Synthesis, Structure Analysis, and Characterization of a New Thiostannate, (C12H25NH3)4[Sn2S6]·2H2O

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Abstract
A new thiostannate, (C12H25NH3)4[Sn2S6]·2H2O, was synthesized from SnCl4, Na2S, and dodecylamine (DDA) in the ethanol−water two-solvent system at room temperature. First a suspension was obtained. With increasing crystallization time, single crystals up to several millimeters in size were found at the bottom of the vessel. The compound was characterized by single-crystal X-ray diffraction, solid state 119Sn CPMAS NMR and 13C CPMAS NMR, IR absorption spectroscopy, and thermal analysis. The crystal data are a = 7.533(2) Å, b = 10.162(2) Å, c = 21.688(4) Å, α = 101.22(3)°, β = 90.76(3)°, γ = 101.82(3)°, triclinic, space group = P1̄, and Z = 1. The structure consists of one [Sn2S6]4- anion, four n-dodecylammonium cations, and two water molecules per unit cell. The [Sn2S6]4- dimers are formed by two edge-sharing [SnS4] tetrahedra. The hydrocarbon chains of the cations are straight with the chain direction running parallel to [001]. The chains are in van der Waals contact to each other with the nitrogen atoms pointing in opposite directions for neighboring chains. The positions of all hydrogen atoms were determined; in particular three positions were found which may suggest that the nitrogen atoms are protonated to form cationic groups. The nonorganic constituents of the structure, i.e., anions, water molecules, and ammonium groups, interact to form an infinite layer-like unit parallel to (001).