Conformation preference and related intramolecular noncovalent interaction of selected short chain chlorinated paraffins

Short chain chlorinated paraffins (SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions (NCIs). A systematic study was conducted to reveal the conformation preference and the related intramolecular NCIs in two C 10 -isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-tetrachlorodecane. The overall conformation profile was determined on the basis of relative energies calculated at the MP2/6-311++G(d,p) level with the geometries optimized by B3LYP/6-311++G(d,p) method. Then, quantum theory of atoms in molecules (QTAIM) has been adopted to identify the NCIs in the selected conformers of the model molecules at both B3LYP/6-311++G(d,p) and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed for the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane (tTt) has its three dihedral angles in the T configuration, and there is no intramolecular NCIs found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configuration for the H–C–C–Cl axis. Not only intramolecular H···Cl contacts but also H···H interactions have been identified as driving forces to compensate the instability from steric crowding of the gauche configuration. The gggg and g′g′g′g′ conformers are the most popular ones, while the populations of tggg and tg′g′g′ conformer are second to those of the gggg and g′g′g′g′ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.