Na4La2Si2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(5), one O(7), and one O(9) atom. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(3), 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(12), one O(2), one O(4), one O(7), and one O(8) atom. In the fourth Na site, Na(4) 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. There are two inequivalent La sites. In the first La site, La(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 LaO6 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 La site, La(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 distorted LaO6 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-46°. 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-45°. 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-39°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one La(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(3), one La(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one La(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one La(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one La(2) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(3), one Na(4), one La(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one La(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(4), one La(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), one La(2), and one S(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one La(2), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one La(2), and one Si(2) atom.
Na4La2Si2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(10), one O(11), one O(5), one O(7), and one O(9) atom. The Na(1)-O(10) bond length is 2.89 Å. The Na(1)-O(11) bond length is 2.82 Å. The Na(1)-O(5) bond length is 2.57 Å. The Na(1)-O(7) bond length is 2.72 Å. The Na(1)-O(9) bond length is 2.79 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(3), and one O(8) atom. The Na(2)-O(11) bond length is 2.44 Å. The Na(2)-O(12) bond length is 2.77 Å. The Na(2)-O(3) bond length is 2.55 Å. The Na(2)-O(8) bond length is 2.54 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(2), one O(4), one O(7), and one O(8) atom. The Na(3)-O(10) bond length is 2.95 Å. The Na(3)-O(12) bond length is 2.49 Å. The Na(3)-O(2) bond length is 2.96 Å. The Na(3)-O(4) bond length is 2.71 Å. The Na(3)-O(7) bond length is 2.50 Å. The Na(3)-O(8) bond length is 2.82 Å. In the fourth Na site, Na(4) 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(4)-O(10) bond length is 2.94 Å. The Na(4)-O(11) bond length is 2.62 Å. The Na(4)-O(12) bond length is 2.49 Å. The Na(4)-O(7) bond length is 2.47 Å. The Na(4)-O(8) bond length is 2.70 Å. The Na(4)-O(9) bond length is 2.98 Å. There are two inequivalent La sites. In the first La site, La(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 LaO6 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 La(1)-O(1) bond length is 2.55 Å. The La(1)-O(2) bond length is 2.25 Å. The La(1)-O(3) bond length is 2.33 Å. The La(1)-O(7) bond length is 2.42 Å. The La(1)-O(8) bond length is 2.32 Å. The La(1)-O(9) bond length is 2.58 Å. In the second La site, La(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 distorted LaO6 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 La(2)-O(10) bond length is 2.50 Å. The La(2)-O(11) bond length is 2.38 Å. The La(2)-O(12) bond length is 2.41 Å. The La(2)-O(4) bond length is 2.31 Å. The La(2)-O(5) bond length is 2.32 Å. The La(2)-O(6) bond length is 2.46 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-46°. The Si(1)-O(11) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(5) bond length is 1.65 Å. The Si(1)-O(8) bond length is 1.66 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-45°. The Si(2)-O(12) bond length is 1.66 Å. The Si(2)-O(3) bond length is 1.65 Å. The Si(2)-O(4) bond length is 1.65 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 La(1)O6 octahedra and corners with two equivalent La(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-39°. 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 1.49 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one La(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(3), one La(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one La(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one La(2), and one Si(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one La(2), and one Si(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one La(2) and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(3), one Na(4), one La(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one La(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(4), one La(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), one La(2), and one S(1) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one La(2), and one Si(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one La(2), and one Si(2) atom.