NaYIrO4 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(6) and four equivalent O(7) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra,  an edgeedge with one Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and faces with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-13°. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(5), one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the second Y site, Y(2) is bonded to one O(4), two equivalent O(7), and four equivalent O(3) atoms to form distorted YO7 pentagonal bipyramids that share corners with two equivalent Ir(1)O6 octahedra, edges with four equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form IrO6 octahedra that share corners with two equivalent Y(2)O7 pentagonal bipyramids, corners with two equivalent Na(1)O6 pentagonal pyramids, edges with two equivalent Ir(1)O6 octahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. In the second Ir site, Ir(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form IrO6 octahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids, edges with two equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and  an edgeedge with one Na(1)O6 pentagonal pyramid. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), two equivalent Y(1), and one Ir(1) atom to form distorted ONa2Y2Ir trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra,  a cornercorner with one O(1)Na2Y2Ir trigonal bipyramid, corners with two equivalent O(3)Y4Ir trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(6)Na4Ir2 octahedra,  an edgeedge with one O(3)Y4Ir trigonal bipyramid, edges with two equivalent O(1)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids, and edges with two equivalent O(4)Y3Ir2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the second O site, O(2) is bonded to two equivalent Na(2), two equivalent Y(1), and one Ir(2) atom to form distorted ONa2Y2Ir trigonal bipyramids that share corners with two equivalent O(6)Na4Ir2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with three equivalent O(3)Y4Ir trigonal bipyramids, corners with four equivalent O(1)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra,  an edgeedge with one O(3)Y4Ir trigonal bipyramid, edges with two equivalent O(1)Na2Y2Ir trigonal bipyramids, and edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the third O site, O(3) is bonded to two equivalent Y(1), two equivalent Y(2), and one Ir(2) atom to form distorted OY4Ir trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(1)Na2Y2Ir trigonal bipyramids, corners with two equivalent O(3)Y4Ir trigonal bipyramids, corners with three equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra,  an edgeedge with one O(1)Na2Y2Ir trigonal bipyramid,  an edgeedge with one O(2)Na2Y2Ir trigonal bipyramid, edges with two equivalent O(4)Y3Ir2 trigonal bipyramids, and edges with three equivalent O(3)Y4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 54°. In the fourth O site, O(4) is bonded to one Y(2), two equivalent Y(1), and two equivalent Ir(1) atoms to form distorted OY3Ir2 trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(6)Na4Ir2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids,  an edgeedge with one O(6)Na4Ir2 octahedra, edges with four equivalent O(1)Na2Y2Ir trigonal bipyramids, and edges with four equivalent O(3)Y4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-38°. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Y(1), and two equivalent Ir(2) atoms. In the sixth O site, O(6) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Ir(1) atoms to form ONa4Ir2 octahedra that share corners with four equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(6)Na4Ir2 octahedra,  an edgeedge with one O(4)Y3Ir2 trigonal bipyramid, edges with four equivalent O(1)Na2Y2Ir trigonal bipyramids, and faces with two equivalent O(7)Na3YIr2 octahedra. The corner-sharing octahedral tilt angles are 37°. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Na(1), one Y(2), and two equivalent Ir(2) atoms to form ONa3YIr2 octahedra that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(6)Na4Ir2 octahedra,  a cornercorner with one O(4)Y3Ir2 trigonal bipyramid, corners with two equivalent O(1)Na2Y2Ir trigonal bipyramids, corners with two equivalent O(3)Y4Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra, edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(3)Y4Ir trigonal bipyramids,  a faceface with one O(7)Na3YIr2 octahedra, and  a faceface with one O(6)Na4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 37-57°.
