NaAsO3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one As(1)O4 tetrahedra,  a cornercorner with one As(2)O4 tetrahedra, corners with three equivalent As(3)O4 tetrahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. In the second Na site, Na(2) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one As(1)O4 tetrahedra,  a cornercorner with one As(3)O4 tetrahedra, corners with three equivalent As(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. In the third Na site, Na(3) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(6) atoms to form NaO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(3)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, and edges with two equivalent Na(3)O6 octahedra. There are three inequivalent As sites. In the first As site, As(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra,  a cornercorner with one As(2)O4 tetrahedra,  a cornercorner with one As(3)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-62°. In the second As site, As(2) is bonded to one O(1), one O(4), one O(6), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. In the third As site, As(3) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-67°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one As(2) and one As(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one As(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one As(1), and one As(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(3), and one As(3) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one As(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one As(1), and one As(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one As(2) atom.
NaAsO3 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom to form distorted NaO6 octahedra that share  a cornercorner with one As(1)O4 tetrahedra,  a cornercorner with one As(2)O4 tetrahedra, corners with three equivalent As(3)O4 tetrahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The Na(1)-O(2) bond length is 2.57 Å. The Na(1)-O(3) bond length is 2.55 Å. The Na(1)-O(5) bond length is 2.32 Å. The Na(1)-O(7) bond length is 2.33 Å. The Na(1)-O(8) bond length is 2.43 Å. The Na(1)-O(9) bond length is 2.27 Å. In the second Na site, Na(2) is bonded to one O(2), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form NaO6 octahedra that share  a cornercorner with one As(1)O4 tetrahedra,  a cornercorner with one As(3)O4 tetrahedra, corners with three equivalent As(2)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The Na(2)-O(2) bond length is 2.46 Å. The Na(2)-O(3) bond length is 2.46 Å. The Na(2)-O(4) bond length is 2.48 Å. The Na(2)-O(6) bond length is 2.32 Å. The Na(2)-O(7) bond length is 2.49 Å. The Na(2)-O(9) bond length is 2.35 Å. In the third Na site, Na(3) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(6) atoms to form NaO6 octahedra that share corners with two equivalent As(1)O4 tetrahedra, corners with two equivalent As(2)O4 tetrahedra, corners with two equivalent As(3)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, and edges with two equivalent Na(3)O6 octahedra. The Na(3)-O(2) bond length is 2.37 Å. The Na(3)-O(3) bond length is 2.33 Å. Both Na(3)-O(5) bond lengths are 2.41 Å. There is one shorter (2.38 Å) and one longer (2.40 Å) Na(3)-O(6) bond length. There are three inequivalent As sites. In the first As site, As(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra,  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra,  a cornercorner with one As(2)O4 tetrahedra,  a cornercorner with one As(3)O4 tetrahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-62°. The As(1)-O(2) bond length is 1.65 Å. The As(1)-O(3) bond length is 1.65 Å. The As(1)-O(4) bond length is 1.77 Å. The As(1)-O(8) bond length is 1.76 Å. In the second As site, As(2) is bonded to one O(1), one O(4), one O(6), and one O(9) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(2)O6 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-67°. The As(2)-O(1) bond length is 1.75 Å. The As(2)-O(4) bond length is 1.77 Å. The As(2)-O(6) bond length is 1.65 Å. The As(2)-O(9) bond length is 1.65 Å. In the third As site, As(3) is bonded to one O(1), one O(5), one O(7), and one O(8) atom to form AsO4 tetrahedra that share  a cornercorner with one Na(2)O6 octahedra, corners with two equivalent Na(3)O6 octahedra, corners with three equivalent Na(1)O6 octahedra,  a cornercorner with one As(1)O4 tetrahedra, and  a cornercorner with one As(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 41-67°. The As(3)-O(1) bond length is 1.76 Å. The As(3)-O(5) bond length is 1.66 Å. The As(3)-O(7) bond length is 1.64 Å. The As(3)-O(8) bond length is 1.78 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one As(2) and one As(3) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one As(1) atom. In the third O site, O(3) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one As(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one As(1), and one As(2) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Na(3), and one As(3) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one As(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one As(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one As(1), and one As(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one As(2) atom.