NaCr2FeO8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1) and four equivalent O(2) atoms. Cr(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form CrO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-47°. Fe(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Cr(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Cr(1), and one Fe(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one Fe(1) atom.
NaCr2FeO8 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.59 Å. All Na(1)-O(2) bond lengths are 2.57 Å. Cr(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form CrO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-47°. The Cr(1)-O(1) bond length is 1.61 Å. The Cr(1)-O(3) bond length is 1.66 Å. Both Cr(1)-O(2) bond lengths are 1.71 Å. Fe(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Cr(1)O4 tetrahedra. Both Fe(1)-O(3) bond lengths are 1.94 Å. All Fe(1)-O(2) bond lengths are 1.95 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1) and one Cr(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Cr(1), and one Fe(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one Fe(1) atom.