Na5ReO6 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(1) and four equivalent O(2) atoms to form distorted 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 Na(1)O6 octahedra, edges with three equivalent Re(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-20°. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Re(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Re(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-20°. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Re(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Re(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. Re(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ReO6 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 four equivalent Na(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Re(1) atom. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Re(1) atom to form a mixture of distorted edge and corner-sharing ONa5Re octahedra. The corner-sharing octahedral tilt angles range from 0-16°.
Na5ReO6 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(1) and four equivalent O(2) atoms to form distorted 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 Na(1)O6 octahedra, edges with three equivalent Re(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-20°. Both Na(1)-O(1) bond lengths are 2.30 Å. There are two shorter (2.31 Å) and two longer (2.35 Å) Na(1)-O(2) bond lengths. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Re(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Re(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with four equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-20°. Both Na(2)-O(1) bond lengths are 2.34 Å. There are two shorter (2.31 Å) and two longer (2.57 Å) Na(2)-O(2) bond lengths. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted NaO6 octahedra that share corners with two equivalent Re(1)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with two equivalent Re(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. Both Na(3)-O(1) bond lengths are 2.71 Å. All Na(3)-O(2) bond lengths are 2.27 Å. Re(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ReO6 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 four equivalent Na(2)O6 octahedra, and edges with six equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Both Re(1)-O(1) bond lengths are 1.89 Å. All Re(1)-O(2) bond lengths are 1.91 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Re(1) atom. In the second O site, O(2) is bonded to one Na(3), two equivalent Na(1), two equivalent Na(2), and one Re(1) atom to form a mixture of distorted edge and corner-sharing ONa5Re octahedra. The corner-sharing octahedral tilt angles range from 0-16°.