The phase equilibria in the quasi-ternary system Tl 2 Se-HgSe-GeSe 2 were investigated by differential-thermal analysis and X-ray diffraction. Phase diagrams of the Tl 2 Se-HgSe and Tl 2 GeSe 3-HgSe systems were constructed, as well as the isothermal section of the Tl 2 Se-HgSe-GeSe 2 system at 520 K. Two intermediate quaternary compounds, Tl 2 HgGeSe 4 and Tl 2 HgGe 2 Se 6 , exist at this temperature. Tl 2 HgGeSe 4 crystallizes in the non-centrosymmetric space group I-42m with the unit cell parameters a = 0.79947(4) nm, c = 0.67617(4) nm.

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