DOE OSTI2020
Na15Mo7N19 crystallizes in the triclinic P-1 space group. The structure is three-dimensional. there are sixteen inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six N3- atoms. There are a spread of Na–N bond distances ranging from 2.60–2.92 Å. In the second Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.43–2.76 Å. In the third Na1+ site, Na1+ is bonded to four N3- atoms to form NaN4 tetrahedra that share corners with two equivalent NaN4 tetrahedra, corners with four MoN4 tetrahedra, and an edgeedge with one NaN4 trigonal pyramid. There are a spread of Na–N bond distances ranging from 2.48–2.68 Å. In the fourth Na1+ site, Na1+ is bonded to four N3- atoms to form distorted NaN4 trigonal pyramids that share corners with three NaN4 tetrahedra, corners with three MoN4 tetrahedra, an edgeedge with one NaN4 tetrahedra, and an edgeedge with one MoN4 tetrahedra. There are a spread of Na–N bond distances ranging from 2.37–2.54 Å. In the fifth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.44–2.79 Å. In the sixth Na1+ site, Na1+ is bonded to four N3- atoms to form distorted NaN4 tetrahedra that share corners with two equivalent NaN4 tetrahedra, corners with five MoN4 tetrahedra, and a cornercorner with one NaN4 trigonal pyramid. There are a spread of Na–N bond distances ranging from 2.38–2.71 Å. In the seventh Na1+ site, Na1+ is bonded in a distorted pentagonal planar geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.43–2.69 Å. In the eighth Na1+ site, Na1+ is bonded in a 4-coordinate geometry to four N3- atoms. There are a spread of Na–N bond distances ranging from 2.35–2.60 Å. In the ninth Na1+ site, Na1+ is bonded to four N3- atoms to form NaN4 tetrahedra that share corners with five MoN4 tetrahedra, corners with two equivalent NaN4 trigonal pyramids, and an edgeedge with one NaN4 tetrahedra. There are a spread of Na–N bond distances ranging from 2.36–2.74 Å. In the tenth Na1+ site, Na1+ is bonded in a 3-coordinate geometry to four N3- atoms. There are a spread of Na–N bond distances ranging from 2.48–3.06 Å. In the eleventh Na1+ site, Na1+ is bonded in a 3-coordinate geometry to three N3- atoms. There are a spread of Na–N bond distances ranging from 2.36–2.60 Å. In the twelfth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.45–3.06 Å. In the thirteenth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.51–2.74 Å. In the fourteenth Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.47–2.81 Å. In the fifteenth Na1+ site, Na1+ is bonded in a 2-coordinate geometry to six N3- atoms. There are a spread of Na–N bond distances ranging from 2.32–3.16 Å. In the sixteenth Na1+ site, Na1+ is bonded in a distorted linear geometry to six N3- atoms. There are a spread of Na–N bond distances ranging from 2.42–3.08 Å. There are seven inequivalent Mo6+ sites. In the first Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share a cornercorner with one NaN4 tetrahedra and corners with three MoN4 tetrahedra. There are a spread of Mo–N bond distances ranging from 1.79–1.93 Å. In the second Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share a cornercorner with one NaN4 tetrahedra and corners with three MoN4 tetrahedra. There are a spread of Mo–N bond distances ranging from 1.78–1.93 Å. In the third Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share a cornercorner with one NaN4 tetrahedra, corners with three MoN4 tetrahedra, and a cornercorner with one NaN4 trigonal pyramid. There are a spread of Mo–N bond distances ranging from 1.80–1.93 Å. In the fourth Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share corners with two MoN4 tetrahedra, corners with three equivalent NaN4 tetrahedra, and a cornercorner with one NaN4 trigonal pyramid. There are a spread of Mo–N bond distances ranging from 1.80–1.97 Å. In the fifth Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share a cornercorner with one NaN4 tetrahedra and corners with three MoN4 tetrahedra. There are a spread of Mo–N bond distances ranging from 1.79–1.91 Å. In the sixth Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share corners with two MoN4 tetrahedra, corners with four NaN4 tetrahedra, a cornercorner with one NaN4 trigonal pyramid, and an edgeedge with one NaN4 trigonal pyramid. There are a spread of Mo–N bond distances ranging from 1.80–1.97 Å. In the seventh Mo6+ site, Mo6+ is bonded to four N3- atoms to form MoN4 tetrahedra that share corners with two MoN4 tetrahedra and corners with three NaN4 tetrahedra. There are a spread of Mo–N bond distances ranging from 1.81–1.96 Å. There are nineteen inequivalent N3- sites. In the first N3- site, N3- is bonded in a 5-coordinate geometry to four Na1+ and one Mo6+ atom. In the second N3- site, N3- is bonded in a 6-coordinate geometry to four Na1+ and two Mo6+ atoms. In the third N3- site, N3- is bonded to four Na1+ and one Mo6+ atom to form distorted corner-sharing NNa4Mo trigonal bipyramids. In the fourth N3- site, N3- is bonded in a distorted rectangular see-saw-like geometry to two Na1+ and two Mo6+ atoms. In the fifth N3- site, N3- is bonded in a 4-coordinate geometry to two Na1+ and two Mo6+ atoms. In the sixth N3- site, N3- is bonded in a 5-coordinate geometry to five Na1+ and one Mo6+ atom. In the seventh N3- site, N3- is bonded in a 5-coordinate geometry to four Na1+ and one Mo6+ atom. In the eighth N3- site, N3- is bonded to three Na1+ and two Mo6+ atoms to form distorted corner-sharing NNa3Mo2 trigonal bipyramids. In the ninth N3- site, N3- is bonded in a 5-coordinate geometry to four Na1+ and one Mo6+ atom. In the tenth N3- site, N3- is bonded in a 6-coordinate geometry to five Na1+ and one Mo6+ atom. In the eleventh N3- site, N3- is bonded in a 5-coordinate geometry to three Na1+ and two Mo6+ atoms. In the twelfth N3- site, N3- is bonded in a 6-coordinate geometry to five Na1+ and one Mo6+ atom. In the thirteenth N3- site, N3- is bonded in a 5-coordinate geometry to three Na1+ and two Mo6+ atoms. In the fourteenth N3- site, N3- is bonded to three Na1+ and two Mo6+ atoms to form NNa3Mo2 trigonal bipyramids that share a cornercorner with one NNa3Mo2 trigonal bipyramid and an edgeedge with one NNa4Mo trigonal bipyramid. In the fifteenth N3- site, N3- is bonded in a 5-coordinate geometry to four Na1+ and one Mo6+ atom. In the sixteenth N3- site, N3- is bonded in a 6-coordinate geometry to four Na1+ and two Mo6+ atoms. In the seventeenth N3- site, N3- is bonded in a 3-coordinate geometry to one Na1+ and two Mo6+ atoms. In the eighteenth N3- site, N3- is bonded in a 6-coordinate geometry to five Na1+ and one Mo6+ atom. In the nineteenth N3- site, N3- is bonded to four Na1+ and one Mo6+ atom to form distorted NNa4Mo trigonal bipyramids that share a cornercorner with one NNa4Mo trigonal bipyramid and an edgeedge with one NNa3Mo2 trigonal bipyramid.