Na3HfGaSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(3), 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. Ga(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 GaO6 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-39°. 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-39°. 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. 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 Ga(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ga(1), and one Si(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Ga(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 distorted 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 bent 150 degrees geometry to one Na(2), one Hf(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ga(1), and one S(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Ga(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ga(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal bipyramidal 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.
Na3HfGaSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(3), one O(7), one O(9), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.45 Å. The Na(1)-O(10) bond length is 2.54 Å. The Na(1)-O(11) bond length is 2.51 Å. The Na(1)-O(3) bond length is 3.01 Å. The Na(1)-O(7) bond length is 2.44 Å. The Na(1)-O(9) bond length is 2.38 Å. There is one shorter (2.83 Å) and one longer (2.89 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 2.39 Å. The Na(2)-O(12) bond length is 2.60 Å. The Na(2)-O(4) bond length is 2.84 Å. The Na(2)-O(6) bond length is 2.82 Å. The Na(2)-O(7) bond length is 2.62 Å. The Na(2)-O(8) bond length is 2.34 Å. There is one shorter (2.59 Å) and one longer (2.83 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 2.70 Å. The Na(3)-O(12) bond length is 2.82 Å. The Na(3)-O(7) bond length is 2.59 Å. The Na(3)-O(8) bond length is 2.46 Å. The Na(3)-O(9) bond length is 2.33 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 2.12 Å. The Hf(1)-O(11) bond length is 1.97 Å. The Hf(1)-O(12) bond length is 2.19 Å. The Hf(1)-O(4) bond length is 2.22 Å. The Hf(1)-O(5) bond length is 1.95 Å. The Hf(1)-O(6) bond length is 1.97 Å. Ga(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 GaO6 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 Ga(1)-O(1) bond length is 1.91 Å. The Ga(1)-O(2) bond length is 1.99 Å. The Ga(1)-O(3) bond length is 2.06 Å. The Ga(1)-O(7) bond length is 2.33 Å. The Ga(1)-O(8) bond length is 1.98 Å. The Ga(1)-O(9) bond length is 2.01 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-39°. 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 1.64 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-39°. The Si(2)-O(11) bond length is 1.65 Å. The Si(2)-O(2) bond length is 1.64 Å. The Si(2)-O(5) bond length is 1.65 Å. The Si(2)-O(8) bond length is 1.64 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 Ga(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. 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 1.48 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 Ga(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ga(1), and one Si(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Ga(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 distorted 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 bent 150 degrees geometry to one Na(2), one Hf(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ga(1), and one S(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Ga(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Ga(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal bipyramidal 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.