NaFe(SO4)2 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(4), and three equivalent O(2) atoms. Fe(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with three equivalent S(1)O4 tetrahedra and corners with three equivalent S(2)O4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(5), and two equivalent O(6) atoms to form SO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-38°. In the second S site, S(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form SO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(1) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(1) atom. In the third O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(2) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one S(2) atom.
NaFe(SO4)2 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), two equivalent O(4), and three equivalent O(2) atoms. The Na(1)-O(1) bond length is 2.36 Å. Both Na(1)-O(4) bond lengths are 2.56 Å. There is one shorter (2.38 Å) and two longer (2.73 Å) Na(1)-O(2) bond lengths. Fe(1) is bonded to one O(3), one O(5), two equivalent O(4), and two equivalent O(6) atoms to form FeO6 octahedra that share corners with three equivalent S(1)O4 tetrahedra and corners with three equivalent S(2)O4 tetrahedra. The Fe(1)-O(3) bond length is 2.01 Å. The Fe(1)-O(5) bond length is 2.04 Å. Both Fe(1)-O(4) bond lengths are 2.05 Å. Both Fe(1)-O(6) bond lengths are 2.00 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(5), and two equivalent O(6) atoms to form SO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-38°. The S(1)-O(1) bond length is 1.44 Å. The S(1)-O(5) bond length is 1.50 Å. Both S(1)-O(6) bond lengths are 1.50 Å. In the second S site, S(2) is bonded to one O(2), one O(3), and two equivalent O(4) atoms to form SO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. The S(2)-O(2) bond length is 1.46 Å. The S(2)-O(3) bond length is 1.48 Å. Both S(2)-O(4) bond lengths are 1.50 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(1) atom. In the second O site, O(6) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(1) atom. In the third O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(2) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one S(2) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one S(2) atom.