title: The structure of chloromethyl thiocyanate, CH2ClSCN, in gas and crystalline phases.
abstract: 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.
authors.affiliation: CEQUINOR (UNLP-CONICET), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115, 1900 La Plata, República Argentina. carlosdv@quimica.unlp.edu.ar.
authors.forename: Y
authors.initials: Y
authors.lastname: Berrueta Martínez
authors.forename: L S
authors.initials: LS
authors.lastname: Rodríguez Pirani
authors.forename: M F
authors.initials: MF
authors.lastname: Erben
authors.forename: C G
authors.initials: CG
authors.lastname: Reuter
authors.forename: Y V
authors.initials: YV
authors.lastname: Vishnevskiy
authors.forename: H G
authors.initials: HG
authors.lastname: Stammler
authors.forename: N W
authors.initials: NW
authors.lastname: Mitzel
authors.forename: C O
authors.initials: CO
authors.lastname: Della Védova