Na2GeS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(2), one S(3), and three equivalent S(1) atoms to form distorted NaS5 trigonal bipyramids that share corners with six equivalent Na(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Na(1)S5 trigonal bipyramids, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Ge(1)S4 tetrahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-84°. In the second Na site, Na(2) is bonded to one S(3), two equivalent S(1), and three equivalent S(2) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(2)S6 octahedra, corners with three equivalent Ge(1)S4 tetrahedra, corners with six equivalent Na(1)S5 trigonal bipyramids, edges with three equivalent Na(2)S6 octahedra, edges with two equivalent Ge(1)S4 tetrahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 24°. Ge(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form GeS4 tetrahedra that share corners with three equivalent Na(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Na(1)S5 trigonal bipyramids, edges with two equivalent Na(2)S6 octahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-66°. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(2), three equivalent Na(1), and one Ge(1) atom to form distorted SNa5Ge octahedra that share corners with two equivalent S(1)Na5Ge octahedra, corners with four equivalent S(2)Na4Ge trigonal bipyramids, edges with three equivalent S(1)Na5Ge octahedra, and edges with three equivalent S(2)Na4Ge trigonal bipyramids. The corner-sharing octahedral tilt angles are 21°. In the second S site, S(2) is bonded to one Na(1), three equivalent Na(2), and one Ge(1) atom to form SNa4Ge trigonal bipyramids that share corners with four equivalent S(1)Na5Ge octahedra, corners with two equivalent S(2)Na4Ge trigonal bipyramids, edges with three equivalent S(1)Na5Ge octahedra, and edges with two equivalent S(2)Na4Ge trigonal bipyramids. The corner-sharing octahedral tilt angles range from 6-82°. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Ge(1) atoms.
Na2GeS3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one S(2), one S(3), and three equivalent S(1) atoms to form distorted NaS5 trigonal bipyramids that share corners with six equivalent Na(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Na(1)S5 trigonal bipyramids, edges with two equivalent Na(2)S6 octahedra, edges with two equivalent Ge(1)S4 tetrahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-84°. The Na(1)-S(2) bond length is 2.82 Å. The Na(1)-S(3) bond length is 3.00 Å. There are a spread of Na(1)-S(1) bond distances ranging from 2.93-2.96 Å. In the second Na site, Na(2) is bonded to one S(3), two equivalent S(1), and three equivalent S(2) atoms to form distorted NaS6 octahedra that share corners with two equivalent Na(2)S6 octahedra, corners with three equivalent Ge(1)S4 tetrahedra, corners with six equivalent Na(1)S5 trigonal bipyramids, edges with three equivalent Na(2)S6 octahedra, edges with two equivalent Ge(1)S4 tetrahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 24°. The Na(2)-S(3) bond length is 2.80 Å. There is one shorter (2.87 Å) and one longer (3.02 Å) Na(2)-S(1) bond length. There are two shorter (2.90 Å) and one longer (3.05 Å) Na(2)-S(2) bond length. Ge(1) is bonded to one S(1), one S(2), and two equivalent S(3) atoms to form GeS4 tetrahedra that share corners with three equivalent Na(2)S6 octahedra, corners with two equivalent Ge(1)S4 tetrahedra, corners with two equivalent Na(1)S5 trigonal bipyramids, edges with two equivalent Na(2)S6 octahedra, and edges with two equivalent Na(1)S5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 26-66°. The Ge(1)-S(1) bond length is 2.18 Å. The Ge(1)-S(2) bond length is 2.17 Å. There is one shorter (2.25 Å) and one longer (2.27 Å) Ge(1)-S(3) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Na(2), three equivalent Na(1), and one Ge(1) atom to form distorted SNa5Ge octahedra that share corners with two equivalent S(1)Na5Ge octahedra, corners with four equivalent S(2)Na4Ge trigonal bipyramids, edges with three equivalent S(1)Na5Ge octahedra, and edges with three equivalent S(2)Na4Ge trigonal bipyramids. The corner-sharing octahedral tilt angles are 21°. In the second S site, S(2) is bonded to one Na(1), three equivalent Na(2), and one Ge(1) atom to form SNa4Ge trigonal bipyramids that share corners with four equivalent S(1)Na5Ge octahedra, corners with two equivalent S(2)Na4Ge trigonal bipyramids, edges with three equivalent S(1)Na5Ge octahedra, and edges with two equivalent S(2)Na4Ge trigonal bipyramids. The corner-sharing octahedral tilt angles range from 6-82°. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), and two equivalent Ge(1) atoms.