Na4ZnGeSi2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(7), one O(9), and two equivalent O(1) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. In the fourth Na site, Na(4) 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. Zn(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 ZnO6 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 in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom. 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-35°. 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-35°. 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-36°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(2), one Zn(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 Zn(1), and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zn(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent 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(1), one Na(2), one Ge(1), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Na(4), one Zn(1), and one Si(1) atom to form distorted ONa3ZnSi trigonal bipyramids that share  a cornercorner with one O(10)Na3SiGe trigonal bipyramid,  an edgeedge with one O(10)Na3SiGe trigonal bipyramid, and  a faceface with one O(8)Na3ZnSi trigonal bipyramid. In the eighth O site, O(8) is bonded to one Na(1), one Na(3), one Na(4), one Zn(1), and one Si(2) atom to form distorted ONa3ZnSi trigonal bipyramids that share corners with three equivalent O(10)Na3SiGe trigonal bipyramids and  a faceface with one O(7)Na3ZnSi trigonal bipyramid. 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 Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Na(4), one Ge(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing ONa3SiGe trigonal bipyramids. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(4), one Ge(1), and one S(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 Ge(1), and one Si(2) atom.
Na4ZnGeSi2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom. The Na(1)-O(10) bond length is 2.66 Å. The Na(1)-O(11) bond length is 2.53 Å. The Na(1)-O(2) bond length is 2.67 Å. The Na(1)-O(3) bond length is 2.87 Å. The Na(1)-O(5) bond length is 2.71 Å. The Na(1)-O(6) bond length is 2.98 Å. The Na(1)-O(7) bond length is 2.38 Å. The Na(1)-O(8) bond length is 2.44 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(7), one O(9), and two equivalent O(1) atoms. The Na(2)-O(11) bond length is 2.57 Å. The Na(2)-O(12) bond length is 2.41 Å. The Na(2)-O(5) bond length is 2.86 Å. The Na(2)-O(6) bond length is 2.75 Å. The Na(2)-O(7) bond length is 2.49 Å. The Na(2)-O(9) bond length is 2.47 Å. There is one shorter (2.45 Å) and one longer (2.97 Å) Na(2)-O(1) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. The Na(3)-O(10) bond length is 2.50 Å. The Na(3)-O(12) bond length is 2.75 Å. The Na(3)-O(3) bond length is 2.36 Å. The Na(3)-O(8) bond length is 2.32 Å. The Na(3)-O(9) bond length is 2.50 Å. There is one shorter (2.77 Å) and one longer (2.85 Å) Na(3)-O(4) bond length. In the fourth Na site, Na(4) 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(4)-O(10) bond length is 2.48 Å. The Na(4)-O(11) bond length is 2.66 Å. The Na(4)-O(12) bond length is 2.56 Å. The Na(4)-O(7) bond length is 2.36 Å. The Na(4)-O(8) bond length is 2.47 Å. The Na(4)-O(9) bond length is 2.63 Å. Zn(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 ZnO6 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 Zn(1)-O(1) bond length is 1.99 Å. The Zn(1)-O(2) bond length is 2.04 Å. The Zn(1)-O(3) bond length is 1.96 Å. The Zn(1)-O(7) bond length is 2.14 Å. The Zn(1)-O(8) bond length is 2.22 Å. The Zn(1)-O(9) bond length is 2.17 Å. Ge(1) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom. The Ge(1)-O(10) bond length is 1.85 Å. The Ge(1)-O(11) bond length is 2.47 Å. The Ge(1)-O(12) bond length is 1.91 Å. The Ge(1)-O(4) bond length is 1.79 Å. The Ge(1)-O(5) bond length is 1.86 Å. The Ge(1)-O(6) bond length is 2.36 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-35°. The Si(1)-O(1) bond length is 1.59 Å. The Si(1)-O(10) bond length is 1.70 Å. The Si(1)-O(4) bond length is 1.69 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-35°. The Si(2)-O(12) bond length is 1.72 Å. The Si(2)-O(3) bond length is 1.59 Å. The Si(2)-O(5) bond length is 1.73 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 Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-36°. 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 1.50 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 3-coordinate geometry to two equivalent Na(2), one Zn(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 Zn(1), and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zn(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent 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(1), one Na(2), one Ge(1), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Na(4), one Zn(1), and one Si(1) atom to form distorted ONa3ZnSi trigonal bipyramids that share  a cornercorner with one O(10)Na3SiGe trigonal bipyramid,  an edgeedge with one O(10)Na3SiGe trigonal bipyramid, and  a faceface with one O(8)Na3ZnSi trigonal bipyramid. In the eighth O site, O(8) is bonded to one Na(1), one Na(3), one Na(4), one Zn(1), and one Si(2) atom to form distorted ONa3ZnSi trigonal bipyramids that share corners with three equivalent O(10)Na3SiGe trigonal bipyramids and  a faceface with one O(7)Na3ZnSi trigonal bipyramid. 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 Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Na(4), one Ge(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing ONa3SiGe trigonal bipyramids. In the eleventh O site, O(11) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), one Na(4), one Ge(1), and one S(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 Ge(1), and one Si(2) atom.