Materials Data on Na2VCu3S4 by Materials Project

Na2VCu3S4 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share a cornercorner with one VS4 tetrahedra, corners with eleven CuS4 tetrahedra, edges with six NaS6 octahedra, edges with two equivalent VS4 tetrahedra, and edges with four CuS4 tetrahedra. There are a spread of Na–S bond distances ranging from 2.80–2.98 Å. In the second Na1+ site, Na1+ is bonded to six S2- atoms to form NaS6 octahedra that share corners with five equivalent VS4 tetrahedra, corners with seven CuS4 tetrahedra, edges with six NaS6 octahedra, an edgeedge with one VS4 tetrahedra, and edges with five CuS4 tetrahedra. There are a spread of Na–S bond distances ranging from 2.79–2.97 Å. V3+ is bonded to four S2- atoms to form VS4 tetrahedra that share corners with six NaS6 octahedra, corners with two equivalent VS4 tetrahedra, corners with four equivalent CuS4 tetrahedra, edges with three NaS6 octahedra, and edges with three CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 21–50°. There are a spread of V–S bond distances ranging from 2.29–2.36 Å. There are three inequivalent Cu1+ sites. In the first Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with six NaS6 octahedra, corners with two equivalent CuS4 tetrahedra, corners with four equivalent VS4 tetrahedra, edges with three NaS6 octahedra, and edges with three CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 20–54°. There are two shorter (2.37 Å) and two longer (2.41 Å) Cu–S bond lengths. In the second Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with six NaS6 octahedra, corners with six CuS4 tetrahedra, edges with three NaS6 octahedra, an edgeedge with one CuS4 tetrahedra, and edges with two equivalent VS4 tetrahedra. The corner-sharing octahedra tilt angles range from 17–50°. There are a spread of Cu–S bond distances ranging from 2.30–2.41 Å. In the third Cu1+ site, Cu1+ is bonded to four S2- atoms to form CuS4 tetrahedra that share corners with six NaS6 octahedra, corners with six CuS4 tetrahedra, edges with three NaS6 octahedra, an edgeedge with one VS4 tetrahedra, and edges with two equivalent CuS4 tetrahedra. The corner-sharing octahedra tilt angles range from 16–52°. There are a spread of Cu–S bond distances ranging from 2.33–2.45 Å. There are four inequivalent S2- sites. In the first S2- site, S2- is bonded in a 7-coordinate geometry to three Na1+, one V3+, and three Cu1+ atoms. In the second S2- site, S2- is bonded in a 7-coordinate geometry to three Na1+, two equivalent V3+, and two Cu1+ atoms. In the third S2- site, S2- is bonded to three Na1+ and four Cu1+ atoms to form distorted edge-sharing SNa3Cu4 pentagonal bipyramids. In the fourth S2- site, S2- is bonded in a 7-coordinate geometry to three Na1+, one V3+, and three Cu1+ atoms.