NaCe3GeS7 crystallizes in the hexagonal P6_3 space group. Na(1) is bonded to six equivalent S(2) atoms to form face-sharing NaS6 octahedra. Ce(1) is bonded in a 8-coordinate geometry to one S(1), three equivalent S(3), and four equivalent S(2) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ce(1) and one Ge(1) atom to form corner-sharing SCe3Ge tetrahedra. In the second S site, S(2) is bonded to two equivalent Na(1) and four equivalent Ce(1) atoms to form distorted SNa2Ce4 pentagonal pyramids that share corners with four equivalent S(2)Na2Ce4 pentagonal pyramids, corners with four equivalent S(1)Ce3Ge tetrahedra, and faces with six equivalent S(2)Na2Ce4 pentagonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ce(1) and one Ge(1) atom.
NaCe3GeS7 crystallizes in the hexagonal P6_3 space group. Na(1) is bonded to six equivalent S(2) atoms to form face-sharing NaS6 octahedra. There are three shorter (2.75 Å) and three longer (2.76 Å) Na(1)-S(2) bond lengths. Ce(1) is bonded in a 8-coordinate geometry to one S(1), three equivalent S(3), and four equivalent S(2) atoms. The Ce(1)-S(1) bond length is 3.03 Å. There are a spread of Ce(1)-S(3) bond distances ranging from 2.88-3.06 Å. There are a spread of Ce(1)-S(2) bond distances ranging from 2.91-3.20 Å. Ge(1) is bonded in a tetrahedral geometry to one S(1) and three equivalent S(3) atoms. The Ge(1)-S(1) bond length is 2.22 Å. All Ge(1)-S(3) bond lengths are 2.25 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Ce(1) and one Ge(1) atom to form corner-sharing SCe3Ge tetrahedra. In the second S site, S(2) is bonded to two equivalent Na(1) and four equivalent Ce(1) atoms to form distorted SNa2Ce4 pentagonal pyramids that share corners with four equivalent S(2)Na2Ce4 pentagonal pyramids, corners with four equivalent S(1)Ce3Ge tetrahedra, and faces with six equivalent S(2)Na2Ce4 pentagonal pyramids. In the third S site, S(3) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Ce(1) and one Ge(1) atom.