Comparison of N···I and N···O Halogen Bonds in Organoiodine Cocrystals of Heterocyclic Aromatic Diazine Mono-N-oxides

Abstract

A series of cocrystals of halogen bond donors 1,4-diiodotetrafluorobenzene (p-F4DIB) and tetraiodoethylene (TIE) with five aromatic heterocyclic diazine mono-N-oxides based on pyrazine, tetramethylpyrazine, quinoxaline, phenazine, and pyrimidine as halogen bonding acceptors were studied. Structural analysis of the mono-N-oxides allows comparison of the competitive occurrence of N···I vs O···I interactions and the relative strength and directionality of these two types of interactions. Of the aromatic heterocyclic diazine mono-N-oxide organoiodine cocrystals examined, six exhibited 1:1 stoichiometry, forming chains that utilized both N···I and O···I interactions. Two cocrystals presented 1:1 stoichiometry with exclusive O···I interactions. Two cocrystals displayed a 2:1 stoichiometryone characterized solely by O···I interactions and the other solely by N···I interactions. We have also compared these interactions to those present in the corresponding diazines, some of which we report here and some which have been previously reported. In addition, a computational analysis using density functional theory (M062X/def2-SVPD) was performed on these two systems and has been compared to the experimental results. The calculated complex formation energies were, on average, 4.7 kJ/mol lower for the I···O halogen bonding interaction as compared to the corresponding N···I interaction. The average I···O interaction distances were calculated to be 0.15 Å shorter than the corresponding I···N interactions.

eutXG: A Machine-Learning Model to Understand and Predict the Melting Point of Novel X-Bonded Deep Eutectic Solvents

“…In the interest of expanding the DES predictive capabilities of eut XG applications, we sought to challenge the system with previously unexplored chemical systems. It is important to note that our own studies of halogen bonding have focused on cataloging supramolecular synthons involving a wide variety of halogen-bonding acceptors. ,, This led to the identification of the first example of a X-DES, composed of 1,3-dithiane and 1,2-diiodotetrafluorobenzene, corresponding to an analogue of the Type V system . Others have begun computational investigations into trihalide-based DES, with experimental data in some systems indicating low MPs that may, if compared to ideality, warrant classification as DES .…”