The two new thiostannate compounds (trenH) 2 Sn 3 S 7 (1) and {[Mn(tren)] 2 Sn 2 S 6 } (2) (tren = tris-2-aminoethylamine) were obtained under solvothermal conditions. Compound 1 crystallizes in the hexagonal space group P6 3 /mmc with a = 13.2642(19), c = 19.078(3) Å, V = 2906.9(7) Å 3 . The layered [Sn 3 S 7 ] 2− anion is constructed by Sn 3 S 4 semi-cubes sharing common edges. The layers are characterized by large hexagonal pores with dimensions of about 11 × 11 Å 2 . Compound 2 crystallizes in the triclinic space group P1 with lattice parameters a = 7.6485(7), b = 8.1062 (7), c = 12.1805(11) Å, α = 97.367(11), β = 103.995(11), γ = 108.762(10) • , V = 676.17(10) Å 3 . The [Sn 2 S 6 ] 4− anion is composed of two edge-sharing SnS 4 tetrahedra and joins two Mn 2+ -centered complexes by Mn-S bond formation. The Mn 2+ cation is in a trigonal-bipyramidal environment of four N atoms of the tren ligand and one S atom of the thiostannate anion. Both compounds are semiconductors with a band gap of 2.96 eV for 1 and of 2.75 eV for 2.