DOE OSTI2020
MnZn4S5 is Chalcopyrite-like structured and crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are two inequivalent Mn2+ sites. In the first Mn2+ site, Mn2+ is bonded to four S2- atoms to form MnS4 tetrahedra that share corners with four MnS4 tetrahedra and corners with eight ZnS4 tetrahedra. All Mn–S bond lengths are 2.40 Å. In the second Mn2+ site, Mn2+ is bonded to four S2- atoms to form MnS4 tetrahedra that share corners with four MnS4 tetrahedra and corners with eight ZnS4 tetrahedra. All Mn–S bond lengths are 2.40 Å. There are eight inequivalent Zn2+ sites. In the first Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with two equivalent MnS4 tetrahedra and corners with ten ZnS4 tetrahedra. All Zn–S bond lengths are 2.37 Å. In the second Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with six MnS4 tetrahedra and corners with six ZnS4 tetrahedra. There are a spread of Zn–S bond distances ranging from 2.34–2.37 Å. In the third Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with four equivalent MnS4 tetrahedra and corners with eight ZnS4 tetrahedra. There are one shorter (2.35 Å) and three longer (2.37 Å) Zn–S bond lengths. In the fourth Zn2+ site, Zn2+ is bonded to four S2- atoms to form corner-sharing ZnS4 tetrahedra. All Zn–S bond lengths are 2.38 Å. In the fifth Zn2+ site, Zn2+ is bonded to four S2- atoms to form corner-sharing ZnS4 tetrahedra. There are two shorter (2.37 Å) and two longer (2.38 Å) Zn–S bond lengths. In the sixth Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with two equivalent MnS4 tetrahedra and corners with ten ZnS4 tetrahedra. There are a spread of Zn–S bond distances ranging from 2.36–2.38 Å. In the seventh Zn2+ site, Zn2+ is bonded to four S2- atoms to form ZnS4 tetrahedra that share corners with two equivalent MnS4 tetrahedra and corners with ten ZnS4 tetrahedra. There are a spread of Zn–S bond distances ranging from 2.35–2.38 Å. In the eighth Zn2+ site, Zn2+ is bonded to four S2- atoms to form corner-sharing ZnS4 tetrahedra. There are three shorter (2.37 Å) and one longer (2.38 Å) Zn–S bond lengths. There are ten inequivalent S2- sites. In the first S2- site, S2- is bonded to one Mn2+ and three Zn2+ atoms to form corner-sharing SMnZn3 tetrahedra. In the second S2- site, S2- is bonded to three Mn2+ and one Zn2+ atom to form corner-sharing SMn3Zn tetrahedra. In the third S2- site, S2- is bonded to two equivalent Mn2+ and two Zn2+ atoms to form corner-sharing SMn2Zn2 tetrahedra. In the fourth S2- site, S2- is bonded to four Zn2+ atoms to form corner-sharing SZn4 tetrahedra. In the fifth S2- site, S2- is bonded to four Zn2+ atoms to form corner-sharing SZn4 tetrahedra. In the sixth S2- site, S2- is bonded to four Zn2+ atoms to form corner-sharing SZn4 tetrahedra. In the seventh S2- site, S2- is bonded to one Mn2+ and three Zn2+ atoms to form corner-sharing SMnZn3 tetrahedra. In the eighth S2- site, S2- is bonded to one Mn2+ and three Zn2+ atoms to form corner-sharing SMnZn3 tetrahedra. In the ninth S2- site, S2- is bonded to four Zn2+ atoms to form corner-sharing SZn4 tetrahedra. In the tenth S2- site, S2- is bonded to four Zn2+ atoms to form corner-sharing SZn4 tetrahedra.