Na2HfZnP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form HfO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. Zn(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form ZnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-37°. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-36°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Hf(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Hf(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Hf(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Hf(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Hf(1), and one P(2) atom.
Na2HfZnP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. The Na(1)-O(10) bond length is 2.47 Å. The Na(1)-O(12) bond length is 2.55 Å. The Na(1)-O(3) bond length is 2.34 Å. The Na(1)-O(8) bond length is 2.33 Å. The Na(1)-O(9) bond length is 2.44 Å. There is one shorter (2.85 Å) and one longer (2.93 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(2)-O(10) bond length is 2.93 Å. The Na(2)-O(11) bond length is 2.71 Å. The Na(2)-O(12) bond length is 2.64 Å. The Na(2)-O(7) bond length is 2.28 Å. The Na(2)-O(8) bond length is 2.45 Å. The Na(2)-O(9) bond length is 2.59 Å. Hf(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form HfO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.04 Å. The Hf(1)-O(11) bond length is 2.15 Å. The Hf(1)-O(12) bond length is 2.12 Å. The Hf(1)-O(4) bond length is 2.02 Å. The Hf(1)-O(5) bond length is 2.02 Å. The Hf(1)-O(6) bond length is 2.16 Å. Zn(1) is bonded to one O(1), one O(2), one O(3), one O(7), one O(8), and one O(9) atom to form ZnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Zn(1)-O(1) bond length is 2.00 Å. The Zn(1)-O(2) bond length is 2.07 Å. The Zn(1)-O(3) bond length is 2.06 Å. The Zn(1)-O(7) bond length is 2.09 Å. The Zn(1)-O(8) bond length is 2.20 Å. The Zn(1)-O(9) bond length is 2.25 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(10) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(7) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-37°. The P(2)-O(12) bond length is 1.58 Å. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.53 Å. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-36°. The S(1)-O(11) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(6) bond length is 1.50 Å. The S(1)-O(9) bond length is 1.47 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zn(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Hf(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Hf(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Hf(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Hf(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Hf(1), and one P(2) atom.