Mesolamellar thiogermanates [CnH2n + 1NH3]4Ge4S10

The mesostructured lamellar phases with the general formula C_nH_2n + 1NH₃]₄Ge₄S₁₀ (n = 12, 14, 16, 18) were synthesized by metathesis of alkyl ammonium chloride surfactants and Na₄Ge₄S₁₀ in aqueous medium. The crystal structures of the phases with n = 12 and 14 were determined by single-crystal X-ray diffraction; C₁₂H₁₃NH₃]₄Ge₄S₁₀ crystallizes in monoclinic C2/c space group (a = 16.149(3), b = 46.576(9) c = 9.147(2) Å, β = 97.13(3)° and Z = 4) and C₁₄H₂₉NH₃]₄Ge₄S₁₀ in the triclinic space group (a = 9.1280(6), b = 16.1992(1), c = 26.971(2) Å, α =73.370(1)°, β = 88.307(1)°, γ = 82.825(1)° and Z = 2). These compounds possess layers of adamantane Ge₄S₁₀]⁴⁻ anions separated by layers of deeply interpenetrated long chain alkylammonium molecules. Strong hydrogen bonding is observed between the terminal sulfur atoms of the Ge₄S₁₀]⁴⁻ clusters and H atoms of the NH₃ groups of the surfactant molecules. Spectroscopic and thermal characterization of these compounds is reported.