Structural effects and hydrogen bonds on N,N’-di(methoxycarbonylsulfenyl)urea, [CH3OC(O)SNH]2CO studied by experimental and theoretical methods N,N’-di(methoxycarbonylsulfenyl)urea“, [CH3OC(O)SNH]2CO: Structural and Vibrational Properties in the

TORRICO VALLEJOS, SONIA; ERBEN, MAURICIO F.; BOESE, ROLAND; PIRO; OSCAR E.; DELLA VEDOVA, CARLOS O.

JOURNAL OF MOLECULAR STRUCTURE

ELSEVIER SCIENCE BV

Año: 2009 vol. 918 p. 146 - 153

0022-2860

Abstract Pure N,N’-di(methoxycarbonylsulfenyl)urea, [CH3OC(O)SNH]2CO, is quantitatively prepared by the hydrolysis reaction of CH3OC(O)SNCO and characterized by 1H NMR, CG-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH3OC(O)SNH]2CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P21212 space group with a = 9.524(2), b = 12.003(1), c = 4.481(1) Å, and Z = 2 moieties in the unit cell. The molecule is sited on a two-fold crystallographic axis (C2) parallel to c and shows the anti-anti conformation (S–N single bonds antiperiplanar with respect to the opposite C–N single bonds in sulfenyl-ureasic group). Neighboring molecules are arranged in a chain motif that extends along the C2-axis and is held by bifurcated NH···O···HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central –SN(H)C(O)N(H)S– skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N–H···O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features.