Anomeric Interactions in Pentafluoroethylimidosulfurous Dichloride, CF3CF2N=SCl2: Structural, Conformational and Configurational Properties in the Gaseous and Condensed Phases

ROBLES, NORMA LIS; ÁLVAREZ, ROSA; CUTÍN, EDGARDO; DELLA VÉDOVA, CARLOS OMAR; ERBEN, MAURICIO FEDERICO; BOESE RONALD; WILLNER HELGE; MEWS R

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

Wiley-VCH Verlag GmbH & Co. KGaA

Lugar: Weinheim, Germany; Año: 2007 vol. 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 usingthe 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, "beta"= 96.391(3) degrees, 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.