Na4CaGeSi2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(11), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(5), one O(6), one O(7), and one O(9) atom. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(3), one O(4), one O(8), and one O(9) 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. Ca(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 CaO6 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(12), one O(4), and one O(5) 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(4), and one O(7) atom to form SiO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-41°. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-32°. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), one Ca(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Ge(1), and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Na(2), one Ge(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Na(2) and one S(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), one Ca(1), and one Si(1) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ca(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(3), one Na(4), one Ge(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ge(1), and one Si(2) atom.
Na4CaGeSi2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(11), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. The Na(1)-O(11) bond length is 2.64 Å. The Na(1)-O(2) bond length is 2.64 Å. The Na(1)-O(3) bond length is 2.88 Å. The Na(1)-O(5) bond length is 2.96 Å. The Na(1)-O(7) bond length is 2.40 Å. The Na(1)-O(8) bond length is 2.65 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(5), one O(6), one O(7), and one O(9) atom. The Na(2)-O(1) bond length is 2.45 Å. The Na(2)-O(11) bond length is 2.57 Å. The Na(2)-O(12) bond length is 2.40 Å. The Na(2)-O(5) bond length is 2.80 Å. The Na(2)-O(6) bond length is 2.73 Å. The Na(2)-O(7) bond length is 2.91 Å. The Na(2)-O(9) bond length is 2.40 Å. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(10), one O(3), one O(4), one O(8), and one O(9) atom. The Na(3)-O(10) bond length is 2.47 Å. The Na(3)-O(3) bond length is 2.27 Å. The Na(3)-O(4) bond length is 2.85 Å. The Na(3)-O(8) bond length is 2.35 Å. The Na(3)-O(9) bond length is 2.76 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 2.36 Å. The Na(4)-O(11) bond length is 2.39 Å. The Na(4)-O(12) bond length is 2.63 Å. The Na(4)-O(7) bond length is 2.32 Å. The Na(4)-O(8) bond length is 2.84 Å. The Na(4)-O(9) bond length is 2.78 Å. Ca(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 CaO6 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 Ca(1)-O(1) bond length is 2.20 Å. The Ca(1)-O(2) bond length is 2.22 Å. The Ca(1)-O(3) bond length is 2.20 Å. The Ca(1)-O(7) bond length is 2.35 Å. The Ca(1)-O(8) bond length is 2.39 Å. The Ca(1)-O(9) bond length is 2.30 Å. Ge(1) is bonded to one O(10), one O(12), one O(4), and one O(5) 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 1.82 Å. The Ge(1)-O(12) bond length is 1.86 Å. The Ge(1)-O(4) bond length is 1.79 Å. The Ge(1)-O(5) bond length is 1.83 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 Ca(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 34-41°. The Si(1)-O(1) bond length is 1.59 Å. The Si(1)-O(10) bond length is 1.71 Å. The Si(1)-O(4) bond length is 1.70 Å. The Si(1)-O(7) bond length is 1.61 Å. In the second Si site, Si(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ge(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 26-32°. The Si(2)-O(12) bond length is 1.73 Å. The Si(2)-O(3) bond length is 1.59 Å. The Si(2)-O(5) bond length is 1.78 Å. The Si(2)-O(8) bond length is 1.61 Å. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-43°. The S(1)-O(11) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.47 Å. The S(1)-O(6) bond length is 1.48 Å. The S(1)-O(9) bond length is 1.50 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), one Ca(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Ge(1), and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Na(2), one Ge(1), and one Si(2) atom. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to one Na(2) and one S(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), one Ca(1), and one Si(1) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ca(1), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(3), one Na(4), one Ge(1), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ge(1), and one Si(2) atom.