Na3LaGeSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. 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 4-coordinate geometry to one O(10), one O(11), one O(12), and one O(8) atom. 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 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. Ge(1) is bonded to one O(10), one O(11), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra and corners with two equivalent Si(2)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 La(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-36°. 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. 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 La(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-39°. 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 La(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 La(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Ge(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 Ge(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one La(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 La(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ge(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(3), one Ge(1), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(1) atom.
Na3LaGeSi2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(9) atom. The Na(1)-O(1) bond length is 2.29 Å. The Na(1)-O(11) bond length is 2.42 Å. The Na(1)-O(9) bond length is 2.35 Å. 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 2.48 Å. The Na(2)-O(12) bond length is 2.52 Å. The Na(2)-O(2) bond length is 2.67 Å. The Na(2)-O(4) bond length is 2.49 Å. The Na(2)-O(6) bond length is 2.80 Å. The Na(2)-O(7) bond length is 2.37 Å. The Na(2)-O(8) bond length is 2.71 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(12), and one O(8) atom. The Na(3)-O(10) bond length is 2.49 Å. The Na(3)-O(11) bond length is 2.48 Å. The Na(3)-O(12) bond length is 2.38 Å. The Na(3)-O(8) bond length is 2.42 Å. 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 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 2.31 Å. The La(1)-O(2) bond length is 2.32 Å. The La(1)-O(3) bond length is 2.24 Å. The La(1)-O(7) bond length is 2.38 Å. The La(1)-O(8) bond length is 2.41 Å. The La(1)-O(9) bond length is 2.39 Å. Ge(1) is bonded to one O(10), one O(11), one O(5), and one O(6) atom to form GeO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra and corners with two equivalent Si(2)O4 tetrahedra. The Ge(1)-O(10) bond length is 1.90 Å. The Ge(1)-O(11) bond length is 1.84 Å. The Ge(1)-O(5) bond length is 1.81 Å. The Ge(1)-O(6) bond length is 1.84 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-36°. The Si(1)-O(1) bond length is 1.60 Å. The Si(1)-O(10) bond length is 1.75 Å. The Si(1)-O(6) bond length is 1.78 Å. The Si(1)-O(9) bond length is 1.61 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 La(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-37°. The Si(2)-O(11) bond length is 1.71 Å. The Si(2)-O(2) bond length is 1.60 Å. The Si(2)-O(5) bond length is 1.72 Å. The Si(2)-O(8) bond length is 1.61 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 La(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-39°. The S(1)-O(12) bond length is 1.48 Å. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.47 Å. The S(1)-O(7) bond length is 1.51 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 La(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 La(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one La(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one S(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Ge(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 Ge(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one La(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 La(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one La(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ge(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(3), one Ge(1), and one Si(2) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one S(1) atom.