Structural characterization of the {3[?BPMTU]+ · 3[X]- · nH2O} salts (BPMTU = 1,3-bis(3-pyridylmethyl)-2-thiourea and X = Cl, Br, I). A polychlorine network based on O ··· Cl- and OH ··· Cl- interactions

Ozturk, I. I., Hadjikakou, S. K., Tsipis, A. C., Malandrinos, G., Kourkoumelis, N., Manos, M. J., Tasiopoulos, A. J., Light, M. E., Hursthouse, M., Bocanegra, P. E., Butler, I. S. and Hadjiliadis, N. (2011) Structural characterization of the {3[?BPMTU]+ · 3[X]- · nH2O} salts (BPMTU = 1,3-bis(3-pyridylmethyl)-2-thiourea and X = Cl, Br, I). A polychlorine network based on O ··· Cl- and OH ··· Cl- interactions. Journal of Coordination Chemistry, 64 (2), 202-221. (doi:10.1080/00958972.2010.545123).

Abstract

Ionic salts with the formulae {3[?BPMTU]+ · 3[X]- · nH2O} (BPMTU = 1,3-bis(3-pyridylmethyl)-2-thiourea, X = Cl- and n = 1.5 (1), X = Br-and n = 1 (2), X = I- and n = 1 (3)) were synthesized. The compounds have been characterized by elemental anaylses, TG-DTA, FT-IR, far-IR, Raman, ESI-MS and 1H, 13C-NMR spectroscopic methods, and X-ray powder diffraction techniques. The crystal structures of 1 and 2 have also been determined by X-ray diffraction at 120(2) and 100(2) K, respectively. In 1, weak lp(Cl-) ? ?*(O-?) hyperconjugative interactions and OH ··· Cl- hydrogen-bonding interactions lead to the formation of 1-D zigzag tetrameric complexes consisting of four chlorides bridged by four waters. Two oxygens of the bridging waters are also coordinated to Cl- of the complex forming a parallelogram-shaped ring. Two chlorides are also anchored by NH ··· Cl- hydrogen bonds in the free space between four tetrameric complexes. Heating 1 at 100°C for 4 h does not remove lattice water and the framework structure is retained. In 2, NH ··· Br- hydrogen-bonding interactions stabilize the supramolecular architecture. In this case, however, only two bromides are bridged by one water through OH ··· Br- hydrogen bonds. The supramolecular interactions existing in the crystal packing of the ionic salts have been analyzed at the density functional theories and ab initio CCSD(T) levels of the theory

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Contributors

Author: M. E. Light

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