Anomeric Interactions in N-Pentafluoroethyl Sulfurdichloride Imide; CF3CF2N=SCl2: Structural, Conformational and Configurational Properties in the Gaseous and Condensed Phases

ROBLES, N.L.; ROSA MARIA SUSANA ALVAREZ; CUTIN, E.; ERBEN,; BOESE,; WILLNER,; MEWS,R.; DELLA VEDOVA, C.

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

WILEY-V C H VERLAG GMBH

Año: 2007 p. 3535 - 3542

1434-1948

The structural, conformational, and configurational properties of pentafluoroethylimidosulfurous dichloride (CF3CF2N=SCl2) have been studied by vibrational spectroscopy [IR (vapor) and Raman (liquid)] and quantum chemical calculations [HF, B3LYP and MP2 approximations using the 6-311+G(d) and 6-311+G(2df) basis sets]. CF3CF2N=SCl2 exists in the liquid phase as a single (Z) form (C–N bond synperiplanar with respect to the Cl–S–Cl plane; C1 symmetry). The structure was also determined by X-ray diffraction analysis of a single crystal grown in situ at low temperature. The crystalline solid at 159 K (monoclinic, P21/c, a = 5.2466(10), b = 15.376(3), c = 18.730(3) Å, β = 96.391(3)°, Z = 8) consists of two crystallographically inequivalent (Z) forms. The results are discussed in terms of both hyperconjugative electronic effects and of natural bond orbital (NBO) calculations.