NaSmGeO4 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 Sm(1)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Sm(1)O6 octahedra, and edges with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-67°. Sm(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form SmO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Sm(1)O6 octahedra, corners with four equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-67°. Ge(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Sm(1)O6 octahedra,  an edgeedge with one Sm(1)O6 octahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-62°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Sm(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Sm(1), and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Sm(1), and one Ge(1) atom.
NaSmGeO4 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 Sm(1)O6 octahedra, corners with two equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Sm(1)O6 octahedra, and edges with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-67°. Both Na(1)-O(1) bond lengths are 2.44 Å. Both Na(1)-O(2) bond lengths are 2.56 Å. Both Na(1)-O(3) bond lengths are 2.45 Å. Sm(1) is bonded to one O(1), one O(3), and four equivalent O(2) atoms to form SmO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent Sm(1)O6 octahedra, corners with four equivalent Ge(1)O4 tetrahedra, edges with two equivalent Na(1)O6 octahedra, and  an edgeedge with one Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-67°. The Sm(1)-O(1) bond length is 2.29 Å. The Sm(1)-O(3) bond length is 2.36 Å. There are two shorter (2.34 Å) and two longer (2.43 Å) Sm(1)-O(2) bond lengths. Ge(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form GeO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Sm(1)O6 octahedra,  an edgeedge with one Sm(1)O6 octahedra, and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-62°. The Ge(1)-O(1) bond length is 1.76 Å. The Ge(1)-O(3) bond length is 1.75 Å. Both Ge(1)-O(2) bond lengths are 1.81 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Sm(1), and one Ge(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Sm(1), and one Ge(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Sm(1), and one Ge(1) atom.