Na3HfInSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(7), one O(9), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(7), one O(8), and two equivalent O(2) atoms. In the third Na site, Na(3) 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 Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. In(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 distorted InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) 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 15-41°. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), 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 27-39°. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 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 27-35°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(2), one In(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one In(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Hf(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(3), one In(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one In(1), and one Si(2) atom to form distorted edge-sharing ONa2InSi trigonal pyramids. In the ninth O site, O(9) is bonded to one Na(1), one Na(3), one In(1), and one Si(1) atom to form distorted edge-sharing ONa2InSi trigonal pyramids. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom.
Na3HfInSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(7), one O(9), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.32 Å. The Na(1)-O(10) bond length is 2.67 Å. The Na(1)-O(11) bond length is 2.50 Å. The Na(1)-O(7) bond length is 2.61 Å. The Na(1)-O(9) bond length is 2.31 Å. There is one shorter (2.93 Å) and one longer (2.97 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(4), one O(6), one O(7), one O(8), and two equivalent O(2) atoms. The Na(2)-O(10) bond length is 2.41 Å. The Na(2)-O(12) bond length is 2.70 Å. The Na(2)-O(4) bond length is 2.90 Å. The Na(2)-O(6) bond length is 2.86 Å. The Na(2)-O(7) bond length is 2.60 Å. The Na(2)-O(8) bond length is 2.41 Å. There is one shorter (2.54 Å) and one longer (2.95 Å) Na(2)-O(2) bond length. In the third Na site, Na(3) 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(3)-O(10) bond length is 2.52 Å. The Na(3)-O(11) bond length is 2.76 Å. The Na(3)-O(12) bond length is 2.87 Å. The Na(3)-O(7) bond length is 2.78 Å. The Na(3)-O(8) bond length is 2.44 Å. The Na(3)-O(9) bond length is 2.34 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 Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Hf(1)-O(10) bond length is 2.13 Å. The Hf(1)-O(11) bond length is 2.00 Å. The Hf(1)-O(12) bond length is 2.24 Å. The Hf(1)-O(4) bond length is 2.32 Å. The Hf(1)-O(5) bond length is 1.98 Å. The Hf(1)-O(6) bond length is 2.00 Å. In(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 distorted InO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The In(1)-O(1) bond length is 2.08 Å. The In(1)-O(2) bond length is 2.11 Å. The In(1)-O(3) bond length is 2.16 Å. The In(1)-O(7) bond length is 2.34 Å. The In(1)-O(8) bond length is 2.14 Å. The In(1)-O(9) bond length is 2.15 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(6), and one O(9) 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 15-41°. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(10) bond length is 1.68 Å. The Si(1)-O(6) bond length is 1.65 Å. The Si(1)-O(9) bond length is 1.64 Å. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(5), 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 27-39°. The Si(2)-O(11) bond length is 1.66 Å. The Si(2)-O(2) bond length is 1.63 Å. The Si(2)-O(5) bond length is 1.67 Å. The Si(2)-O(8) bond length is 1.63 Å. S(1) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SO4 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 27-35°. The S(1)-O(12) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.47 Å. The S(1)-O(4) bond length is 1.49 Å. The S(1)-O(7) bond length is 1.48 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(2), one In(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one In(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(2), one Hf(1), and one S(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to two equivalent Na(1), one Hf(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted linear geometry to one Na(2), one Hf(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(3), one In(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one In(1), and one Si(2) atom to form distorted edge-sharing ONa2InSi trigonal pyramids. In the ninth O site, O(9) is bonded to one Na(1), one Na(3), one In(1), and one Si(1) atom to form distorted edge-sharing ONa2InSi trigonal pyramids. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Hf(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(1), and one S(1) atom.