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

doi:10.1016/j.molstruc.2015.02.085

Journal of Molecular Structure

Volume 1091, 5 July 2015, Pages 210-221

https://doi.org/10.1016/j.molstruc.2015.02.085 Get rights and content

Highlights

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

Abstract

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 N single bond H⋯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.

Graphical abstract

Introduction

The nonlinear optical (NLO) properties of metal complexes of thiourea have fascinated substantial attention in the last few years. In general, the presence of π-electron delocalization in the molecular structure is found to enhance NLO properties. Thiourea is capable of forming coordinate bonds through sulfur with various metals, and many of them possessing NLO activities and some of them centrosymmetric in nature. Tris(thiourea)zinc(II) sulfate is a semiorganic NLO material which finds applications in the area of laser technology, optical communication, data storage technology and optical computing because it has high resistance to laser induced damage, high nonlinearity, wide transparency, low angular sensitivity and good mechanical hardness compared to many organic NLO crystals [1], [2], [3], [4]. It belongs to the orthorhombic system with noncentrosymmetric space group Pca2₁ (four molecules in the unit cell) and point group mm2. The crystal structure, growth, kinetics, morphology, Z-scan study, high pressure electrical resistivity, neutron diffraction study, doping studies and second harmonic generation (SHG) efficiency on ZTS have been extensively studied [5], [6], [7], [8], [9], [10], [11], [12], [13], [14], [15], [16], [17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28], [29], [30], [31], [32], [33], [34], [35], [36], [37], [38], [39], [40], [41], [42].

Recently, we have investigated the effect of doping on the growth and properties of ZTS [23], [24], [25], [26], [27], [28], [29], [30], [31], [32], [33]. The molecular structure, spectroscopic (FT-IR, FT Raman, UV–vis), NBO, thermochemical analysis of bis(thiourea)zinc(II) chloride crystals [43] and crystal growth, characterization and theoretical studies of alkaline earth metal-doped tetrakis(thiourea)nickel(II) chloride [44] have been reported from our laboratories. As far as we know, there is no reference in literature regarding the theoretical calculations on ZTS. As a continuation, the molecular structure, FT-IR and UV–vis spectral analyses of ZTS have been performed using B3LYP/LANL2DZ level of theory and the results are compared with experimental findings. The UV spectroscopic studies along with molecular frontier orbital energies (HOMO and LUMO), electronegativity (χ), chemical hardness (η), softness (S), molecular electrostatic potential maps were also derived.

Section snippets

Synthesis and crystal growth

ZTS was synthesized as reported earlier [23] and the crystals are grown by slow evaporation technique from an aqueous solution. High quality and transparent crystals were harvested after a period of 15–20 days (Fig.S1, see in supplementary data).

Characterization studies

The structural analysis of ZTS was carried out for a selected colorless tablet of approximately 0.30 × 0.20 × 0.20 mm³ using Bruker AXS (Kappa Apex II) X-ray diffractometer. The structure was solved and refined by SHELXS97 [45]. Fourier transform infrared

Molecular geometry

The structural analysis of ZTS was carried out by single crystal XRD analysis. The molecular structure (Fig. 1a) and crystal packing diagram (Fig. 1b) are given. Analysis of the geometry of molecules in the crystal suggests that the strongest interactions responsible for the packing of the molecules in the crystal lattice of ZTS are the H single bond O⋯H (along b–c axis) and NH⋯O (along b axis) intermolecular hydrogen bonds showing supramolecular frameworks (Fig. 2). It crystallizes in the orthorhombic

Conclusions

Transparent trigonal-shape single crystals of tris(thiourea)zinc(II) sulfate were grown and characterized by single crystal XRD, FT-IR and UV–vis analyses. The observed geometrical parameters coincide well with the calculated parameters. The theoretically obtained FT-IR spectrum resembles the experimental pattern and the results are in close agreement. The powder X-ray diffraction study reveals the structure and crystallinity of the grown crystal and simulated pattern coincides with

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

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis and crystal growth

Characterization studies

Molecular geometry

Conclusions

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