Na5WNO4 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one N(1), two equivalent O(1), and two equivalent O(2) atoms. In the second Na site, Na(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with four equivalent W(1)NO4 trigonal bipyramids and edges with two equivalent Na(2)O4 trigonal pyramids. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one N(1), two equivalent O(1), and two equivalent O(2) atoms. W(1) is bonded to one N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted WNO4 trigonal bipyramids that share corners with eight equivalent Na(2)O4 trigonal pyramids. N(1) is bonded in a 3-coordinate geometry to one Na(3), two equivalent Na(1), and one W(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one W(1) atom to form a mixture of corner, face, and edge-sharing ONa5W octahedra. The corner-sharing octahedral tilt angles range from 19-43°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one W(1) atom to form a mixture of distorted corner, face, and edge-sharing ONa5W octahedra. The corner-sharing octahedral tilt angles range from 19-43°.
Na5WNO4 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one N(1), two equivalent O(1), and two equivalent O(2) atoms. The Na(1)-N(1) bond length is 2.40 Å. There is one shorter (2.40 Å) and one longer (2.47 Å) Na(1)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.56 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with four equivalent W(1)NO4 trigonal bipyramids and edges with two equivalent Na(2)O4 trigonal pyramids. There is one shorter (2.30 Å) and one longer (2.43 Å) Na(2)-O(1) bond length. There is one shorter (2.31 Å) and one longer (2.54 Å) Na(2)-O(2) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one N(1), two equivalent O(1), and two equivalent O(2) atoms. The Na(3)-N(1) bond length is 2.88 Å. Both Na(3)-O(1) bond lengths are 2.29 Å. Both Na(3)-O(2) bond lengths are 2.27 Å. W(1) is bonded to one N(1), two equivalent O(1), and two equivalent O(2) atoms to form distorted WNO4 trigonal bipyramids that share corners with eight equivalent Na(2)O4 trigonal pyramids. The W(1)-N(1) bond length is 1.81 Å. Both W(1)-O(1) bond lengths are 1.98 Å. Both W(1)-O(2) bond lengths are 1.99 Å. N(1) is bonded in a 3-coordinate geometry to one Na(3), two equivalent Na(1), and one W(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one W(1) atom to form a mixture of corner, face, and edge-sharing ONa5W octahedra. The corner-sharing octahedral tilt angles range from 19-43°. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one W(1) atom to form a mixture of distorted corner, face, and edge-sharing ONa5W octahedra. The corner-sharing octahedral tilt angles range from 19-43°.