Na2TeO4 crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Te(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing TeO6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Te(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), and two equivalent Te(1) atoms to form a mixture of distorted corner and edge-sharing ONa2Te2 trigonal pyramids.
Na2TeO4 crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Na(1)-O(2) bond lengths are 2.33 Å. There are two shorter (2.56 Å) and two longer (2.61 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Na(2)-O(2) bond lengths are 2.53 Å. There are two shorter (2.21 Å) and two longer (2.29 Å) Na(2)-O(1) bond lengths. Te(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form edge-sharing TeO6 octahedra. Both Te(1)-O(1) bond lengths are 1.85 Å. There are two shorter (1.98 Å) and two longer (2.03 Å) Te(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one Te(1) atom. In the second O site, O(2) is bonded to one Na(1), one Na(2), and two equivalent Te(1) atoms to form a mixture of distorted corner and edge-sharing ONa2Te2 trigonal pyramids.