Na2PdO6 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Pd(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PdO6 octahedra that share corners with four equivalent O(1)Na2PdO tetrahedra. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one Pd(1) atom. In the second O site, O(1) is bonded to two equivalent Na(1), one Pd(1), and one O(1) atom to form distorted ONa2PdO tetrahedra that share  a cornercorner with one Pd(1)O6 octahedra, corners with five equivalent O(1)Na2PdO tetrahedra, and edges with two equivalent O(1)Na2PdO tetrahedra. The corner-sharing octahedral tilt angles are 66°.
Na2PdO6 crystallizes in the monoclinic C2/m space group. 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 2.40 Å. There are two shorter (2.47 Å) and two longer (2.70 Å) Na(1)-O(1) bond lengths. Pd(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PdO6 octahedra that share corners with four equivalent O(1)Na2PdO tetrahedra. Both Pd(1)-O(2) bond lengths are 1.89 Å. All Pd(1)-O(1) bond lengths are 2.11 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one Pd(1) atom. In the second O site, O(1) is bonded to two equivalent Na(1), one Pd(1), and one O(1) atom to form distorted ONa2PdO tetrahedra that share  a cornercorner with one Pd(1)O6 octahedra, corners with five equivalent O(1)Na2PdO tetrahedra, and edges with two equivalent O(1)Na2PdO tetrahedra. The corner-sharing octahedral tilt angles are 66°. The O(1)-O(1) bond length is 1.37 Å.