Na4PtO4 crystallizes in the monoclinic C2/m space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a T-shaped geometry to one O(3) and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form NaO5 trigonal bipyramids that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Pt(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the third Na site, Na(3) is bonded in a see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. In the fourth Na site, Na(4) is bonded to one O(3), two equivalent O(2), and three equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(4)O6 octahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, edges with three equivalent Na(4)O6 octahedra, edges with five equivalent Pt(1)O6 octahedra, and edges with three equivalent Na(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-17°. Pt(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form PtO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra, corners with two equivalent Pt(1)O6 octahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Pt(1)O6 octahedra, edges with five equivalent Na(4)O6 octahedra, and edges with three equivalent Na(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-16°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one Pt(1) atom to form ONa5Pt octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(1)Na5Pt octahedra,  an edgeedge with one O(4)Na4Pt2 octahedra,  an edgeedge with one O(1)Na5Pt octahedra, edges with two equivalent O(2)Na4Pt2 octahedra, and edges with three equivalent O(3)Na5Pt octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(4), and two equivalent Pt(1) atoms to form ONa4Pt2 octahedra that share  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(2)Na4Pt2 octahedra,  an edgeedge with one O(2)Na4Pt2 octahedra, edges with two equivalent O(1)Na5Pt octahedra, edges with three equivalent O(3)Na5Pt octahedra, and edges with five equivalent O(4)Na4Pt2 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the third O site, O(3) is bonded to one Na(1), one Na(3), one Na(4), two equivalent Na(2), and one Pt(1) atom to form distorted ONa5Pt octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra, corners with two equivalent O(3)Na5Pt octahedra, edges with three equivalent O(2)Na4Pt2 octahedra, edges with three equivalent O(4)Na4Pt2 octahedra, and edges with three equivalent O(1)Na5Pt octahedra. The corner-sharing octahedral tilt angles range from 2-26°. In the fourth O site, O(4) is bonded to one Na(2), three equivalent Na(4), and two equivalent Pt(1) atoms to form distorted ONa4Pt2 octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(4)Na4Pt2 octahedra,  an edgeedge with one O(1)Na5Pt octahedra, edges with three equivalent O(4)Na4Pt2 octahedra, edges with three equivalent O(3)Na5Pt octahedra, and edges with five equivalent O(2)Na4Pt2 octahedra. The corner-sharing octahedral tilt angles range from 5-17°.
Na4PtO4 crystallizes in the monoclinic C2/m space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a T-shaped geometry to one O(3) and two equivalent O(1) atoms. The Na(1)-O(3) bond length is 2.25 Å. There is one shorter (2.16 Å) and one longer (2.29 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form NaO5 trigonal bipyramids that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, edges with three equivalent Na(4)O6 octahedra, and edges with three equivalent Pt(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(2) bond length is 2.25 Å. The Na(2)-O(4) bond length is 2.36 Å. Both Na(2)-O(3) bond lengths are 2.33 Å. In the third Na site, Na(3) is bonded in a see-saw-like geometry to one O(2), one O(3), and two equivalent O(1) atoms. The Na(3)-O(2) bond length is 2.18 Å. The Na(3)-O(3) bond length is 2.32 Å. Both Na(3)-O(1) bond lengths are 2.29 Å. In the fourth Na site, Na(4) is bonded to one O(3), two equivalent O(2), and three equivalent O(4) atoms to form distorted NaO6 octahedra that share  a cornercorner with one Pt(1)O6 octahedra, corners with two equivalent Na(4)O6 octahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, edges with three equivalent Na(4)O6 octahedra, edges with five equivalent Pt(1)O6 octahedra, and edges with three equivalent Na(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 16-17°. The Na(4)-O(3) bond length is 2.57 Å. There is one shorter (2.30 Å) and one longer (2.41 Å) Na(4)-O(2) bond length. There are two shorter (2.29 Å) and one longer (2.63 Å) Na(4)-O(4) bond length. Pt(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form PtO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra, corners with two equivalent Pt(1)O6 octahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid,  an edgeedge with one Pt(1)O6 octahedra, edges with five equivalent Na(4)O6 octahedra, and edges with three equivalent Na(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-16°. The Pt(1)-O(1) bond length is 2.09 Å. The Pt(1)-O(3) bond length is 2.06 Å. Both Pt(1)-O(2) bond lengths are 2.27 Å. There is one shorter (2.07 Å) and one longer (2.11 Å) Pt(1)-O(4) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), two equivalent Na(3), and one Pt(1) atom to form ONa5Pt octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(1)Na5Pt octahedra,  an edgeedge with one O(4)Na4Pt2 octahedra,  an edgeedge with one O(1)Na5Pt octahedra, edges with two equivalent O(2)Na4Pt2 octahedra, and edges with three equivalent O(3)Na5Pt octahedra. The corner-sharing octahedral tilt angles range from 2-17°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(4), and two equivalent Pt(1) atoms to form ONa4Pt2 octahedra that share  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(2)Na4Pt2 octahedra,  an edgeedge with one O(2)Na4Pt2 octahedra, edges with two equivalent O(1)Na5Pt octahedra, edges with three equivalent O(3)Na5Pt octahedra, and edges with five equivalent O(4)Na4Pt2 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. In the third O site, O(3) is bonded to one Na(1), one Na(3), one Na(4), two equivalent Na(2), and one Pt(1) atom to form distorted ONa5Pt octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(4)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra, corners with two equivalent O(3)Na5Pt octahedra, edges with three equivalent O(2)Na4Pt2 octahedra, edges with three equivalent O(4)Na4Pt2 octahedra, and edges with three equivalent O(1)Na5Pt octahedra. The corner-sharing octahedral tilt angles range from 2-26°. In the fourth O site, O(4) is bonded to one Na(2), three equivalent Na(4), and two equivalent Pt(1) atoms to form distorted ONa4Pt2 octahedra that share  a cornercorner with one O(2)Na4Pt2 octahedra,  a cornercorner with one O(1)Na5Pt octahedra,  a cornercorner with one O(3)Na5Pt octahedra, corners with two equivalent O(4)Na4Pt2 octahedra,  an edgeedge with one O(1)Na5Pt octahedra, edges with three equivalent O(4)Na4Pt2 octahedra, edges with three equivalent O(3)Na5Pt octahedra, and edges with five equivalent O(2)Na4Pt2 octahedra. The corner-sharing octahedral tilt angles range from 5-17°.