Na2VO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. There are two 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 distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-19°. 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 four equivalent V(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-19°. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-17°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 5-15°.
Na2VO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fdd2 space group. There are two 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 distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-19°. There is one shorter (2.35 Å) and one longer (2.36 Å) Na(1)-O(1) bond length. There is one shorter (2.38 Å) and one longer (2.49 Å) Na(1)-O(2) bond length. There is one shorter (2.27 Å) and one longer (2.28 Å) Na(1)-O(3) bond length. 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 four equivalent V(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-19°. There is one shorter (2.28 Å) and one longer (2.44 Å) Na(2)-O(1) bond length. There is one shorter (2.25 Å) and one longer (2.47 Å) Na(2)-O(2) bond length. There is one shorter (2.41 Å) and one longer (2.47 Å) Na(2)-O(3) bond length. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent V(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-17°. There is one shorter (1.92 Å) and one longer (2.10 Å) V(1)-O(1) bond length. There is one shorter (1.96 Å) and one longer (2.04 Å) V(1)-O(2) bond length. There is one shorter (1.89 Å) and one longer (2.17 Å) V(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing ONa4V2 octahedra. The corner-sharing octahedral tilt angles range from 5-15°.