Structure, Morphology and Optical Properties of Chiral N-(4-X-phenyl)-N-[1(S)-1-phenylethyl]thiourea, X= Cl, Br, and NO2

Abstract

Three new enantiopure aryl-thioureas have been synthesized, N-(4-X-phenyl)-N-[1(S)-1-phenylethyl]thiourea, X= Cl, Br, and NO2 (compounds 1-3, respectively). Large single crystals of up to 0.5 cm3 were grown from methanol/ethanol solutions. Molecular structures were derived from X-ray diffraction studies and the crystal morphology was compared to calculations employing the Bravais-Friedel, Donnay-Harker model. Molecular packing was further studied with Hirshfeld surface calculations. Semi-empirical classical model calculations of refractive indices, optical rotation and the electro-optic effect were performed with OPTACT on the basis of experimentally determined refractive indices. Compound 3 (space group P 1 (No. 1)) was estimated to possess a large electro-optic coefficient r333 of approximately 30 pm/V, whereas 1 and 2 (space Group P 21 (No. 4) exhibit much smaller effects.

Enantiopure (S)-butan-2-yl N-(4-x-phenyl)thiocarbamates, x = NO2, OCH3, F, and Cl

“…The number drops considerably, to 93, in a search for 'ring synthon in phenylthiocarbamates'. 'Ring synthon in chiral phenylthiocarbamates' yields only one reasonable result, already included here (Kaminsky et al, 2010).…”

“…This research is part of an undergraduate study into creating new chiral model compounds from reacting a chiral moiety with another molecule to combine specific features of both. Initially, isothiocyanates were reacted with -methylbenzylamine to form chiral thiourea derivatives (Kaminsky et al, 2010), whereas here, the poisonous isothiocyanates were reacted with (S)-2-butanol to form thiocarbamates with possible protein-docking capability (Bull & Breese, 1978;Du et al 2020). Specifically, (S)-butan-2-yl-N-(4-x-phenyl)thiocarbamates were synthesized from enantiopure (S)-2-butanol and 4-x-phenylisothiocyanate, x = NO 2 , OCH 3 , F, and Cl.…”

Electronic Structure, Optical, and Elastic Properties of AgGaS2 Crystal: Theoretical Study

“…DES model of calculations is based on classical polarizability theory of optical activity [36] and can be successfully applied to determine the parameters of electrogyration, electro-optic, and second-harmonic generation effects. [37] There are many results of validation of the DES approach (see, e.g., [37][38][39][40] ).…”

Optical Activity of Langatate Crystals

“…It should be noticed that the calculation method described in the work [7] could be applied to inorganic molecular and ionic crystals and it is valid only for the visible spectral region where there is no absorption and no linear or circular dichroism edges. In particular, the calculations based on this method have been successfully extended to determine the parameters of electrogyration, electrooptic and second-harmonic generation effects, using the model called as Dipole Electron Shifting (DES) [10][11][12][13]. In general, the calculations need correct and very precise data on the crystalline structure (i.e., the coordinates r S of the S atoms in the crystalline lattice) and the electronic polarizabilities α S of the individual atoms (e. g., the electronic polarizability volume…”

“…This is because the calculation technique suggested in the work [7] is rather simple and purely classical. It has been successfully utilized in the crystal optical studies [9][10][11][12][13] and, in particular, for Ca 3 Ga 2 Ge 4 O 14 (CGG), Sr 3 Ga 2 Ge 4 O 14 (SGG), La 3 Ga 5 SiO 14 (LGS), La 3 Ga 5 GeO 14 (LGG), La 3 Ga 5.5 Nb 0.5 O 14 (LGN) langasite family crystals [14] For this reason we have chosen the method for calculating optical parameters of the langatate compound.…”