Na2RuO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Ru(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. In the second Na site, Na(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Ru(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Ru(1)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. In the third Na site, Na(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-15°. Ru(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form RuO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), and two equivalent Ru(1) atoms to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), and two equivalent Ru(1) atoms to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.
Na2RuO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Ru(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-15°. Both Na(1)-O(2) bond lengths are 2.37 Å. There are two shorter (2.29 Å) and two longer (2.49 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Ru(1)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with four equivalent Ru(1)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Na(2)-O(2) bond lengths are 2.23 Å. All Na(2)-O(1) bond lengths are 2.41 Å. In the third Na site, Na(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-15°. Both Na(3)-O(2) bond lengths are 2.25 Å. All Na(3)-O(1) bond lengths are 2.26 Å. Ru(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form RuO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Ru(1)-O(2) bond lengths are 2.05 Å. There are two shorter (1.98 Å) and two longer (2.08 Å) Ru(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), one Na(3), two equivalent Na(1), and two equivalent Ru(1) atoms to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second O site, O(2) is bonded to one Na(2), one Na(3), two equivalent Na(1), and two equivalent Ru(1) atoms to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-9°.