The structure of chloromethyl thiocyanate, CH2ClSCN, in gas and crystalline phases

BERRUETA MARTINEZ, YANINA; RODRIGUEZ PIRANI, LUCAS S.; ERBEN, MAURICIO F.; REUTER, CHRISTIAN G.; VISHNEVSKIY, YURY V.; STAMMLER, HANS G.; MITZEL, NORBERT W.; DELLA VÉDOVA, CARLOS O.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ROYAL SOC CHEMISTRY

Lugar: CAMBRIDGE; Año: 2015 vol. 17 p. 15805 - 15812

1463-9076

The structural and conformational properties of chloromethyl thiocyanate, CH2ClSCN, were studied in the solid phase and in the gas phase using in situ low-temperature single-crystal X-ray diffraction experiments (XRD) and gas electron diffraction (GED), respectively. Depending on the mutual orientation of the Cl-C bond and the -SCN group, two conformations, gauche and anti, were found to coexist in the gas phase. The gauche conformer, with a dihedral angle φ(ClC-SC) = 71.8(4)°, is the most stable form, with an abundance of 89(3)% at ambient temperature. High level quantum-chemical calculations at the CCSD(T)/cc-pVTZ level of approximation reproduce these experimental results. In the solid state only gauche conformers were found to be present. The crystal structure shows specific intermolecular interactions including chalcogen-type interactions. The experimental electron density distribution was determined by high-angle X-ray diffraction. The atoms in molecules (AIM) theory was applied to analyze the charge density topology for a better characterization of intermolecular interactions present in the crystal.