Combined theoretical and experimental studies on the molecular structure, spectral and Hirshfeld surface studies of NLO tris(thiourea)zinc(II) sulfate crystals

• Experimental studies on ZTS are supported by theoretical calculation.
• Intermolecular hydrogen bond interaction revealed by Hirshfeld surface analysis.
• First-order molecular hyperpolarizability is estimated.

Transparent single crystals of tris(thiourea)zinc(II) sulfate (ZTS) were grown by slow evaporation technique at room temperature from an aqueous solution containing zinc sulfate and thiourea in the molar ratio 1:3. The experimental and theoretical studies on the molecular structure and vibrational spectra of ZTS were investigated by single crystal X-ray diffraction, FT-IR and density functional theory (DFT). The recorded X-ray diffraction bond parameters are compared with theoretical values calculated at B3LYP/LANL2DZ level. The observed vibrational patterns were compared with the computed wave numbers. The energy and oscillator strength calculated by TD-DFT results complement with the experimental findings. The first-order molecular hyperpolarizability, polarizability, dipole moment and HOMO–LUMO band gap energies were derived. The molecular stability and bond strength were investigated by applying the natural bond orbital analysis (NBO). Information about the size, shape, charge density distribution and site of chemical reactivity of the molecule has been obtained by mapping electron density with molecular electrostatic potential (MEP) using the same level of basis set. Intermolecular hydrogen bonding was investigated by means of the Hirshfeld surfaces, and the role of the NH⋯O interactions as driving force for crystal structure formation has been demonstrated. The percentages of hydrogen bonding interactions are analyzed by Fingerprint plots of Hirshfeld surface.

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