Crystal structures and theoretical investigation of anti-/syn-2,4-diphenylpentane- and 2,4-di-p-tolylpentane-2,4-diols

Abstract

2,4-diphenylpentane- and 2,4-di-p-tolylpentane-2,4-diols were investigated employing experimental and density functional theory (DFT) method at B3LYP/6-31G (d) level. The structure of syn-2,4-di-p-tolylpentane-2,4-diol (2b) was characterized by X-ray diffraction and compared with the crystal structures of anti- and syn-2,4-diphenylpentane-2,4-diols (1a and 1b). X-ray diffraction indicates that inter and intra-molecular hydrogen bonds are formed in the crystal structures. There is π-π staking interaction in 1b and 2b. Good linear correlations and similar results are found between the experimental ¹H and ¹³C NMR chemical shifts (δ_exp) and GIAO (Gauge Independent Atomic Orbital) method calculated magnetic isotropic shielding tensors (δ_calc). HOMO and LUMO molecular orbitals were calculated at the same levels with the different results. UV-vis absorption spectra of the compounds were recorded in EtOH, MeCN, n-BuOH and cyclohexane with different dielectric constants. It is found that the solvent effect is obvious when ɛ is 24.85(EtOH), 35.69(MeCN) and it is weak when ɛ is decreased to 17.33(n-BuOH), 1.18 (cyclohexane).

Keywords

X-ray crystallography / hydrogen bonds / nuclear magnetic resonance (NMR) / density function theory (DFT) / UV-vis absorption / solvent effect

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