Na2RuO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-16°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-14°. 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(3) atoms to form RuO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. In the second Ru site, Ru(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form RuO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 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(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Na(1), one Na(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
Na2RuO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-16°. Both Na(1)-O(1) bond lengths are 2.31 Å. Both Na(1)-O(2) bond lengths are 2.30 Å. Both Na(1)-O(3) bond lengths are 2.31 Å. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with three equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-16°. There is one shorter (2.30 Å) and one longer (2.51 Å) Na(2)-O(1) bond length. There is one shorter (2.32 Å) and one longer (2.57 Å) Na(2)-O(2) bond length. Both Na(2)-O(3) bond lengths are 2.43 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Ru(1)O6 octahedra, corners with two equivalent Ru(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Ru(1)O6 octahedra, edges with two equivalent Ru(2)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-14°. Both Na(3)-O(1) bond lengths are 2.48 Å. Both Na(3)-O(2) bond lengths are 2.49 Å. Both Na(3)-O(3) bond lengths are 2.28 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(3) atoms to form RuO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ru(2)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-13°. Both Ru(1)-O(1) bond lengths are 2.04 Å. Both Ru(1)-O(2) bond lengths are 2.05 Å. Both Ru(1)-O(3) bond lengths are 2.09 Å. In the second Ru site, Ru(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form RuO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Ru(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-12°. Both Ru(2)-O(1) bond lengths are 2.08 Å. Both Ru(2)-O(2) bond lengths are 2.04 Å. Both Ru(2)-O(3) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 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(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Na(1), one Na(3), two equivalent Na(2), one Ru(1), and one Ru(2) atom to form a mixture of corner and edge-sharing ONa4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.