Na2PtO6 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with four equivalent O(1)Na2PtO tetrahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Pt(1)O6 octahedra. Pt(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PtO6 octahedra that share corners with four equivalent O(1)Na2PtO tetrahedra and edges with six equivalent Na(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one Pt(1) atom. In the second O site, O(1) is bonded to two equivalent Na(1), one Pt(1), and one O(1) atom to form distorted ONa2PtO tetrahedra that share  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with five equivalent O(1)Na2PtO tetrahedra, and edges with two equivalent O(1)Na2PtO tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°.
Na2PtO6 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with four equivalent O(1)Na2PtO tetrahedra, edges with three equivalent Na(1)O6 octahedra, and edges with three equivalent Pt(1)O6 octahedra. Both Na(1)-O(2) bond lengths are 2.36 Å. There are two shorter (2.44 Å) and two longer (2.68 Å) Na(1)-O(1) bond lengths. Pt(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form PtO6 octahedra that share corners with four equivalent O(1)Na2PtO tetrahedra and edges with six equivalent Na(1)O6 octahedra. Both Pt(1)-O(2) bond lengths are 1.88 Å. All Pt(1)-O(1) bond lengths are 2.09 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one Pt(1) atom. In the second O site, O(1) is bonded to two equivalent Na(1), one Pt(1), and one O(1) atom to form distorted ONa2PtO tetrahedra that share  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, corners with five equivalent O(1)Na2PtO tetrahedra, and edges with two equivalent O(1)Na2PtO tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°. The O(1)-O(1) bond length is 1.40 Å.