Na2Sn2Si2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) 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 second Na site, Na(2) 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. There are two inequivalent Sn sites. In the first Sn site, Sn(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 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. In the second Sn site, Sn(2) 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 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(11), one O(2), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-41°. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. S(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-34°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Sn(1) and one S(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Sn(1), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sn(1) and one Si(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Sn(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Sn(2) and one Si(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Sn(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Sn(1), and one Si(2) atom to form distorted face-sharing ONa2SiSn trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Sn(1), and one Si(1) atom to form distorted face-sharing ONa2SiSn trigonal pyramids. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(2), and one S(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Sn(2), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Sn(2), and one Si(2) atom.
Na2Sn2Si2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) 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(1)-O(10) bond length is 2.48 Å. The Na(1)-O(12) bond length is 2.37 Å. The Na(1)-O(4) bond length is 2.55 Å. The Na(1)-O(6) bond length is 2.97 Å. The Na(1)-O(7) bond length is 2.49 Å. The Na(1)-O(8) bond length is 2.39 Å. There is one shorter (2.73 Å) and one longer (2.78 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) 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(2)-O(10) bond length is 2.75 Å. The Na(2)-O(11) bond length is 2.43 Å. The Na(2)-O(12) bond length is 2.52 Å. The Na(2)-O(7) bond length is 2.46 Å. The Na(2)-O(8) bond length is 2.62 Å. The Na(2)-O(9) bond length is 2.66 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(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 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(1) bond length is 2.23 Å. The Sn(1)-O(2) bond length is 1.99 Å. The Sn(1)-O(3) bond length is 1.97 Å. The Sn(1)-O(7) bond length is 2.05 Å. The Sn(1)-O(8) bond length is 2.01 Å. The Sn(1)-O(9) bond length is 2.22 Å. In the second Sn site, Sn(2) 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 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(2)-O(10) bond length is 2.20 Å. The Sn(2)-O(11) bond length is 2.01 Å. The Sn(2)-O(12) bond length is 2.06 Å. The Sn(2)-O(4) bond length is 2.02 Å. The Sn(2)-O(5) bond length is 1.99 Å. The Sn(2)-O(6) bond length is 2.13 Å. There are two inequivalent Si sites. In the first Si site, Si(1) 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 Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-41°. The Si(1)-O(11) bond length is 1.63 Å. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(5) bond length is 1.62 Å. The Si(1)-O(8) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. The Si(2)-O(12) bond length is 1.66 Å. The Si(2)-O(3) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.66 Å. S(1) is bonded to one O(1), one O(10), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Sn(1)O6 octahedra and corners with two equivalent Sn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-34°. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(10) bond length is 1.49 Å. The S(1)-O(6) bond length is 1.49 Å. The S(1)-O(9) bond length is 1.48 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Sn(1) and one S(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Sn(1), and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sn(1) and one Si(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Sn(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Sn(2) and one Si(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Sn(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Sn(1), and one Si(2) atom to form distorted face-sharing ONa2SiSn trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(2), one Sn(1), and one Si(1) atom to form distorted face-sharing ONa2SiSn trigonal pyramids. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(2), and one S(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Sn(2), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Sn(2), and one Si(2) atom.