DOE OSTI2020
Na19Zr11S30 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are eight inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with two NaS6 octahedra, corners with four ZrS6 octahedra, edges with five ZrS6 octahedra, and edges with seven NaS6 octahedra. The corner-sharing octahedra tilt angles range from 7–11°. There are a spread of Na–S bond distances ranging from 2.78–2.96 Å. In the second Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share a cornercorner with one NaS6 octahedra, corners with five ZrS6 octahedra, edges with four ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 6–9°. There are a spread of Na–S bond distances ranging from 2.80–2.97 Å. In the third Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with two equivalent NaS6 octahedra, corners with four ZrS6 octahedra, edges with four ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 9–10°. There are a spread of Na–S bond distances ranging from 2.81–2.98 Å. In the fourth Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with two equivalent NaS6 octahedra, corners with four ZrS6 octahedra, edges with four ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 8–10°. There are a spread of Na–S bond distances ranging from 2.76–2.96 Å. In the fifth Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with two equivalent NaS6 octahedra, corners with four ZrS6 octahedra, edges with five ZrS6 octahedra, and edges with seven NaS6 octahedra. The corner-sharing octahedra tilt angles range from 7–12°. There are a spread of Na–S bond distances ranging from 2.75–2.94 Å. In the sixth Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with six ZrS6 octahedra, edges with four equivalent ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 7–8°. There are two shorter (2.90 Å) and four longer (2.93 Å) Na–S bond lengths. In the seventh Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with six NaS6 octahedra, edges with six NaS6 octahedra, and edges with six ZrS6 octahedra. The corner-sharing octahedra tilt angles range from 9–12°. There are four shorter (2.81 Å) and two longer (2.82 Å) Na–S bond lengths. In the eighth Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with six NaS6 octahedra, edges with six NaS6 octahedra, and edges with six ZrS6 octahedra. The corner-sharing octahedra tilt angles range from 9–11°. There are two shorter (2.80 Å) and four longer (2.82 Å) Na–S bond lengths. There are four inequivalent Zr+3.73+ sites. In the first Zr+3.73+ site, Zr+3.73+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with six NaS6 octahedra, edges with four ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 7–10°. There are four shorter (2.59 Å) and two longer (2.68 Å) Zr–S bond lengths. In the second Zr+3.73+ site, Zr+3.73+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with six NaS6 octahedra, edges with four ZrS6 octahedra, and edges with eight NaS6 octahedra. The corner-sharing octahedra tilt angles range from 7–9°. There are a spread of Zr–S bond distances ranging from 2.57–2.66 Å. In the third Zr+3.73+ site, Zr+3.73+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with six NaS6 octahedra, edges with three ZrS6 octahedra, and edges with nine NaS6 octahedra. The corner-sharing octahedra tilt angles range from 8–9°. There are a spread of Zr–S bond distances ranging from 2.58–2.61 Å. In the fourth Zr+3.73+ site, Zr+3.73+ is bonded to six S2- atoms to form ZrS6 octahedra that share corners with six NaS6 octahedra, edges with six NaS6 octahedra, and edges with six ZrS6 octahedra. The corner-sharing octahedra tilt angles range from 6–7°. There are four shorter (2.66 Å) and two longer (2.67 Å) Zr–S bond lengths. There are ten inequivalent S2- sites. In the first S2- site, S2- is bonded to four Na1+ and two Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 1–9°. In the second S2- site, S2- is bonded to three Na1+ and three Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa3Zr3 octahedra. The corner-sharing octahedra tilt angles range from 0–6°. In the third S2- site, S2- is bonded to four Na1+ and two equivalent Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 0–9°. In the fourth S2- site, S2- is bonded to four Na1+ and two Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 0–10°. In the fifth S2- site, S2- is bonded to four Na1+ and two Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 0–7°. In the sixth S2- site, S2- is bonded to four Na1+ and two equivalent Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 0–8°. In the seventh S2- site, S2- is bonded to four Na1+ and two equivalent Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 0–7°. In the eighth S2- site, S2- is bonded to four Na1+ and two equivalent Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 1–4°. In the ninth S2- site, S2- is bonded to four Na1+ and two equivalent Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa4Zr2 octahedra. The corner-sharing octahedra tilt angles range from 1–8°. In the tenth S2- site, S2- is bonded to three Na1+ and three Zr+3.73+ atoms to form a mixture of edge and corner-sharing SNa3Zr3 octahedra. The corner-sharing octahedra tilt angles range from 0–4°.