NaMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second Mn site, Mn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Mn(1), and four equivalent Mn(2) atoms to form ONaMn5 octahedra that share corners with six equivalent O(1)NaMn5 octahedra, edges with four equivalent O(1)NaMn5 octahedra, and edges with eight equivalent O(2)Na2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form ONa2Mn4 octahedra that share corners with six equivalent O(2)Na2Mn4 octahedra, edges with four equivalent O(2)Na2Mn4 octahedra, and edges with eight equivalent O(1)NaMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
NaMn3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Na(1)-O(1) bond lengths are 2.32 Å. There are two shorter (2.31 Å) and two longer (2.38 Å) Na(1)-O(2) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent Na(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with eight equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Mn(1)-O(1) bond lengths are 1.96 Å. There are two shorter (1.93 Å) and two longer (2.33 Å) Mn(1)-O(2) bond lengths. In the second Mn site, Mn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Mn(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Mn(1)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. There is one shorter (2.14 Å) and one longer (2.17 Å) Mn(2)-O(2) bond length. There are a spread of Mn(2)-O(1) bond distances ranging from 2.15-2.33 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Mn(1), and four equivalent Mn(2) atoms to form ONaMn5 octahedra that share corners with six equivalent O(1)NaMn5 octahedra, edges with four equivalent O(1)NaMn5 octahedra, and edges with eight equivalent O(2)Na2Mn4 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Mn(1), and two equivalent Mn(2) atoms to form ONa2Mn4 octahedra that share corners with six equivalent O(2)Na2Mn4 octahedra, edges with four equivalent O(2)Na2Mn4 octahedra, and edges with eight equivalent O(1)NaMn5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.