Na2Zn(GeS3)2 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(3), one S(4), one S(5), and one S(6) atom to form distorted NaS5 trigonal bipyramids that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with four equivalent Ge(2)S4 tetrahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(1), one S(4), one S(5), one S(6), and two equivalent S(2) atoms. Zn(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with three equivalent Na(1)S5 trigonal bipyramids. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(2), one S(3), one S(4), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra,  a cornercorner with one Na(1)S5 trigonal bipyramid, and  an edgeedge with one Na(1)S5 trigonal bipyramid. In the second Ge site, Ge(2) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, and corners with four equivalent Na(1)S5 trigonal bipyramids. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one Ge(2) atom. In the second S site, S(2) is bonded to two equivalent Na(2), one Zn(1), and one Ge(1) atom to form distorted SNa2ZnGe tetrahedra that share corners with two equivalent S(2)Na2ZnGe tetrahedra, corners with three equivalent S(5)Na2ZnGe tetrahedra,  a cornercorner with one S(6)Na2Ge2 trigonal pyramid, and  an edgeedge with one S(6)Na2Ge2 trigonal pyramid. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one Na(1), one Zn(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom. In the fifth S site, S(5) is bonded to one Na(1), one Na(2), one Zn(1), and one Ge(2) atom to form SNa2ZnGe tetrahedra that share corners with three equivalent S(2)Na2ZnGe tetrahedra and corners with three equivalent S(6)Na2Ge2 trigonal pyramids. In the sixth S site, S(6) is bonded to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom to form a mixture of corner and edge-sharing SNa2Ge2 trigonal pyramids.
Na2Zn(GeS3)2 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(1), one S(3), one S(4), one S(5), and one S(6) atom to form distorted NaS5 trigonal bipyramids that share  a cornercorner with one Ge(1)S4 tetrahedra, corners with three equivalent Zn(1)S4 tetrahedra, corners with four equivalent Ge(2)S4 tetrahedra, and  an edgeedge with one Ge(1)S4 tetrahedra. The Na(1)-S(1) bond length is 2.88 Å. The Na(1)-S(3) bond length is 2.97 Å. The Na(1)-S(4) bond length is 3.08 Å. The Na(1)-S(5) bond length is 2.84 Å. The Na(1)-S(6) bond length is 2.95 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(1), one S(4), one S(5), one S(6), and two equivalent S(2) atoms. The Na(2)-S(1) bond length is 3.37 Å. The Na(2)-S(4) bond length is 3.11 Å. The Na(2)-S(5) bond length is 2.82 Å. The Na(2)-S(6) bond length is 2.88 Å. There is one shorter (2.99 Å) and one longer (3.24 Å) Na(2)-S(2) bond length. Zn(1) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form ZnS4 tetrahedra that share corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra, and corners with three equivalent Na(1)S5 trigonal bipyramids. The Zn(1)-S(1) bond length is 2.38 Å. The Zn(1)-S(2) bond length is 2.37 Å. The Zn(1)-S(3) bond length is 2.38 Å. The Zn(1)-S(5) bond length is 2.37 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(2), one S(3), one S(4), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(2)S4 tetrahedra,  a cornercorner with one Na(1)S5 trigonal bipyramid, and  an edgeedge with one Na(1)S5 trigonal bipyramid. The Ge(1)-S(2) bond length is 2.21 Å. The Ge(1)-S(3) bond length is 2.19 Å. The Ge(1)-S(4) bond length is 2.30 Å. The Ge(1)-S(6) bond length is 2.29 Å. In the second Ge site, Ge(2) is bonded to one S(1), one S(4), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Zn(1)S4 tetrahedra, corners with two equivalent Ge(1)S4 tetrahedra, and corners with four equivalent Na(1)S5 trigonal bipyramids. The Ge(2)-S(1) bond length is 2.20 Å. The Ge(2)-S(4) bond length is 2.28 Å. The Ge(2)-S(5) bond length is 2.21 Å. The Ge(2)-S(6) bond length is 2.29 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(1), and one Ge(2) atom. In the second S site, S(2) is bonded to two equivalent Na(2), one Zn(1), and one Ge(1) atom to form distorted SNa2ZnGe tetrahedra that share corners with two equivalent S(2)Na2ZnGe tetrahedra, corners with three equivalent S(5)Na2ZnGe tetrahedra,  a cornercorner with one S(6)Na2Ge2 trigonal pyramid, and  an edgeedge with one S(6)Na2Ge2 trigonal pyramid. In the third S site, S(3) is bonded in a trigonal non-coplanar geometry to one Na(1), one Zn(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom. In the fifth S site, S(5) is bonded to one Na(1), one Na(2), one Zn(1), and one Ge(2) atom to form SNa2ZnGe tetrahedra that share corners with three equivalent S(2)Na2ZnGe tetrahedra and corners with three equivalent S(6)Na2Ge2 trigonal pyramids. In the sixth S site, S(6) is bonded to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom to form a mixture of corner and edge-sharing SNa2Ge2 trigonal pyramids.