Vibrational spectra and molecular structure of isomeric 1-(adamantan-1-ylcarbonyl)-3-(dichlorophenyl)thioureas

ASHRAF, S.; SAEED, AAMER; SIMPSON, J.; ERBEN, MAURICIO FEDERICO

JOURNAL OF MOLECULAR STRUCTURE

ELSEVIER SCIENCE BV

Lugar: Amsterdam; Año: 2017 vol. 1129 p. 283 - 291

0022-2860

1-(adamantan-1-ylcarbonyl)-3-(2,3-dichlorophenyl)thiourea, 1, and 1-(adamantan-1-ylcarbonyl)-3-(2,5-dichlorophenyl)thiourea, 2, were synthesized in reasonable yields from admanantyl-1-carbonyl chlorideand ammonium thiocyanate followed by treatment of the resulting adamantane-1-carbonylisothiocyanate with the 2,3- and 2,5-dichloroanilines. A complete vibrational analysis was performed on the basis of FTIR and Raman spectra. The formation of intramolecular NeH/O and intermolecular NeH/S hydrogen bonds in the solids affect vibrational modes, with low frequency values observed for the n(C]O) and n(C]S) stretching modes. Structural data obtained by single-crystal X-raydiffraction at low temperature confirm this picture. Compound 1 crystallizes in the triclinic system and compound 2 crystallizes with two unique molecules in the asymmetric unit of the orthorhombic unitcell. The molecular structures reveal that the carbonylthiourea units in 1 and both molecules of 2 are planar due in part to the formation of intramolecular NeH/O]C hydrogen bonds that generate S (6) rings. Moreover, the crystal structures are stabilized by an extensive series of classical and non-classical hydrogen bonds and, in the case of 1 by an intermolecular Cl/Cl halogen bond.