Na3YSnSi2SO12 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 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. 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. Y(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 YO6 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. Sn(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 distorted SnO6 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-34°. 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 Y(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Y(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Y(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Sn(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 Sn(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Sn(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 Y(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Y(1), and one Si(2) atom to form distorted corner-sharing ONa2YSi trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Y(1), and one Si(1) atom. 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 Sn(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(3), one Sn(1), and one Si(2) atom to form distorted corner-sharing ONa2SiSn trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Na(2), one Na(3), one Sn(1), and one S(1) atom.
Na3YSnSi2SO12 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 2.37 Å. The Na(1)-O(10) bond length is 2.82 Å. The Na(1)-O(11) bond length is 2.43 Å. The Na(1)-O(7) bond length is 2.72 Å. The Na(1)-O(9) bond length is 2.35 Å. There is one shorter (2.84 Å) and one longer (2.94 Å) Na(1)-O(5) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.40 Å. The Na(2)-O(12) bond length is 2.67 Å. The Na(2)-O(2) bond length is 2.57 Å. The Na(2)-O(4) bond length is 2.81 Å. The Na(2)-O(6) bond length is 2.79 Å. The Na(2)-O(7) bond length is 2.57 Å. The Na(2)-O(8) bond length is 2.46 Å. 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 2.49 Å. The Na(3)-O(11) bond length is 2.55 Å. The Na(3)-O(12) bond length is 2.76 Å. The Na(3)-O(7) bond length is 2.95 Å. The Na(3)-O(8) bond length is 2.47 Å. The Na(3)-O(9) bond length is 2.50 Å. Y(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 YO6 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 Y(1)-O(1) bond length is 2.17 Å. The Y(1)-O(2) bond length is 2.18 Å. The Y(1)-O(3) bond length is 2.18 Å. The Y(1)-O(7) bond length is 2.32 Å. The Y(1)-O(8) bond length is 2.24 Å. The Y(1)-O(9) bond length is 2.24 Å. Sn(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 distorted SnO6 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 Sn(1)-O(10) bond length is 2.07 Å. The Sn(1)-O(11) bond length is 2.03 Å. The Sn(1)-O(12) bond length is 2.34 Å. The Sn(1)-O(4) bond length is 2.46 Å. The Sn(1)-O(5) bond length is 2.01 Å. The Sn(1)-O(6) bond length is 2.00 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. The Si(1)-O(1) bond length is 1.60 Å. The Si(1)-O(10) bond length is 1.70 Å. The Si(1)-O(6) bond length is 1.69 Å. The Si(1)-O(9) bond length is 1.62 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-46°. The Si(2)-O(11) bond length is 1.68 Å. The Si(2)-O(2) bond length is 1.61 Å. The Si(2)-O(5) bond length is 1.69 Å. The Si(2)-O(8) bond length is 1.62 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 Y(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-34°. 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 1.49 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 Y(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Y(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Y(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Na(2), one Sn(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 Sn(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Sn(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 Y(1), and one S(1) atom. In the eighth O site, O(8) is bonded to one Na(2), one Na(3), one Y(1), and one Si(2) atom to form distorted corner-sharing ONa2YSi trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Y(1), and one Si(1) atom. 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 Sn(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Na(3), one Sn(1), and one Si(2) atom to form distorted corner-sharing ONa2SiSn trigonal pyramids. In the twelfth O site, O(12) is bonded in a distorted single-bond geometry to one Na(2), one Na(3), one Sn(1), and one S(1) atom.