OZnSn3 tetrahedra. In the seventeenth O2- site, O2- is bonded in a 4-coordinate geometry to one Zn2+ and three Sn3+ atoms. In the eighteenth O2- site, O2- is bonded to one Zn2+ and three Sn3+ atoms to form distorted OZnSn3 tetrahedra that share corners with nine OZn2Sn2 tetrahedra and an edgeedge with one OSn4 trigonal pyramid.