Assembly of two new hybrid chloride materials with potential NLO properties: Structure elucidation, empirical and computational studies

Abstract

This paper deals with the crystal structure of two new non-centrosymmetric hybrid compounds obtained from an aqueous solution by slow evaporation method and characterized by various techniques mainly single-crystal X-ray diffraction. In the atomic arrangement of 2-methylbenzylammonium chloride (1), the organic cations and the chloride anions are linked to each other via N–H…Cl hydrogen bonds; organic cations in zigzag distribution along b-axis in z = 0 and z = ½ are also close enough to enable a C–H…π interaction to occur. In 3-methylbenzylammonium chloride (2), the organic cations are linked together by C–H…π interactions and through N–H…Cl and C–H…Cl hydrogen bonds to form a two-dimensional network. To support experimental results, DFT calculations have been accomplished via the B3LYP method and 6-311++G(d,p) basis set on molecular geometry, vibrational, and electronic properties. The non-covalent interactions were studied quantitatively using the Hirshfeld surfaces (HS) associated with 2D fingerprint plots. The NLO properties have been also investigated by DFT and compared to the urea reference.