Disulfuryl Dichloride ClSO₂OSO₂Cl: A Conformation and Polymorphism Chameleon

Abstract

Disulfuryl dichloride ClSO OSO Cl was characterized by vibrational spectroscopy in the gaseous and liquid phase as well as in the Ar-matrix. By varying the temperature, certain bands could be assigned to several conformers. Gas-phase electron diffraction revealed a dominance of the anti-conformer at ambient temperature. The same conformation was found in the solid state. Via the in situ technique for crystallization, not less than four different modifications were identified. Among these different modifications, the structural parameters of the molecules remain relatively constant, but the aggregation pattern changes. Although the molecules aggregate by chlorine⋅⋅⋅oxygen contacts in each modification, the geometrical parameters of these interaction show significant differences and were evaluated and are in part inconsistent with the halogen bonding concept.

Preparation and Properties of Chlorosulfuryl Chloroformate, ClC(O)OSO2Cl

“…The conformation of all three chlorosulfuryl species is gauche regarding the orientation of the O–C single bond relative to that of the S–Cl bond. In comparison to the recently investigated symmetric pyrosulfuryl dichloride, a shorter bond of the sulfur atom to the bridging oxygen atom is observed for ClSO 2 OSO 2 Cl and a longer S–Cl bond is found in the latter case. Furthermore, the gas-phase structure was as well determined by using a one-conformer model like in the current investigation, in spite of the fact that quantum-chemical calculations suggested a multiconformer composition.…”

“…The vapor-phase FTIR and FT-Raman spectra of liquid ClC­(O)­OSO 2 Cl recorded for samples prepared by both synthetic methods described previously are identical, indicating the high purity of the samples. These spectra (Figure ) were analyzed together with the FTIR spectrum of the compound isolated in an argon matrix in a 1:1000 proportion, the prediction of quantum-chemical calculations, and a comparison with the spectra of related molecules (e.g., refs , – , , , and ). Selected experimental wavenumbers of ClC­(O)­OSO 2 Cl for the vapor-phase FTIR, argon-matrix FTIR, and liquid Raman are listed in Table .…”

“…The potential energy scan was performed using the Firefly program with the O3LYP/cc-pvtz level of theory (which earlier proved to provide a good description of related molecules like ClSO 2 OSO 2 Cl). Optimizations of the conformers were carried out using the Gaussian 09 , version D01 .…”

“…Very recently, we reported the extreme polymorphism of disulfuryl dichloride, ClSO 2 OSO 2 Cl, in its crystalline form of appearance and its conformational behavior in the gas phase, unraveled by vibrational spectroscopy and gas-phase electron diffraction (GED). 1 The reaction between sulfur trioxide and carbon tetrachloride to afford this disulfuryl dichloride was first reported by Schuẗzenberger in 1869 2 and interpreted by eq 1:…”

“…In spite of the fact that they have been widely used for more than a century, many aspects of their spectroscopic and structural chemistry are still to be uncovered. Very recently, we reported the extreme polymorphism of disulfuryl dichloride, ClSO 2 OSO 2 Cl, in its crystalline form of appearance and its conformational behavior in the gas phase, unraveled by vibrational spectroscopy and gas-phase electron diffraction (GED) …”