CsSmGeS4 crystallizes in the orthorhombic P2_12_12_1 space group. Cs(1) is bonded in a 8-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. Sm(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted see-saw-like geometry to one Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to three equivalent Cs(1), one Sm(1), and one Ge(1) atom to form distorted corner-sharing SCs3SmGe trigonal bipyramids.
CsSmGeS4 crystallizes in the orthorhombic P2_12_12_1 space group. Cs(1) is bonded in a 8-coordinate geometry to one S(1), two equivalent S(2), two equivalent S(3), and three equivalent S(4) atoms. The Cs(1)-S(1) bond length is 3.49 Å. There is one shorter (3.80 Å) and one longer (3.86 Å) Cs(1)-S(2) bond length. There is one shorter (3.72 Å) and one longer (3.94 Å) Cs(1)-S(3) bond length. There are a spread of Cs(1)-S(4) bond distances ranging from 3.60-3.67 Å. Sm(1) is bonded in a 7-coordinate geometry to one S(4), two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms. The Sm(1)-S(4) bond length is 2.88 Å. There is one shorter (2.86 Å) and one longer (3.02 Å) Sm(1)-S(1) bond length. Both Sm(1)-S(2) bond lengths are 2.89 Å. There is one shorter (2.92 Å) and one longer (2.95 Å) Sm(1)-S(3) bond length. Ge(1) is bonded in a tetrahedral geometry to one S(1), one S(2), one S(3), and one S(4) atom. The Ge(1)-S(1) bond length is 2.23 Å. The Ge(1)-S(2) bond length is 2.24 Å. The Ge(1)-S(3) bond length is 2.24 Å. The Ge(1)-S(4) bond length is 2.21 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a distorted see-saw-like geometry to one Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent Sm(1), and one Ge(1) atom. In the fourth S site, S(4) is bonded to three equivalent Cs(1), one Sm(1), and one Ge(1) atom to form distorted corner-sharing SCs3SmGe trigonal bipyramids.