Na3RuO4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with six equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Na(6)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Na(5)O6 octahedra, corners with two equivalent Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-20°. In the third Na site, Na(3) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Ru(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-21°. In the fourth Na site, Na(4) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ru(2)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with four equivalent Na(3)O6 octahedra, and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-19°. In the fifth Na site, Na(5) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-20°. In the sixth Na site, Na(6) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ru(2)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with six equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the second Ru site, Ru(2) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form RuO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Na(6)O6 octahedra, corners with four equivalent Na(5)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Na(4), two equivalent Na(3), one Ru(2), and two equivalent Ru(1) atoms to form ONa3Ru3 octahedra that share  a cornercorner with one O(1)Na3Ru3 octahedra, corners with four equivalent O(2)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(2)Na5Ru octahedra, edges with two equivalent O(5)Na5Ru octahedra, and edges with six equivalent O(4)Na4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(5), two equivalent Na(3), and one Ru(1) atom to form distorted ONa5Ru octahedra that share corners with two equivalent O(1)Na3Ru3 octahedra, corners with two equivalent O(2)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(2)Na5Ru octahedra, edges with four equivalent O(4)Na4Ru2 octahedra, and edges with four equivalent O(5)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-20°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(6), two equivalent Na(1), two equivalent Na(3), and one Ru(2) atom. In the fourth O site, O(4) is bonded to one Na(2), one Na(3), one Na(4), one Na(5), one Ru(1), and one Ru(2) atom to form distorted ONa4Ru2 octahedra that share corners with three equivalent O(4)Na4Ru2 octahedra, corners with three equivalent O(5)Na5Ru octahedra, edges with two equivalent O(4)Na4Ru2 octahedra, edges with two equivalent O(5)Na5Ru octahedra, edges with three equivalent O(1)Na3Ru3 octahedra, and edges with four equivalent O(2)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(3), one Na(5), one Na(6), and one Ru(2) atom to form ONa5Ru octahedra that share corners with three equivalent O(4)Na4Ru2 octahedra, corners with three equivalent O(5)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(4)Na4Ru2 octahedra, edges with two equivalent O(5)Na5Ru octahedra, and edges with four equivalent O(2)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
Na3RuO4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with six equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Na(6)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-21°. Both Na(1)-O(2) bond lengths are 2.34 Å. Both Na(1)-O(3) bond lengths are 2.31 Å. Both Na(1)-O(5) bond lengths are 2.39 Å. In the second Na site, Na(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with two equivalent Na(4)O6 octahedra, corners with two equivalent Na(5)O6 octahedra, corners with two equivalent Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-20°. Both Na(2)-O(2) bond lengths are 2.37 Å. Both Na(2)-O(4) bond lengths are 2.28 Å. Both Na(2)-O(5) bond lengths are 2.30 Å. In the third Na site, Na(3) is bonded to one O(1), one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, corners with three equivalent Ru(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-21°. The Na(3)-O(1) bond length is 2.46 Å. The Na(3)-O(3) bond length is 2.25 Å. The Na(3)-O(4) bond length is 2.45 Å. The Na(3)-O(5) bond length is 2.32 Å. There is one shorter (2.27 Å) and one longer (2.60 Å) Na(3)-O(2) bond length. In the fourth Na site, Na(4) is bonded to two equivalent O(1) and four equivalent O(4) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ru(2)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with four equivalent Na(3)O6 octahedra, and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-19°. Both Na(4)-O(1) bond lengths are 2.38 Å. All Na(4)-O(4) bond lengths are 2.30 Å. In the fifth Na site, Na(5) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Ru(2)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-20°. Both Na(5)-O(2) bond lengths are 2.25 Å. Both Na(5)-O(4) bond lengths are 2.59 Å. Both Na(5)-O(5) bond lengths are 2.47 Å. In the sixth Na site, Na(6) is bonded to two equivalent O(3) and four equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent Ru(2)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. Both Na(6)-O(3) bond lengths are 2.75 Å. All Na(6)-O(5) bond lengths are 2.26 Å. There are two inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form RuO6 octahedra that share corners with six equivalent Na(3)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra,  an edgeedge with one Ru(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with two equivalent Na(4)O6 octahedra, edges with two equivalent Na(5)O6 octahedra, and edges with two equivalent Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Ru(1)-O(1) bond lengths are 2.13 Å. Both Ru(1)-O(2) bond lengths are 1.88 Å. Both Ru(1)-O(4) bond lengths are 1.99 Å. In the second Ru site, Ru(2) is bonded to one O(1), one O(3), two equivalent O(4), and two equivalent O(5) atoms to form RuO6 octahedra that share  a cornercorner with one Na(4)O6 octahedra,  a cornercorner with one Na(6)O6 octahedra, corners with four equivalent Na(5)O6 octahedra,  an edgeedge with one Na(4)O6 octahedra,  an edgeedge with one Na(6)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. The Ru(2)-O(1) bond length is 2.13 Å. The Ru(2)-O(3) bond length is 1.87 Å. Both Ru(2)-O(4) bond lengths are 2.11 Å. Both Ru(2)-O(5) bond lengths are 1.90 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Na(4), two equivalent Na(3), one Ru(2), and two equivalent Ru(1) atoms to form ONa3Ru3 octahedra that share  a cornercorner with one O(1)Na3Ru3 octahedra, corners with four equivalent O(2)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(2)Na5Ru octahedra, edges with two equivalent O(5)Na5Ru octahedra, and edges with six equivalent O(4)Na4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), one Na(2), one Na(5), two equivalent Na(3), and one Ru(1) atom to form distorted ONa5Ru octahedra that share corners with two equivalent O(1)Na3Ru3 octahedra, corners with two equivalent O(2)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(2)Na5Ru octahedra, edges with four equivalent O(4)Na4Ru2 octahedra, and edges with four equivalent O(5)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-20°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Na(6), two equivalent Na(1), two equivalent Na(3), and one Ru(2) atom. In the fourth O site, O(4) is bonded to one Na(2), one Na(3), one Na(4), one Na(5), one Ru(1), and one Ru(2) atom to form distorted ONa4Ru2 octahedra that share corners with three equivalent O(4)Na4Ru2 octahedra, corners with three equivalent O(5)Na5Ru octahedra, edges with two equivalent O(4)Na4Ru2 octahedra, edges with two equivalent O(5)Na5Ru octahedra, edges with three equivalent O(1)Na3Ru3 octahedra, and edges with four equivalent O(2)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fifth O site, O(5) is bonded to one Na(1), one Na(2), one Na(3), one Na(5), one Na(6), and one Ru(2) atom to form ONa5Ru octahedra that share corners with three equivalent O(4)Na4Ru2 octahedra, corners with three equivalent O(5)Na5Ru octahedra,  an edgeedge with one O(1)Na3Ru3 octahedra, edges with two equivalent O(4)Na4Ru2 octahedra, edges with two equivalent O(5)Na5Ru octahedra, and edges with four equivalent O(2)Na5Ru octahedra. The corner-sharing octahedral tilt angles range from 0-10°.