NaMnO2 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)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 1-15°. In the second Na site, Na(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Na(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 1-15°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-15°.
NaMnO2 is Caswellsilverite-like structured and crystallizes in the triclinic P1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)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 1-15°. The Na(1)-O(2) bond length is 2.47 Å. The Na(1)-O(4) bond length is 2.46 Å. Both Na(1)-O(1) bond lengths are 2.25 Å. Both Na(1)-O(3) bond lengths are 2.26 Å. In the second Na site, Na(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form NaO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Na(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 1-15°. The Na(2)-O(1) bond length is 2.45 Å. The Na(2)-O(3) bond length is 2.48 Å. Both Na(2)-O(2) bond lengths are 2.26 Å. Both Na(2)-O(4) bond lengths are 2.25 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form MnO6 octahedra that share corners with two equivalent Na(2)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. The Mn(1)-O(1) bond length is 1.91 Å. The Mn(1)-O(3) bond length is 1.91 Å. There is one shorter (2.23 Å) and one longer (2.27 Å) Mn(1)-O(2) bond length. There is one shorter (2.24 Å) and one longer (2.28 Å) Mn(1)-O(4) bond length. In the second Mn site, Mn(2) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Mn(2)O6 octahedra, edges with four equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. The Mn(2)-O(2) bond length is 1.91 Å. The Mn(2)-O(4) bond length is 1.91 Å. There is one shorter (2.24 Å) and one longer (2.28 Å) Mn(2)-O(1) bond length. There is one shorter (2.24 Å) and one longer (2.26 Å) Mn(2)-O(3) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-14°. In the third O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Mn(1), and two equivalent Mn(2) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), one Mn(2), and two equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Mn3 octahedra. The corner-sharing octahedral tilt angles range from 1-15°.