((Fluoroformyl)imido)sulfuryl Difluoride, FC(O)NS(O)F₂:  Structural, Conformational, and Configurational Properties in the Gaseous and Condensed Phases

Abstract

Structural, conformational, and configurational properties of the gaseous molecule ((fluoroformyl)imido)sulfuryl difluoride, FC(O)N=S(O)F(2), have been studied by vibrational spectroscopy (IR (gas) and Raman (liquid)) and quantum chemical calculations (HF, MP2, and B3LYP with 6-31+G* and 6-311+G* basis sets); in addition, the solid-state structure has been determined by X-ray crystallography. FC(O)N=S(O)F(2) exists in the gas phase as a mixture of a favored antiperiplanar-synperiplanar form (the S=O double bond antiperiplanar with respect to the C-N single bond, and the C=O group synperiplanar with respect to the S=N double bond) in equilibrium with less abundant antiperiplanar-antiperiplanar, synclinal-synperiplanar, and synclinal-antiperiplanar structures. The crystalline solid at 163 K (monoclinic, P2(1)/c, a = 5.1323(7) A, b = 15.942(2) A, c = 16.798(2) A, beta = 95.974(3) degrees , Z = 12) consists of three similar antiperiplanar-synperiplanar forms.

Structure and Conformational Properties of N-Pentafluorosulfur(sulfuroxide difluoride imide) SF5NS(O)F2: Vibrational Analysis, Gas Electron Diffraction, and Quantum Chemical Calculations

“…The characteristic bands centered at 1446 and 1277 cm -1 in the IR spectrum of the gas phase and at 1437 and 1272 cm -1 in the Raman spectrum of the liquid phase are straightforwardly assigned to the antisymmetric and symmetric NSO stretching modes, respectively, in fair agreement with the data reported for the related molecules FSO 2 NS(O)F 2 , NCNS(O)F 2 , and FCONS(O)F 2 . The band assigned to the NSO symmetric mode in the IR (gas) spectrum (1277 cm -1 ) shows a well-defined shoulder at lower wavenumbers (at approximately 1263 cm -1 ) demonstrating the presence of a second conformer, which possesses anticlinal orientation of the N−S bond with respect to the SF 2 group, according to the theoretical calculations.…”

“…The observed IR (gas) and Raman (liquid) spectra have been assigned on the basis of their calculated vibrational frequencies and intensities (Table ). Furthermore, characteristic wavenumbers of the NS(O)F 2 moiety in the related molecules FSO 2 NS(O)F 2 , NCNS(O)F 2 , and FCONS(O)F 2 have been taken into account. For assignment of the modes belonging to the SF 5 N group additional calculations (MP2) were performed for SF 5 NCO and SF 5 NSF 2 , for which no experimental data are available.…”

Organoelement Compounds Crystallized In Situ: Weak Intermolecular Interactions and Lattice Energies

“…To investigate the conformational flexibility of this compound, Cutín and colleagues [44] carried out a gas electron diffraction experiment. Later, Roland Boese et al [45] used X-ray diffraction with the in situ crystallization method to determine the structure of the related solid-phase compound ((fluoroformyl)imidosulfuryl difluoride, compound 27). It revealed that compound 27 is in the antiperiplanar-synperiplanar conformation.…”

Gas phase structure of ((fluoroformyl)imido)sulfuryl difluoride, FC(O)NS(O)F2

“…Syn implies synperiplanar or synclinal and anti implies antiperiplanar or anticlinal. The crystal structure, a vibrational analysis and quantum chemical calculation of FC(O)NaS(O)F 2 have been reported recently [11]. According to these calculations all four conformers correspond to stable structures with the syn-syn form being lowest in energy (in Ref.…”