Crystal structural characterization of three chlorosalicylato titanocene compounds

Abstract

Three chlorosalicylato titanocene compounds, namely [(MeCp)₂Ti(O,O′)(OCC₆H₃-5-Cl)]₂ (1), [(MeCp)₂Ti(O,O′)(OCC₆H₂-3,5-Cl₂)] (2) and [(MeCp)₂Ti(O,O′)(OCC₆H-3,5,6-Cl₃)] (3) have been synthesized via the reaction of (MeCp)₂TiCl₂ [MeCp = η⁵-(CH₃)C₅H₄] with the corresponding substituted chlorosalicylic acids in aqueous-organic systems in high yields and characterized by elemental analysis, IR and ¹H NMR spectra. Single-crystal X-ray diffraction analysis shows that geometries at titanium (IV) atoms are distorted tetrahedrons and the exhibited frameworks are constructed through weak interactions, which are H-bonding, π–π stacking and C–H···π interactions. Additional weak interactions, such as Cl···Cl interactions in compound 1, are also present, which help to form and stabilize crystalline materials. It is noticeable that the discriminating framework structures of three compounds due to their weak interactions existing conspicuous changes which result from the number of chlorine atoms on substituted chlorosalicylates.

Graphical Abstract

Three to four coordinated chlorosalicylato titanocene compounds, [(MeCp)₂Ti(O,O′)(OCC₆H₃-5-Cl)]₂ (1), [(MeCp)₂Ti(O,O′)(OCC₆H₂-3,5-Cl₂)] (2) and [(MeCp)₂Ti(O,O′)(OCC₆H-3,5,6-Cl₃)] (3) have been synthesized in aqueous-organic system in high yields. Single-crystal X-ray diffraction analysis shows that geometries at titanium (IV) atoms are distorted tetrahedrons and the exhibited frameworks are constructed through weak interactions. The number of chlorine atoms on substituted chlorosalicylates has an effect on their framework structures.