Na2UTeO7 crystallizes in the orthorhombic Ama2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share corners with two equivalent Te(1)O6 octahedra and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. U(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms. Te(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form TeO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Na(1)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 33°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one U(1) atom. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), and one U(1) atom to form distorted ONa3U tetrahedra that share corners with two equivalent O(2)Na3U tetrahedra, corners with four equivalent O(3)Na2UTe trigonal pyramids, and edges with two equivalent O(3)Na2UTe trigonal pyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one U(1), and one Te(1) atom to form distorted ONa2UTe trigonal pyramids that share corners with two equivalent O(2)Na3U tetrahedra, corners with two equivalent O(3)Na2UTe trigonal pyramids,  an edgeedge with one O(2)Na3U tetrahedra, and  an edgeedge with one O(3)Na2UTe trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1), one U(1), and two equivalent Te(1) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one U(1), and one Te(1) atom.
Na2UTeO7 crystallizes in the orthorhombic Ama2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share corners with two equivalent Te(1)O6 octahedra and edges with two equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The Na(1)-O(1) bond length is 2.37 Å. The Na(1)-O(2) bond length is 2.48 Å. The Na(1)-O(4) bond length is 2.77 Å. Both Na(1)-O(3) bond lengths are 2.37 Å. Both Na(1)-O(5) bond lengths are 2.62 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Na(2)-O(1) bond lengths are 2.65 Å. Both Na(2)-O(2) bond lengths are 2.47 Å. Both Na(2)-O(3) bond lengths are 2.75 Å. Both Na(2)-O(5) bond lengths are 2.89 Å. U(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms. The U(1)-O(1) bond length is 1.87 Å. The U(1)-O(2) bond length is 1.89 Å. The U(1)-O(4) bond length is 2.58 Å. Both U(1)-O(3) bond lengths are 2.34 Å. Both U(1)-O(5) bond lengths are 2.24 Å. Te(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form TeO6 octahedra that share corners with two equivalent Te(1)O6 octahedra, corners with two equivalent Na(1)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles are 33°. Both Te(1)-O(3) bond lengths are 1.92 Å. Both Te(1)-O(4) bond lengths are 1.99 Å. Both Te(1)-O(5) bond lengths are 1.93 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(2), and one U(1) atom. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), and one U(1) atom to form distorted ONa3U tetrahedra that share corners with two equivalent O(2)Na3U tetrahedra, corners with four equivalent O(3)Na2UTe trigonal pyramids, and edges with two equivalent O(3)Na2UTe trigonal pyramids. In the third O site, O(3) is bonded to one Na(1), one Na(2), one U(1), and one Te(1) atom to form distorted ONa2UTe trigonal pyramids that share corners with two equivalent O(2)Na3U tetrahedra, corners with two equivalent O(3)Na2UTe trigonal pyramids,  an edgeedge with one O(2)Na3U tetrahedra, and  an edgeedge with one O(3)Na2UTe trigonal pyramid. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1), one U(1), and two equivalent Te(1) atoms. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one U(1), and one Te(1) atom.