Na2AsTe2 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(3), one Te(4), two equivalent Te(1), and two equivalent Te(2) atoms to form distorted NaTe6 octahedra that share corners with three equivalent Na(2)Te6 octahedra, corners with four equivalent Na(1)Te6 octahedra,  a cornercorner with one As(2)NaTe2As tetrahedra, corners with three equivalent As(1)NaTe2As trigonal pyramids,  an edgeedge with one As(2)NaTe2As tetrahedra, and faces with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 30-44°. In the second Na site, Na(2) is bonded to one Te(2), one Te(3), two equivalent Te(1), and two equivalent Te(4) atoms to form NaTe6 octahedra that share corners with three equivalent Na(1)Te6 octahedra, corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent As(2)NaTe2As tetrahedra, corners with two equivalent As(1)NaTe2As trigonal pyramids,  an edgeedge with one As(1)NaTe2As trigonal pyramid, and faces with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 30-44°. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Te(1), one Te(2), one Te(3), and two equivalent Te(4) atoms. In the fourth Na site, Na(4) is bonded in a distorted hexagonal planar geometry to one As(1), one As(2), one Te(1), one Te(2), and two equivalent Te(3) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Na(4), one As(2), one Te(1), and one Te(4) atom to form distorted AsNaTe2As trigonal pyramids that share corners with two equivalent Na(2)Te6 octahedra, corners with three equivalent Na(1)Te6 octahedra,  a cornercorner with one Te(1)Na6As pentagonal bipyramid, corners with two equivalent Te(2)Na5As pentagonal pyramids,  a cornercorner with one As(2)NaTe2As tetrahedra, and  an edgeedge with one Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 72-95°. In the second As site, As(2) is bonded to one Na(4), one As(1), one Te(2), and one Te(3) atom to form distorted AsNaTe2As tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with two equivalent Na(2)Te6 octahedra, corners with two equivalent Te(1)Na6As pentagonal bipyramids,  a cornercorner with one Te(2)Na5As pentagonal pyramid,  a cornercorner with one As(1)NaTe2As trigonal pyramid, and  an edgeedge with one Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 76-99°. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(2), and one As(1) atom to form TeNa6As pentagonal bipyramids that share corners with two equivalent Te(2)Na5As pentagonal pyramids, corners with two equivalent As(2)NaTe2As tetrahedra,  a cornercorner with one As(1)NaTe2As trigonal pyramid, edges with two equivalent Te(1)Na6As pentagonal bipyramids, and edges with three equivalent Te(2)Na5As pentagonal pyramids. In the second Te site, Te(2) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one As(2) atom to form distorted TeNa5As pentagonal pyramids that share corners with two equivalent Te(1)Na6As pentagonal bipyramids, corners with two equivalent Te(2)Na5As pentagonal pyramids,  a cornercorner with one As(2)NaTe2As tetrahedra, corners with two equivalent As(1)NaTe2As trigonal pyramids, and edges with three equivalent Te(1)Na6As pentagonal bipyramids. In the third Te site, Te(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one As(2) atom. In the fourth Te site, Te(4) is bonded in a 6-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), and one As(1) atom.
