Na2CdGe2S6 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(2), one S(3), one S(4), 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 Cd(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(2), one S(3), one S(4), one S(6), and two equivalent S(5) atoms. Cd(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form CdS4 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(1), one S(3), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Cd(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(2), one S(3), one S(4), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Cd(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 trigonal non-coplanar geometry to one Na(1), one Cd(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Cd(1), and one Ge(2) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom. In the fourth S site, S(4) is bonded to one Na(1), one Na(2), one Cd(1), and one Ge(2) atom to form SNa2CdGe tetrahedra that share corners with three equivalent S(5)Na2CdGe tetrahedra and corners with three equivalent S(6)Na2Ge2 tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Na(2), one Cd(1), and one Ge(1) atom to form distorted SNa2CdGe tetrahedra that share  a cornercorner with one S(6)Na2Ge2 tetrahedra, corners with two equivalent S(5)Na2CdGe tetrahedra, corners with three equivalent S(4)Na2CdGe tetrahedra, and  an edgeedge with one S(6)Na2Ge2 tetrahedra. 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 edge and corner-sharing SNa2Ge2 tetrahedra.
Na2CdGe2S6 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(2), one S(3), one S(4), 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 Cd(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 3.02 Å. The Na(1)-S(2) bond length is 2.89 Å. The Na(1)-S(3) bond length is 3.07 Å. The Na(1)-S(4) bond length is 2.85 Å. The Na(1)-S(6) bond length is 3.05 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one S(2), one S(3), one S(4), one S(6), and two equivalent S(5) atoms. The Na(2)-S(2) bond length is 3.16 Å. The Na(2)-S(3) bond length is 3.29 Å. The Na(2)-S(4) bond length is 2.86 Å. The Na(2)-S(6) bond length is 2.90 Å. There is one shorter (2.96 Å) and one longer (3.26 Å) Na(2)-S(5) bond length. Cd(1) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form CdS4 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 Cd(1)-S(1) bond length is 2.57 Å. The Cd(1)-S(2) bond length is 2.58 Å. The Cd(1)-S(4) bond length is 2.57 Å. The Cd(1)-S(5) bond length is 2.56 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one S(1), one S(3), one S(5), and one S(6) atom to form GeS4 tetrahedra that share corners with two equivalent Cd(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(1) bond length is 2.18 Å. The Ge(1)-S(3) bond length is 2.31 Å. The Ge(1)-S(5) bond length is 2.20 Å. The Ge(1)-S(6) bond length is 2.29 Å. In the second Ge site, Ge(2) 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 Cd(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(2) bond length is 2.20 Å. The Ge(2)-S(3) bond length is 2.28 Å. The Ge(2)-S(4) 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 trigonal non-coplanar geometry to one Na(1), one Cd(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Cd(1), and one Ge(2) atom. In the third S site, S(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ge(1), and one Ge(2) atom. In the fourth S site, S(4) is bonded to one Na(1), one Na(2), one Cd(1), and one Ge(2) atom to form SNa2CdGe tetrahedra that share corners with three equivalent S(5)Na2CdGe tetrahedra and corners with three equivalent S(6)Na2Ge2 tetrahedra. In the fifth S site, S(5) is bonded to two equivalent Na(2), one Cd(1), and one Ge(1) atom to form distorted SNa2CdGe tetrahedra that share  a cornercorner with one S(6)Na2Ge2 tetrahedra, corners with two equivalent S(5)Na2CdGe tetrahedra, corners with three equivalent S(4)Na2CdGe tetrahedra, and  an edgeedge with one S(6)Na2Ge2 tetrahedra. 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 edge and corner-sharing SNa2Ge2 tetrahedra.