DOE OSTI2020
Na16W3(NO3)4 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are sixteen inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to five O2- atoms to form NaO5 square pyramids that share corners with two equivalent NaO5 square pyramids, a cornercorner with one WNO3 tetrahedra, corners with two NaN2O2 tetrahedra, corners with two equivalent NaNO3 trigonal pyramids, an edgeedge with one NaO5 square pyramid, edges with two WNO3 tetrahedra, and an edgeedge with one NaNO3 trigonal pyramid. There are a spread of Na–O bond distances ranging from 2.31–2.56 Å. In the second Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.17–2.91 Å. In the third Na1+ site, Na1+ is bonded in a 2-coordinate geometry to four O2- atoms. There are a spread of Na–O bond distances ranging from 2.18–2.99 Å. In the fourth Na1+ site, Na1+ is bonded in a 1-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.16–2.96 Å. In the fifth Na1+ site, Na1+ is bonded to two N+2.50- and two O2- atoms to form distorted NaN2O2 tetrahedra that share corners with two NaO5 square pyramids, a cornercorner with one NaNO3 tetrahedra, corners with three WNO3 tetrahedra, and corners with two NaNO3 trigonal pyramids. There are one shorter (2.29 Å) and one longer (2.42 Å) Na–N bond lengths. There are one shorter (2.35 Å) and one longer (2.42 Å) Na–O bond lengths. In the sixth Na1+ site, Na1+ is bonded in a 4-coordinate geometry to two N+2.50- and two O2- atoms. There are one shorter (2.55 Å) and one longer (2.58 Å) Na–N bond lengths. There are one shorter (2.22 Å) and one longer (2.57 Å) Na–O bond lengths. In the seventh Na1+ site, Na1+ is bonded to two N+2.50- and two O2- atoms to form distorted NaN2O2 tetrahedra that share a cornercorner with one NaO5 square pyramid, a cornercorner with one NaNO3 tetrahedra, corners with three WNO3 tetrahedra, and corners with two NaNO3 trigonal pyramids. There are one shorter (2.51 Å) and one longer (2.57 Å) Na–N bond lengths. There are one shorter (2.22 Å) and one longer (2.55 Å) Na–O bond lengths. In the eighth Na1+ site, Na1+ is bonded in a distorted rectangular see-saw-like geometry to two N+2.50- and two O2- atoms. There are one shorter (2.32 Å) and one longer (2.50 Å) Na–N bond lengths. There are one shorter (2.40 Å) and one longer (2.47 Å) Na–O bond lengths. In the ninth Na1+ site, Na1+ is bonded in a 2-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.18–3.04 Å. In the tenth Na1+ site, Na1+ is bonded to five O2- atoms to form distorted NaO5 square pyramids that share a cornercorner with one NaN2O2 tetrahedra, corners with two equivalent WNO3 tetrahedra, a cornercorner with one NaNO3 trigonal pyramid, edges with two NaO5 square pyramids, an edgeedge with one NaNO3 tetrahedra, and an edgeedge with one WNO3 tetrahedra. There are a spread of Na–O bond distances ranging from 2.18–2.72 Å. In the eleventh Na1+ site, Na1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.80 Å. In the twelfth Na1+ site, Na1+ is bonded to five O2- atoms to form distorted NaO5 square pyramids that share corners with two equivalent NaO5 square pyramids, a cornercorner with one NaN2O2 tetrahedra, a cornercorner with one WNO3 tetrahedra, a cornercorner with one NaNO3 trigonal pyramid, an edgeedge with one NaO5 square pyramid, an edgeedge with one NaNO3 tetrahedra, and an edgeedge with one WNO3 tetrahedra. There are a spread of Na–O bond distances ranging from 2.13–2.68 Å. In the thirteenth Na1+ site, Na1+ is bonded to one N+2.50- and three O2- atoms to form distorted NaNO3 trigonal pyramids that share a cornercorner with one NaO5 square pyramid, corners with two NaN2O2 tetrahedra, corners with four WNO3 tetrahedra, and an edgeedge with one NaO5 square pyramid. The Na–N bond length is 2.46 Å. There are two shorter (2.40 Å) and one longer (2.56 Å) Na–O bond lengths. In the fourteenth Na1+ site, Na1+ is bonded to one N+2.50- and three O2- atoms to form distorted NaNO3 tetrahedra that share a cornercorner with one NaO5 square pyramid, corners with two NaN2O2 tetrahedra, corners with three WNO3 tetrahedra, and edges with two NaO5 square pyramids. The Na–N bond length is 2.40 Å. There are a spread of Na–O bond distances ranging from 2.44–2.55 Å. In the fifteenth Na1+ site, Na1+ is bonded to one N+2.50- and three