Na2AsTe2 crystallizes in the orthorhombic P2_12_12_1 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one Te(3), one Te(4), two equivalent Te(1), and two equivalent Te(2) atoms to form distorted NaTe6 octahedra that share corners with three equivalent Na(2)Te6 octahedra, corners with four equivalent Na(1)Te6 octahedra,  a cornercorner with one As(2)NaTe2As tetrahedra, corners with three equivalent As(1)NaTe2As trigonal pyramids,  an edgeedge with one As(2)NaTe2As tetrahedra, and faces with two equivalent Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 30-44°. The Na(1)-Te(3) bond length is 3.62 Å. The Na(1)-Te(4) bond length is 3.22 Å. There is one shorter (3.17 Å) and one longer (3.37 Å) Na(1)-Te(1) bond length. There is one shorter (3.30 Å) and one longer (3.37 Å) Na(1)-Te(2) bond length. In the second Na site, Na(2) is bonded to one Te(2), one Te(3), two equivalent Te(1), and two equivalent Te(4) atoms to form NaTe6 octahedra that share corners with three equivalent Na(1)Te6 octahedra, corners with four equivalent Na(2)Te6 octahedra, corners with two equivalent As(2)NaTe2As tetrahedra, corners with two equivalent As(1)NaTe2As trigonal pyramids,  an edgeedge with one As(1)NaTe2As trigonal pyramid, and faces with two equivalent Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 30-44°. The Na(2)-Te(2) bond length is 3.22 Å. The Na(2)-Te(3) bond length is 3.35 Å. There is one shorter (3.26 Å) and one longer (3.34 Å) Na(2)-Te(1) bond length. There is one shorter (3.26 Å) and one longer (3.43 Å) Na(2)-Te(4) bond length. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one Te(1), one Te(2), one Te(3), and two equivalent Te(4) atoms. The Na(3)-Te(1) bond length is 3.41 Å. The Na(3)-Te(2) bond length is 3.22 Å. The Na(3)-Te(3) bond length is 3.40 Å. There is one shorter (3.28 Å) and one longer (3.68 Å) Na(3)-Te(4) bond length. In the fourth Na site, Na(4) is bonded in a distorted hexagonal planar geometry to one As(1), one As(2), one Te(1), one Te(2), and two equivalent Te(3) atoms. The Na(4)-As(1) bond length is 3.11 Å. The Na(4)-As(2) bond length is 3.09 Å. The Na(4)-Te(1) bond length is 3.17 Å. The Na(4)-Te(2) bond length is 3.41 Å. There is one shorter (3.24 Å) and one longer (3.27 Å) Na(4)-Te(3) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded to one Na(4), one As(2), one Te(1), and one Te(4) atom to form distorted AsNaTe2As trigonal pyramids that share corners with two equivalent Na(2)Te6 octahedra, corners with three equivalent Na(1)Te6 octahedra,  a cornercorner with one Te(1)Na6As pentagonal bipyramid, corners with two equivalent Te(2)Na5As pentagonal pyramids,  a cornercorner with one As(2)NaTe2As tetrahedra, and  an edgeedge with one Na(2)Te6 octahedra. The corner-sharing octahedral tilt angles range from 72-95°. The As(1)-As(2) bond length is 2.53 Å. The As(1)-Te(1) bond length is 2.62 Å. The As(1)-Te(4) bond length is 2.63 Å. In the second As site, As(2) is bonded to one Na(4), one As(1), one Te(2), and one Te(3) atom to form distorted AsNaTe2As tetrahedra that share  a cornercorner with one Na(1)Te6 octahedra, corners with two equivalent Na(2)Te6 octahedra, corners with two equivalent Te(1)Na6As pentagonal bipyramids,  a cornercorner with one Te(2)Na5As pentagonal pyramid,  a cornercorner with one As(1)NaTe2As trigonal pyramid, and  an edgeedge with one Na(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 76-99°. The As(2)-Te(2) bond length is 2.62 Å. The As(2)-Te(3) bond length is 2.65 Å. There are four inequivalent Te sites. In the first Te site, Te(1) is bonded to one Na(3), one Na(4), two equivalent Na(1), two equivalent Na(2), and one As(1) atom to form TeNa6As pentagonal bipyramids that share corners with two equivalent Te(2)Na5As pentagonal pyramids, corners with two equivalent As(2)NaTe2As tetrahedra,  a cornercorner with one As(1)NaTe2As trigonal pyramid, edges with two equivalent Te(1)Na6As pentagonal bipyramids, and edges with three equivalent Te(2)Na5As pentagonal pyramids. In the second Te site, Te(2) is bonded to one Na(2), one Na(3), one Na(4), two equivalent Na(1), and one As(2) atom to form distorted TeNa5As pentagonal pyramids that share corners with two equivalent Te(1)Na6As pentagonal bipyramids, corners with two equivalent Te(2)Na5As pentagonal pyramids,  a cornercorner with one As(2)NaTe2As tetrahedra, corners with two equivalent As(1)NaTe2As trigonal pyramids, and edges with three equivalent Te(1)Na6As pentagonal bipyramids. In the third Te site, Te(3) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one As(2) atom. In the fourth Te site, Te(4) is bonded in a 6-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(3), and one As(1) atom.