Structural, Hirshfeld Surface Analysis, Morphological Approach, and Spectroscopic Study of New Hybrid Iodobismuthate Containing Tetranuclear 0D Cluster Bi₄I₁₆·4(C₆H₉N₂) 2(H₂O)

• Main Author: Hela Ferjani
• Format: Article
• Language: English
• Published: MDPI AG 2020-05-01
• Series: Crystals
• Subjects: iodobismuthate; tetranuclear cluster; 1-allylimidazole; crystal morphology; Hirshfeld surface analysis; infrared and Raman spectroscopy
• Online Access: https://www.mdpi.com/2073-4352/10/5/397

The Bi₄I₁₆·4(C₆H₉N₂) 2(H₂O) compound was synthesized by slow evaporation at room temperature. It exhibits a zero-dimensional (0D) tetrameric structure, comprising [Bi₄I₁₆]⁴⁻ distorted octahedra, with strong I⋯I interactions among adjacent anionic clusters. We used Hirshfeld surface analysis to discuss the strength of hydrogen bonds and to quantify the inter-contacts (two-dimensional (2D) fingerprint plots). It revealed that the hydrogen bonding interactions H⋯I (56.3%), π–π stacking (11.7%), and I⋯I interactions (5.9%) play the major role in the stability of the crystal structure. The crystal morphology was simulated using Bravais–Friedel, Donnay–Harker (BFDH) and growth morphology (GM) methods. The experimental habit of the title compound was adequately reproduced by the two models. The calculated results show that the crystal morphology of the title compound in a vacuum is dominated by five facets: (020), (011), (110), (10−1), and (11−1). The (020) facet is the largest among all the facets calculated. Projection of the facet showed that there are a few polar groups on the (020) facet. In the 50–400 and 400–4000 cm⁻¹ frequency regions, we measured the Raman and infrared spectra, respectively, of the title compound, and we assigned the observed vibration modes.