NaRuFeO4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Ru(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(4) atoms to form RuO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Fe(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form FeO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ru(1), and two equivalent Fe(1) atoms to form distorted ONa2Fe2Ru trigonal bipyramids that share corners with four equivalent O(2)Na2Fe3 square pyramids, corners with three equivalent O(4)Na2Ru3 trigonal bipyramids, corners with four equivalent O(1)Na2Fe2Ru trigonal bipyramids, edges with three equivalent O(2)Na2Fe3 square pyramids, and edges with two equivalent O(4)Na2Ru3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent Fe(1) atoms to form ONa2Fe3 square pyramids that share corners with two equivalent O(4)Na2Ru3 trigonal bipyramids, corners with four equivalent O(1)Na2Fe2Ru trigonal bipyramids, edges with four equivalent O(2)Na2Fe3 square pyramids,  an edgeedge with one O(4)Na2Ru3 trigonal bipyramid, and edges with three equivalent O(1)Na2Fe2Ru trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Ru(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded to two equivalent Na(1) and three equivalent Ru(1) atoms to form distorted ONa2Ru3 trigonal bipyramids that share corners with two equivalent O(2)Na2Fe3 square pyramids, corners with three equivalent O(1)Na2Fe2Ru trigonal bipyramids,  an edgeedge with one O(2)Na2Fe3 square pyramid, edges with two equivalent O(1)Na2Fe2Ru trigonal bipyramids, and edges with four equivalent O(4)Na2Ru3 trigonal bipyramids.
NaRuFeO4 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There is one shorter (2.61 Å) and one longer (2.67 Å) Na(1)-O(1) bond length. Both Na(1)-O(2) bond lengths are 2.36 Å. Both Na(1)-O(3) bond lengths are 2.64 Å. Both Na(1)-O(4) bond lengths are 2.49 Å. Ru(1) is bonded to one O(1), two equivalent O(3), and three equivalent O(4) atoms to form RuO6 octahedra that share corners with four equivalent Fe(1)O6 octahedra and edges with four equivalent Ru(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Ru(1)-O(1) bond length is 1.98 Å. Both Ru(1)-O(3) bond lengths are 2.01 Å. There is one shorter (2.01 Å) and two longer (2.08 Å) Ru(1)-O(4) bond lengths. Fe(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form FeO6 octahedra that share corners with four equivalent Ru(1)O6 octahedra and edges with four equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Fe(1)-O(3) bond length is 2.20 Å. Both Fe(1)-O(1) bond lengths are 2.03 Å. There are two shorter (2.01 Å) and one longer (2.05 Å) Fe(1)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Ru(1), and two equivalent Fe(1) atoms to form distorted ONa2Fe2Ru trigonal bipyramids that share corners with four equivalent O(2)Na2Fe3 square pyramids, corners with three equivalent O(4)Na2Ru3 trigonal bipyramids, corners with four equivalent O(1)Na2Fe2Ru trigonal bipyramids, edges with three equivalent O(2)Na2Fe3 square pyramids, and edges with two equivalent O(4)Na2Ru3 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent Fe(1) atoms to form ONa2Fe3 square pyramids that share corners with two equivalent O(4)Na2Ru3 trigonal bipyramids, corners with four equivalent O(1)Na2Fe2Ru trigonal bipyramids, edges with four equivalent O(2)Na2Fe3 square pyramids,  an edgeedge with one O(4)Na2Ru3 trigonal bipyramid, and edges with three equivalent O(1)Na2Fe2Ru trigonal bipyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Ru(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded to two equivalent Na(1) and three equivalent Ru(1) atoms to form distorted ONa2Ru3 trigonal bipyramids that share corners with two equivalent O(2)Na2Fe3 square pyramids, corners with three equivalent O(1)Na2Fe2Ru trigonal bipyramids,  an edgeedge with one O(2)Na2Fe3 square pyramid, edges with two equivalent O(1)Na2Fe2Ru trigonal bipyramids, and edges with four equivalent O(4)Na2Ru3 trigonal bipyramids.