O2- atoms to form distorted NaNO3 trigonal pyramids that share corners with three NaO5 square pyramids, corners with two NaN2O2 tetrahedra, and corners with three WNO3 tetrahedra. The Na–N bond length is 2.38 Å. There are a spread of Na–O bond distances ranging from 2.13–2.54 Å. In the sixteenth Na1+ site, Na1+ is bonded in a distorted rectangular see-saw-like geometry to one N+2.50- and three O2- atoms. The Na–N bond length is 2.62 Å. There are a spread of Na–O bond distances ranging from 2.25–2.75 Å. There are three inequivalent W6+ sites. In the first W6+ site, W6+ is bonded to one N+2.50- and three O2- atoms to form WNO3 tetrahedra that share corners with two NaN2O2 tetrahedra, corners with three NaNO3 trigonal pyramids, and edges with two NaO5 square pyramids. The W–N bond length is 1.80 Å. There is one shorter (1.87 Å) and two longer (1.88 Å) W–O bond length. In the second W6+ site, W6+ is bonded to one N+2.50- and three O2- atoms to form WNO3 tetrahedra that share corners with three NaO5 square pyramids, corners with four NaN2O2 tetrahedra, a cornercorner with one NaNO3 trigonal pyramid, and an edgeedge with one NaO5 square pyramid. The W–N bond length is 1.79 Å. There are a spread of W–O bond distances ranging from 1.88–1.90 Å. In the third W6+ site, W6+ is bonded to one N+2.50- and three O2- atoms to form WNO3 tetrahedra that share a cornercorner with one NaO5 square pyramid, corners with three NaN2O2 tetrahedra, corners with three NaNO3 trigonal pyramids, and an edgeedge with one NaO5 square pyramid. The W–N bond length is 1.80 Å. There is one shorter (1.87 Å) and two longer (1.88 Å) W–O bond length. There are four inequivalent N+2.50- sites. In the first N+2.50- site, N+2.50- is bonded in a trigonal non-coplanar geometry to three Na1+ atoms. In the second N+2.50- site, N+2.50- is bonded to three Na1+ and one W6+ atom to form distorted NNa3W tetrahedra that share a cornercorner with one ONa5W octahedra and corners with three ONa4W square pyramids. The corner-sharing octahedral tilt angles are 62°. In the third N+2.50- site, N+2.50- is bonded in a rectangular see-saw-like geometry to three Na1+ and one W6+ atom. In the fourth N+2.50- site, N+2.50- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one W6+ atom. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom. In the second O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom. In the third O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom. In the fourth O2- site, O2- is bonded to five Na1+ atoms to form ONa5 square pyramids that share corners with two ONa4W square pyramids, a cornercorner with one ONa5 trigonal bipyramid, an edgeedge with one ONa5W octahedra, and an edgeedge with one ONa5 trigonal bipyramid. In the fifth O2- site, O2- is bonded to five Na1+ atoms to form ONa5 square pyramids that share corners with two ONa4W square pyramids, corners with two equivalent NNa3W tetrahedra, and a cornercorner with one ONa5 trigonal bipyramid. In the sixth O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom. In the seventh O2- site, O2- is bonded to five Na1+ and one W6+ atom to form distorted ONa5W octahedra that share corners with two equivalent ONa4W square pyramids, a cornercorner with one NNa3W tetrahedra, and an edgeedge with one ONa5W octahedra. In the eighth O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom. In the ninth O2- site, O2- is bonded to five Na1+ atoms to form ONa5 trigonal bipyramids that share corners with two ONa5 square pyramids, an edgeedge with one ONa5W octahedra, and an edgeedge with one ONa5 square pyramid. In the tenth O2- site, O2- is bonded to four Na1+ and one W6+ atom to form distorted ONa4W square pyramids that share corners with two equivalent ONa5W octahedra, corners with two ONa5 square pyramids, a cornercorner with one NNa3W tetrahedra, and an edgeedge with one ONa5W octahedra. The corner-sharing octahedra tilt angles range from 17–23°. In the eleventh O2- site, O2- is bonded to five Na1+ and one W6+ atom to form distorted ONa5W octahedra that share an edgeedge with one ONa5W octahedra, edges with two ONa4W square pyramids, and an edgeedge with one ONa5 trigonal bipyramid. In the twelfth O2- site, O2- is bonded in a 6-coordinate geometry to five Na1+ and one W6+ atom.