title: Conformational preference of chlorothioformate species: molecular structure of ethyl chlorothioformate, ClC(O)SCH2CH3, in the solid phase and NBO analysis.
abstract: The molecular structure of ethyl chlorothioformate, ClC(O)SCH(2)CH(3), has been investigated in the solid phase by X-ray diffraction analysis at low temperature using a miniature zone-melting procedure and IR laser radiation. The crystalline solid consists exclusively of molecules with the synperiplanar conformation with respect to the C=O double bond and the S-C single bond, and gauche orientation of the ethyl group (syn-gauche). These results coincide with previous studies devoted to gas-phase conformational properties. The conformational preference for the ClC(O)SY (Y = Cl, CF(3), CH(3) and CH(2)CH(3)) series of molecules was rationalized using the natural bond orbital (NBO) scheme. It was found that both resonance (mesomeric) and anomeric (hyperconjugation) intermolecular charge-transfer interactions are important for describing the syn ↔ anti equilibrium, also illustrating the effect of electronegativity of the substituent in the conformation preference of the ClC(O)S- moiety. On the basis of the atoms in molecules (AIM) theory, intermolecular interactions have been characterized in the B3LYP/6-31G** periodic boundary electron density.
authors.affiliation: CEQUINOR (UNLP-CONICET CCT La Plata), Departamento de Química, Facultad de Ciencias Exactas, Universidad Nacional de La Plata, 47 esq. 115 (B1900AJL), CC 962, La Plata, Buenos Aires, Argentina.
authors.forename: Lucas
authors.initials: L
authors.lastname: Rodríguez Pirani
authors.forename: Mauricio F
authors.initials: MF
authors.lastname: Erben
authors.forename: Roland
authors.initials: R
authors.lastname: Boese
authors.forename: C Gustavo
authors.initials: CG
authors.lastname: Pozzi
authors.forename: Adolfo C
authors.initials: AC
authors.lastname: Fantoni
authors.forename: Carlos O
authors.initials: CO
authors.lastname: Della Védova