NaAsO6 crystallizes in the monoclinic P2_1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(6), two equivalent O(4), and three equivalent O(3) atoms. As(1) is bonded in a trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one As(1), and one O(4) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one O(4) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one O(1), and one O(3) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one O(6) atom. In the sixth O site, O(6) is bonded in a water-like geometry to one Na(1) and one O(5) atom.
NaAsO6 crystallizes in the monoclinic P2_1 space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(6), two equivalent O(4), and three equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.36 Å. The Na(1)-O(6) bond length is 2.56 Å. There is one shorter (2.66 Å) and one longer (2.68 Å) Na(1)-O(4) bond length. There are a spread of Na(1)-O(3) bond distances ranging from 2.41-2.72 Å. As(1) is bonded in a trigonal non-coplanar geometry to one O(1) and two equivalent O(2) atoms. The As(1)-O(1) bond length is 1.80 Å. There is one shorter (1.82 Å) and one longer (1.85 Å) As(1)-O(2) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one As(1), and one O(4) atom. The O(1)-O(4) bond length is 1.78 Å. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent As(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one O(4) atom. The O(3)-O(4) bond length is 1.32 Å. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one O(1), and one O(3) atom. In the fifth O site, O(5) is bonded in a single-bond geometry to one O(6) atom. The O(5)-O(6) bond length is 1.26 Å. In the sixth O site, O(6) is bonded in a water-like geometry to one Na(1) and one O(5) atom.