Structures of Trichloromethyl Thiocyanate, CCl3SCN, in Gaseous and Crystalline State

Martinez YB, Pirani LSR, Erben MF, et al. Structures of Trichloromethyl Thiocyanate, CCl3SCN, in Gaseous and Crystalline State. CHEMPHYSCHEM. 2016;17(10):1463-1467.Trichloromethyl thiocyanate, CCl3SCN, was structurally studied in both the gas and crystal phases by means of gas electron diffraction (GED) and single-crystal X-ray diffraction (XRD), respectively. Both experimental studies and quantum chemical calculations indicate a staggered orientation of the CCl3 group relative to the SCN group. This conclusion is supported by the similarity of the C-SCN bond length to that of the anti-structure of CH2ClSCN (Berrueta Martinez et al. Phys. Chem. Chem. Phys. 2015, 17, 15805-15812).([1]) Bond lengths and angles are similar for gas and crystal CCl3SCN structures; however, the crystal structure presents different intermolecular interactions. These include halogen and chalcogen type interactions, the geometry of which was studied. Characteristic C-Y center dot center dot center dot N angles (Y=Cl or S) close to 180 degrees provide evidence for typical sigma-hole interactions along the halogen/chalcogen-carbon bond in N center dot center dot center dot Cl and N center dot center dot center dot S, intermolecular units