Vanadium-Containing Anionic Chelate for Spectrophotometric Determination of Hydroxyzine Hydrochloride in...

Four azo dyes known to form anionic complexes with V(V) were investigated as potential liquid-liquid extraction-spectrophotometric reagents for the antihistamine medication hydroxyzine hydrochloride (HZH). A stable ion-association complex suitable for analytical purposes was obtained with 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR). The molar absorption coefficient, limit of detection, linear working range, and relative standard deviation in the analysis of real pharmaceutical samples (tablets and syrup) were 3.50 × 10⁴ L mol^-1 cm^-1, 0.13 μg mL^-1, 0.43-12.2 μg mL^-1, and ≤2.7%, respectively. After elucidating the molar ratio in the extracted ion-association complex (HZH:V = 1:1), the ground-state equilibrium geometries of the two constituent ions-HZH⁺ and [VO₂(HTAR)]^--were optimized at the B3LYP level of theory using 6-311++G** basis functions. The cation and anion were then paired in four different ways to find the most likely structure of the extracted species. In the lowest-energy structure, the VO₂ group interacts predominantly with the heterochain of the cation. A hydrogen bond is present (V-O···H-O; 1.714 Å) involving the terminal oxygen of this chain.