Na2ZnGeP2SO12 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(2), one O(3), one O(8), one O(9), and two equivalent O(4) 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. 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 P(1)O4 tetrahedra, corners with two equivalent P(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(12), one O(4), one O(5), and one O(6) atom to form GeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-41°. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. 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 and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-36°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zn(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 Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ge(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ge(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ge(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded to one Na(1), one Na(2), one Zn(1), and one S(1) atom to form distorted corner-sharing ONa2ZnS trigonal pyramids. In the tenth O site, O(10) is bonded to one Na(1), one Na(2), one Ge(1), and one P(1) atom to form distorted ONa2GeP trigonal pyramids that share corners with two equivalent O(9)Na2ZnS trigonal pyramids and  a faceface with one O(12)Na2GeP trigonal pyramid. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ge(1), and one S(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Ge(1), and one P(2) atom to form distorted ONa2GeP trigonal pyramids that share corners with two equivalent O(9)Na2ZnS trigonal pyramids and  a faceface with one O(10)Na2GeP trigonal pyramid.
Na2ZnGeP2SO12 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(2), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. The Na(1)-O(10) bond length is 2.35 Å. The Na(1)-O(12) bond length is 2.58 Å. The Na(1)-O(2) bond length is 2.89 Å. The Na(1)-O(3) bond length is 2.40 Å. The Na(1)-O(8) bond length is 2.28 Å. The Na(1)-O(9) bond length is 2.41 Å. Both Na(1)-O(4) bond lengths are 2.71 Å. 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 2.61 Å. The Na(2)-O(11) bond length is 2.47 Å. The Na(2)-O(12) bond length is 2.48 Å. The Na(2)-O(7) bond length is 2.33 Å. The Na(2)-O(8) bond length is 2.57 Å. The Na(2)-O(9) bond length is 2.60 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 P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Zn(1)-O(1) bond length is 1.96 Å. The Zn(1)-O(2) bond length is 1.99 Å. The Zn(1)-O(3) bond length is 1.99 Å. The Zn(1)-O(7) bond length is 2.04 Å. The Zn(1)-O(8) bond length is 2.12 Å. The Zn(1)-O(9) bond length is 2.14 Å. Ge(1) 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 GeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Ge(1)-O(10) bond length is 1.91 Å. The Ge(1)-O(11) bond length is 2.10 Å. The Ge(1)-O(12) bond length is 1.96 Å. The Ge(1)-O(4) bond length is 1.90 Å. The Ge(1)-O(5) bond length is 1.87 Å. The Ge(1)-O(6) bond length is 2.09 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-41°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(10) bond length is 1.61 Å. The P(1)-O(4) bond length is 1.62 Å. The P(1)-O(7) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Zn(1)O6 octahedra and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-40°. The P(2)-O(12) bond length is 1.61 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.53 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 and corners with two equivalent Ge(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-36°. The S(1)-O(11) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(6) bond length is 1.52 Å. The S(1)-O(9) bond length is 1.47 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zn(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 Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ge(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ge(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ge(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Zn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded to one Na(1), one Na(2), one Zn(1), and one S(1) atom to form distorted corner-sharing ONa2ZnS trigonal pyramids. In the tenth O site, O(10) is bonded to one Na(1), one Na(2), one Ge(1), and one P(1) atom to form distorted ONa2GeP trigonal pyramids that share corners with two equivalent O(9)Na2ZnS trigonal pyramids and  a faceface with one O(12)Na2GeP trigonal pyramid. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ge(1), and one S(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Ge(1), and one P(2) atom to form distorted ONa2GeP trigonal pyramids that share corners with two equivalent O(9)Na2ZnS trigonal pyramids and  a faceface with one O(10)Na2GeP trigonal pyramid.