NaFeO2 crystallizes in the orthorhombic P2_12_12_1 space group. Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Na(1)O4 tetrahedra, corners with six equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O4 tetrahedra. Fe(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form FeO4 tetrahedra that share corners with four equivalent Fe(1)O4 tetrahedra, corners with six equivalent Na(1)O4 tetrahedra, and  an edgeedge with one Na(1)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing ONa2Fe2 trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing ONa2Fe2 trigonal pyramids.
NaFeO2 crystallizes in the orthorhombic P2_12_12_1 space group. Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with four equivalent Na(1)O4 tetrahedra, corners with six equivalent Fe(1)O4 tetrahedra, and  an edgeedge with one Fe(1)O4 tetrahedra. There is one shorter (2.32 Å) and one longer (2.41 Å) Na(1)-O(1) bond length. There is one shorter (2.30 Å) and one longer (2.39 Å) Na(1)-O(2) bond length. Fe(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form FeO4 tetrahedra that share corners with four equivalent Fe(1)O4 tetrahedra, corners with six equivalent Na(1)O4 tetrahedra, and  an edgeedge with one Na(1)O4 tetrahedra. There is one shorter (1.89 Å) and one longer (1.90 Å) Fe(1)-O(1) bond length. There is one shorter (1.90 Å) and one longer (1.92 Å) Fe(1)-O(2) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing ONa2Fe2 trigonal pyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form a mixture of corner and edge-sharing ONa2Fe2 trigonal pyramids.