NaSmHf4O12 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(4) atoms. Sm(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(1) atoms. Hf(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form corner-sharing HfO6 octahedra. The corner-sharing octahedral tilt angles range from 21-30°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Hf(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Sm(1) and two equivalent Hf(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Hf(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Hf(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Hf(1) atoms.
NaSmHf4O12 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(4) atoms. Both Na(1)-O(3) bond lengths are 2.38 Å. Both Na(1)-O(4) bond lengths are 2.39 Å. Sm(1) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(5), and four equivalent O(1) atoms. Both Sm(1)-O(2) bond lengths are 2.46 Å. Both Sm(1)-O(5) bond lengths are 2.56 Å. All Sm(1)-O(1) bond lengths are 2.44 Å. Hf(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form corner-sharing HfO6 octahedra. The corner-sharing octahedral tilt angles range from 21-30°. The Hf(1)-O(2) bond length is 2.15 Å. The Hf(1)-O(3) bond length is 2.02 Å. The Hf(1)-O(4) bond length is 2.02 Å. The Hf(1)-O(5) bond length is 2.18 Å. There is one shorter (2.06 Å) and one longer (2.08 Å) Hf(1)-O(1) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Hf(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Sm(1) and two equivalent Hf(1) atoms. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Hf(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Hf(1) atoms. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Sm(1) and two equivalent Hf(1) atoms.