NaMnAsO4 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. 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 four equivalent Mn(1)O6 octahedra, corners with two equivalent As(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-69°. Mn(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form MnO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, corners with four equivalent As(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°. As(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form AsO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Mn(1), and one As(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one As(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one As(1) atom.
NaMnAsO4 is Spinel-derived structured and crystallizes in the orthorhombic Pnma space group. 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 four equivalent Mn(1)O6 octahedra, corners with two equivalent As(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-69°. Both Na(1)-O(1) bond lengths are 2.51 Å. Both Na(1)-O(2) bond lengths are 2.36 Å. Both Na(1)-O(3) bond lengths are 2.43 Å. Mn(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form MnO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra, corners with four equivalent As(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one As(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 45-69°. The Mn(1)-O(2) bond length is 2.19 Å. The Mn(1)-O(3) bond length is 2.11 Å. There are two shorter (2.20 Å) and two longer (2.37 Å) Mn(1)-O(1) bond lengths. As(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form AsO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-61°. The As(1)-O(2) bond length is 1.71 Å. The As(1)-O(3) bond length is 1.73 Å. Both As(1)-O(1) bond lengths are 1.74 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(1), two equivalent Mn(1), and one As(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one As(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Mn(1), and one As(1) atom.