NaTbIrO4 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(3) and four equivalent O(4) 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 Tb(2)O7 pentagonal bipyramids, and faces with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-13°. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms. There are two inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 9-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. In the second Tb site, Tb(2) is bonded to one O(1), two equivalent O(4), and four equivalent O(7) atoms to form distorted TbO7 pentagonal bipyramids that share corners with two equivalent Ir(1)O6 octahedra, edges with four equivalent Ir(2)O6 octahedra, edges with two equivalent Tb(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(3), and two equivalent O(5) atoms to form IrO6 octahedra that share corners with two equivalent Tb(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(6), one O(7), two equivalent O(2), and two equivalent O(4) 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 Tb(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 one Tb(2), two equivalent Tb(1), and two equivalent Ir(1) atoms to form distorted OTb3Ir2 trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(3)Na4Ir2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids,  an edgeedge with one O(3)Na4Ir2 octahedra, edges with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, and edges with four equivalent O(7)Tb4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-38°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Tb(1), and two equivalent Ir(2) atoms. In the third O site, O(3) 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(4)Na3TbIr2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(3)Na4Ir2 octahedra,  an edgeedge with one O(1)Tb3Ir2 trigonal bipyramid, edges with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, and faces with two equivalent O(4)Na3TbIr2 octahedra. The corner-sharing octahedral tilt angles are 37°. In the fourth O site, O(4) is bonded to one Na(2), two equivalent Na(1), one Tb(2), and two equivalent Ir(2) atoms to form ONa3TbIr2 octahedra that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(3)Na4Ir2 octahedra,  a cornercorner with one O(1)Tb3Ir2 trigonal bipyramid, corners with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra, edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(7)Tb4Ir trigonal bipyramids,  a faceface with one O(4)Na3TbIr2 octahedra, and  a faceface with one O(3)Na4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 37-57°. In the fifth O site, O(5) is bonded to two equivalent Na(2), two equivalent Tb(1), and one Ir(1) atom to form distorted ONa2Tb2Ir trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra,  a cornercorner with one O(5)Na2Tb2Ir trigonal bipyramid, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(3)Na4Ir2 octahedra,  an edgeedge with one O(7)Tb4Ir trigonal bipyramid, edges with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids, and edges with two equivalent O(1)Tb3Ir2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the sixth O site, O(6) is bonded to two equivalent Na(2), two equivalent Tb(1), and one Ir(2) atom to form distorted ONa2Tb2Ir trigonal bipyramids that share corners with two equivalent O(3)Na4Ir2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with three equivalent O(7)Tb4Ir trigonal bipyramids, corners with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra,  an edgeedge with one O(7)Tb4Ir trigonal bipyramid, edges with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, and edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the seventh O site, O(7) is bonded to two equivalent Tb(1), two equivalent Tb(2), and one Ir(2) atom to form distorted OTb4Ir trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, corners with three equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra,  an edgeedge with one O(5)Na2Tb2Ir trigonal bipyramid,  an edgeedge with one O(6)Na2Tb2Ir trigonal bipyramid, edges with two equivalent O(1)Tb3Ir2 trigonal bipyramids, and edges with three equivalent O(7)Tb4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 53°.
