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By analyzing the DSC heating curves and the resulting phase diagrams of the systems of dibromodimethylsilane and 2-, 3- or 4-methylpyridine the existence of the congruently melting addition compounds ((CH3)2SiBr2)2 · (3-methylpyridine) and (CH3)2SiBr2 · (4-methylpyridine)2, and the incongruently melting addition compounds ((CH3)2SiBr2)2 · (2-methylpyridine) and ((CH3)2SiBr2)2 · (4-methylpyridine) could be proved.