Pb2GeS4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(1) atoms. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one S(3), one S(4), and two equivalent S(2) 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 1-coordinate geometry to two equivalent Pb(1) and one Ge(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Pb(1), two equivalent Pb(2), and one Ge(1) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Pb(1), one Pb(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one Ge(1) atom.
Pb2GeS4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded in a 5-coordinate geometry to one S(2), one S(3), one S(4), and two equivalent S(1) atoms. The Pb(1)-S(2) bond length is 2.87 Å. The Pb(1)-S(3) bond length is 2.85 Å. The Pb(1)-S(4) bond length is 3.16 Å. There is one shorter (2.81 Å) and one longer (3.21 Å) Pb(1)-S(1) bond length. In the second Pb site, Pb(2) is bonded in a 4-coordinate geometry to one S(3), one S(4), and two equivalent S(2) atoms. The Pb(2)-S(3) bond length is 2.86 Å. The Pb(2)-S(4) bond length is 2.84 Å. There is one shorter (2.98 Å) and one longer (2.99 Å) Pb(2)-S(2) 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 2.22 Å. The Ge(1)-S(2) bond length is 2.21 Å. The Ge(1)-S(3) bond length is 2.23 Å. The Ge(1)-S(4) bond length is 2.20 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 1-coordinate geometry to two equivalent Pb(1) and one Ge(1) atom. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Pb(1), two equivalent Pb(2), and one Ge(1) atom. In the third S site, S(3) is bonded in a 3-coordinate geometry to one Pb(1), one Pb(2), and one Ge(1) atom. In the fourth S site, S(4) is bonded in a distorted single-bond geometry to one Pb(1), one Pb(2), and one Ge(1) atom.