NaTbIrO4 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(3) and four equivalent O(4) 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 Tb(2)O7 pentagonal bipyramids, and faces with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 9-13°. Both Na(1)-O(3) bond lengths are 2.39 Å. All Na(1)-O(4) bond lengths are 2.49 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(5), and two equivalent O(6) atoms. The Na(2)-O(2) bond length is 2.30 Å. The Na(2)-O(3) bond length is 2.48 Å. The Na(2)-O(4) bond length is 2.63 Å. Both Na(2)-O(5) bond lengths are 2.47 Å. Both Na(2)-O(6) bond lengths are 2.45 Å. There are two inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 9-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. The Tb(1)-O(1) bond length is 2.78 Å. There is one shorter (2.63 Å) and one longer (2.91 Å) Tb(1)-O(2) bond length. Both Tb(1)-O(5) bond lengths are 2.29 Å. Both Tb(1)-O(6) bond lengths are 2.31 Å. Both Tb(1)-O(7) bond lengths are 2.54 Å. In the second Tb site, Tb(2) is bonded to one O(1), two equivalent O(4), and four equivalent O(7) atoms to form distorted TbO7 pentagonal bipyramids that share corners with two equivalent Ir(1)O6 octahedra, edges with four equivalent Ir(2)O6 octahedra, edges with two equivalent Tb(2)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 53°. The Tb(2)-O(1) bond length is 2.33 Å. Both Tb(2)-O(4) bond lengths are 2.37 Å. All Tb(2)-O(7) bond lengths are 2.33 Å. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form IrO6 octahedra that share corners with two equivalent Tb(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 2.05 Å. Both Ir(1)-O(3) bond lengths are 2.06 Å. Both Ir(1)-O(5) bond lengths are 2.02 Å. In the second Ir site, Ir(2) is bonded to one O(6), one O(7), two equivalent O(2), and two equivalent O(4) 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 Tb(2)O7 pentagonal bipyramids, and  an edgeedge with one Na(1)O6 pentagonal pyramid. The Ir(2)-O(6) bond length is 2.02 Å. The Ir(2)-O(7) bond length is 2.10 Å. Both Ir(2)-O(2) bond lengths are 2.03 Å. Both Ir(2)-O(4) bond lengths are 2.09 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Tb(2), two equivalent Tb(1), and two equivalent Ir(1) atoms to form distorted OTb3Ir2 trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(3)Na4Ir2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids,  an edgeedge with one O(3)Na4Ir2 octahedra, edges with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, and edges with four equivalent O(7)Tb4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles range from 0-38°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Tb(1), and two equivalent Ir(2) atoms. In the third O site, O(3) 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(4)Na3TbIr2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(3)Na4Ir2 octahedra,  an edgeedge with one O(1)Tb3Ir2 trigonal bipyramid, edges with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, and faces with two equivalent O(4)Na3TbIr2 octahedra. The corner-sharing octahedral tilt angles are 37°. In the fourth O site, O(4) is bonded to one Na(2), two equivalent Na(1), one Tb(2), and two equivalent Ir(2) atoms to form ONa3TbIr2 octahedra that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(3)Na4Ir2 octahedra,  a cornercorner with one O(1)Tb3Ir2 trigonal bipyramid, corners with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra, edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(7)Tb4Ir trigonal bipyramids,  a faceface with one O(4)Na3TbIr2 octahedra, and  a faceface with one O(3)Na4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 37-57°. In the fifth O site, O(5) is bonded to two equivalent Na(2), two equivalent Tb(1), and one Ir(1) atom to form distorted ONa2Tb2Ir trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra,  a cornercorner with one O(5)Na2Tb2Ir trigonal bipyramid, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, corners with four equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(3)Na4Ir2 octahedra,  an edgeedge with one O(7)Tb4Ir trigonal bipyramid, edges with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids, and edges with two equivalent O(1)Tb3Ir2 trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the sixth O site, O(6) is bonded to two equivalent Na(2), two equivalent Tb(1), and one Ir(2) atom to form distorted ONa2Tb2Ir trigonal bipyramids that share corners with two equivalent O(3)Na4Ir2 octahedra, corners with two equivalent O(1)Tb3Ir2 trigonal bipyramids, corners with three equivalent O(7)Tb4Ir trigonal bipyramids, corners with four equivalent O(5)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra,  an edgeedge with one O(7)Tb4Ir trigonal bipyramid, edges with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, and edges with two equivalent O(6)Na2Tb2Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 52°. In the seventh O site, O(7) is bonded to two equivalent Tb(1), two equivalent Tb(2), and one Ir(2) atom to form distorted OTb4Ir trigonal bipyramids that share corners with two equivalent O(4)Na3TbIr2 octahedra, corners with two equivalent O(5)Na2Tb2Ir trigonal bipyramids, corners with two equivalent O(7)Tb4Ir trigonal bipyramids, corners with three equivalent O(6)Na2Tb2Ir trigonal bipyramids, edges with two equivalent O(4)Na3TbIr2 octahedra,  an edgeedge with one O(5)Na2Tb2Ir trigonal bipyramid,  an edgeedge with one O(6)Na2Tb2Ir trigonal bipyramid, edges with two equivalent O(1)Tb3Ir2 trigonal bipyramids, and edges with three equivalent O(7)Tb4Ir trigonal bipyramids. The corner-sharing octahedral tilt angles are 53°.