Na3HfInSi(PO6)2 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(11), one O(2), one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. Hf(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form HfO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. Si(1) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-40°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-39°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one In(1), and one Si(1) atom to form corner-sharing ONa2InSi trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Hf(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one In(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one Hf(1), and one Si(1) atom to form distorted corner-sharing ONa2HfSi trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), one In(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Hf(1), and one P(1) atom.
Na3HfInSi(PO6)2 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.34 Å. The Na(1)-O(11) bond length is 2.67 Å. The Na(1)-O(12) bond length is 2.50 Å. The Na(1)-O(2) bond length is 2.70 Å. The Na(1)-O(5) bond length is 2.56 Å. The Na(1)-O(6) bond length is 2.47 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.36 Å. The Na(2)-O(10) bond length is 2.61 Å. The Na(2)-O(11) bond length is 2.77 Å. The Na(2)-O(12) bond length is 2.79 Å. The Na(2)-O(2) bond length is 2.44 Å. The Na(2)-O(7) bond length is 2.89 Å. The Na(2)-O(8) bond length is 2.81 Å. The Na(2)-O(9) bond length is 2.74 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(11), one O(2), one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. The Na(3)-O(11) bond length is 2.47 Å. The Na(3)-O(2) bond length is 2.90 Å. The Na(3)-O(5) bond length is 2.59 Å. The Na(3)-O(6) bond length is 2.46 Å. The Na(3)-O(7) bond length is 2.54 Å. The Na(3)-O(8) bond length is 2.85 Å. There is one shorter (2.70 Å) and one longer (3.00 Å) Na(3)-O(4) bond length. Hf(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form HfO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.03 Å. The Hf(1)-O(12) bond length is 2.11 Å. The Hf(1)-O(2) bond length is 2.17 Å. The Hf(1)-O(3) bond length is 2.03 Å. The Hf(1)-O(6) bond length is 2.07 Å. The Hf(1)-O(7) bond length is 2.13 Å. In(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The In(1)-O(1) bond length is 2.11 Å. The In(1)-O(11) bond length is 2.19 Å. The In(1)-O(4) bond length is 2.15 Å. The In(1)-O(5) bond length is 2.22 Å. The In(1)-O(8) bond length is 2.02 Å. The In(1)-O(9) bond length is 2.17 Å. Si(1) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(10) bond length is 1.67 Å. The Si(1)-O(6) bond length is 1.65 Å. The Si(1)-O(8) bond length is 1.61 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-40°. The P(1)-O(11) bond length is 1.55 Å. The P(1)-O(12) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Hf(1)O6 octahedra and corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-39°. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(9) bond length is 1.53 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(2), one In(1), and one Si(1) atom to form corner-sharing ONa2InSi trigonal pyramids. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Hf(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one In(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded to one Na(1), one Na(3), one Hf(1), and one Si(1) atom to form distorted corner-sharing ONa2HfSi trigonal pyramids. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(2), one Na(3), one In(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Hf(1), and one P(1) atom.