NaYIrO4 crystallizes in the orthorhombic Amm2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(6) and four equivalent O(7) atoms to form distorted NaO6 pentagonal pyramids that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra,  an edgeedge with one Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and faces with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 10-13°. Both Na(1)-O(6) bond lengths are 2.40 Å. All Na(1)-O(7) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(5), one O(6), one O(7), two equivalent O(1), and two equivalent O(2) atoms. The Na(2)-O(5) bond length is 2.30 Å. The Na(2)-O(6) bond length is 2.49 Å. The Na(2)-O(7) bond length is 2.64 Å. Both Na(2)-O(1) bond lengths are 2.48 Å. Both Na(2)-O(2) bond lengths are 2.45 Å. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 9-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. The Y(1)-O(4) bond length is 2.78 Å. Both Y(1)-O(1) bond lengths are 2.29 Å. Both Y(1)-O(2) bond lengths are 2.30 Å. Both Y(1)-O(3) bond lengths are 2.54 Å. There is one shorter (2.62 Å) and one longer (2.91 Å) Y(1)-O(5) bond length. In the second Y site, Y(2) is bonded to one O(4), two equivalent O(7), and four equivalent O(3) atoms to form distorted YO7 pentagonal bipyramids that share corners with two equivalent Ir(1)O6 octahedra, edges with four equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 53°. The Y(2)-O(4) bond length is 2.31 Å. Both Y(2)-O(7) bond lengths are 2.37 Å. All Y(2)-O(3) bond lengths are 2.32 Å. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form IrO6 octahedra that share corners with two equivalent Y(2)O7 pentagonal bipyramids, corners with two equivalent Na(1)O6 pentagonal pyramids, edges with two equivalent Ir(1)O6 octahedra, and  an edgeedge with one Na(1)O6 pentagonal pyramid. Both Ir(1)-O(1) bond lengths are 2.01 Å. Both Ir(1)-O(4) bond lengths are 2.05 Å. Both Ir(1)-O(6) bond lengths are 2.06 Å. In the second Ir site, Ir(2) is bonded to one O(2), one O(3), two equivalent O(5), and two equivalent O(7) atoms to form IrO6 octahedra that share corners with two equivalent Na(1)O6 pentagonal pyramids, edges with two equivalent Ir(2)O6 octahedra, edges with two equivalent Y(2)O7 pentagonal bipyramids, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Ir(2)-O(2) bond length is 2.02 Å. The Ir(2)-O(3) bond length is 2.10 Å. Both Ir(2)-O(5) bond lengths are 2.03 Å. Both Ir(2)-O(7) bond lengths are 2.08 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2), two equivalent Y(1), and one Ir(1) atom to form distorted ONa2Y2Ir trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra,  a cornercorner with one O(1)Na2Y2Ir trigonal bipyramid, corners with two equivalent O(3)Y4Ir trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(6)Na4Ir2 octahedra,  an edgeedge with one O(3)Y4Ir trigonal bipyramid, edges with two equivalent O(1)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids, and edges with two equivalent O(4)Y3Ir2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the second O site, O(2) is bonded to two equivalent Na(2), two equivalent Y(1), and one Ir(2) atom to form distorted ONa2Y2Ir trigonal bipyramids that share corners with two equivalent O(6)Na4Ir2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with three equivalent O(3)Y4Ir trigonal bipyramids, corners with four equivalent O(1)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra,  an edgeedge with one O(3)Y4Ir trigonal bipyramid, edges with two equivalent O(1)Na2Y2Ir trigonal bipyramids, and edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the third O site, O(3) is bonded to two equivalent Y(1), two equivalent Y(2), and one Ir(2) atom to form distorted OY4Ir trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(1)Na2Y2Ir trigonal bipyramids, corners with two equivalent O(3)Y4Ir trigonal bipyramids, corners with three equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra,  an edgeedge with one O(1)Na2Y2Ir trigonal bipyramid,  an edgeedge with one O(2)Na2Y2Ir trigonal bipyramid, edges with two equivalent O(4)Y3Ir2 trigonal bipyramids, and edges with three equivalent O(3)Y4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 54°. In the fourth O site, O(4) is bonded to one Y(2), two equivalent Y(1), and two equivalent Ir(1) atoms to form distorted OY3Ir2 trigonal bipyramids that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(6)Na4Ir2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids,  an edgeedge with one O(6)Na4Ir2 octahedra, edges with four equivalent O(1)Na2Y2Ir trigonal bipyramids, and edges with four equivalent O(3)Y4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-38°. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Y(1), and two equivalent Ir(2) atoms. In the sixth O site, O(6) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Ir(1) atoms to form ONa4Ir2 octahedra that share corners with four equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(4)Y3Ir2 trigonal bipyramids, corners with four equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(6)Na4Ir2 octahedra,  an edgeedge with one O(4)Y3Ir2 trigonal bipyramid, edges with four equivalent O(1)Na2Y2Ir trigonal bipyramids, and faces with two equivalent O(7)Na3YIr2 octahedra. The corner-sharing octahedral tilt angles are 37°. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Na(1), one Y(2), and two equivalent Ir(2) atoms to form ONa3YIr2 octahedra that share corners with two equivalent O(7)Na3YIr2 octahedra, corners with two equivalent O(6)Na4Ir2 octahedra,  a cornercorner with one O(4)Y3Ir2 trigonal bipyramid, corners with two equivalent O(1)Na2Y2Ir trigonal bipyramids, corners with two equivalent O(3)Y4Ir trigonal bipyramids, edges with two equivalent O(7)Na3YIr2 octahedra, edges with two equivalent O(2)Na2Y2Ir trigonal bipyramids, edges with two equivalent O(3)Y4Ir trigonal bipyramids,  a faceface with one O(7)Na3YIr2 octahedra, and  a faceface with one O(6)Na4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 37-57°.