Trichloromethyl thiocyanate, CCl
3SCN, 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 CCl
3 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 CH
2ClSCN (Berrueta
Martínez et al.
Phys. Chem. Chem. Phys. 2015,
17, 15805–15812).[
1] Bond lengths and angles are similar for gas and crystal CCl
3SCN 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⋅⋅⋅N angles (Y=Cl or S) close to 180° provide evidence for typical σ-hole interactions along the halogen/chalcogen−carbon bond in N⋅⋅⋅Cl and N⋅⋅⋅S, intermolecular units.