NaZrTaSi2SO12 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. Zr(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 ZrO6 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. Ta(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 TaO6 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(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-39°. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-35°. S(1) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. There are twelve inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Ta(1) and one Si(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one S(1) atom. In the fourth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(2) atom. In the fifth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one Si(1) atom. In the sixth O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one Si(2) atom. In the seventh O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one S(1) atom. In the eighth O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the ninth O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the tenth O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one S(1) atom. In the eleventh O site, O(4) is bonded in a bent 150 degrees geometry to one Ta(1) and one Si(1) atom. In the twelfth O site, O(5) is bonded in a bent 150 degrees geometry to one Ta(1) and one S(1) atom.
NaZrTaSi2SO12 crystallizes in the monoclinic Cc space group. Na(1) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(1)-O(10) bond length is 2.64 Å. The Na(1)-O(11) bond length is 2.58 Å. The Na(1)-O(12) bond length is 2.76 Å. The Na(1)-O(7) bond length is 2.57 Å. The Na(1)-O(8) bond length is 2.81 Å. The Na(1)-O(9) bond length is 2.50 Å. Zr(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 ZrO6 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 Zr(1)-O(1) bond length is 1.95 Å. The Zr(1)-O(2) bond length is 2.00 Å. The Zr(1)-O(3) bond length is 2.29 Å. The Zr(1)-O(7) bond length is 2.00 Å. The Zr(1)-O(8) bond length is 2.30 Å. The Zr(1)-O(9) bond length is 2.07 Å. Ta(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 TaO6 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 Ta(1)-O(10) bond length is 1.99 Å. The Ta(1)-O(11) bond length is 1.97 Å. The Ta(1)-O(12) bond length is 2.09 Å. The Ta(1)-O(4) bond length is 1.95 Å. The Ta(1)-O(5) bond length is 2.14 Å. The Ta(1)-O(6) bond length is 1.92 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(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-39°. The Si(1)-O(1) bond length is 1.61 Å. The Si(1)-O(10) bond length is 1.65 Å. The Si(1)-O(4) bond length is 1.66 Å. The Si(1)-O(7) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-35°. The Si(2)-O(11) bond length is 1.66 Å. The Si(2)-O(2) bond length is 1.60 Å. The Si(2)-O(6) bond length is 1.67 Å. The Si(2)-O(9) bond length is 1.62 Å. S(1) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form SO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Ta(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-35°. The S(1)-O(12) bond length is 1.52 Å. The S(1)-O(3) bond length is 1.45 Å. The S(1)-O(5) bond length is 1.50 Å. The S(1)-O(8) bond length is 1.46 Å. There are twelve inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Ta(1) and one Si(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one S(1) atom. In the fourth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(2) atom. In the fifth O site, O(10) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one Si(1) atom. In the sixth O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one Si(2) atom. In the seventh O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Ta(1), and one S(1) atom. In the eighth O site, O(1) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the ninth O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the tenth O site, O(3) is bonded in a bent 150 degrees geometry to one Zr(1) and one S(1) atom. In the eleventh O site, O(4) is bonded in a bent 150 degrees geometry to one Ta(1) and one Si(1) atom. In the twelfth O site, O(5) is bonded in a bent 150 degrees geometry to one Ta(1) and one S(1) atom.