Abstract
Carbon disulfide, CS2, mp = 161.7 K, has been crystallized in situ in a diamond-anvil cell at 295 K and 1.26 GPa to give an orthorhombic Cmca structure. No phase transitions occur with further increasing pressure till the polymerization onset at 8 GPa. The crystal structure was determined by direct methods from single-crystal X-ray diffraction at 295 K at two pressure points: 1.8 and 3.7 GPa (esd’s in the lengths of CS bond 0.0001 nm). The molecular rearrangements have been rationalized by the close packing and equidistant S···S intermolecular interactions enforced by pressure. Although only slight lengthening of the covalent double CS bond has been observed till 3.7 GPa, the intensified intermolecular S···S and C···S interactions reveal the possible reaction pathways of pressure-induced polymerization of CS2.
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