Can halogen bond energy be reliably estimated from electron density properties at bond critical point? The case of the (A)_nZ—Y•••X⁻(X, Y = F, Cl, Br) interactions

Abstract

Relationships between the Y•••X bond critical point (BCP) properties or the Y•••X distance and the halogen bond interaction energy were analyzed in detail by theoretical methods for the series of structures [(A)nZ—Y•••X]− (X,Y = F, Cl, Br; totally 441 structures). No relationship was found for the whole set of structures or for the series [(A)nZ—F•••X]−, [(A)nZ—Cl•••X]−, and [(A)nZ—Br•••X]−. The interaction energies may be roughly estimated from the BCP properties for the series [(A)nZ—Y•••F]−, [(A)nZ—Y•••Cl]−, and [(A)nZ—Y•••Br]− as well as for [(A)nZ—Y•••X]− (when (A)nZ is variable, X and Y are constant) with the mean absolute deviation values 2.04‐4.38 kcal/mol. The corresponding recommended relationships are provided and they are significantly different from the popular dependencies deduced previously for other types of noncovalent interactions. Tremendous effect of the computational method and basis set on the relationships under analysis was discovered. Computational results clearly indicate that, for practical purposes, the Eint(BCP property) dependencies should be established not simply for each global type of interactions (hydrogen bond, halogen bond, chalcogen bond, etc.) but for each combination of the first and second order atoms taking into account also the computational method and basis set.

Identification of the Tetrel Bonds between Halide Anions and Carbon Atom of Methyl Groups Using Electronic Criterion

“…This finding has been discussed by us earlier for the halogen bonds formed by different atoms or fragments that play the role of halogen acceptors [45]. This fact has recently been illustrated in detail in Reference [46], where the large series of non-covalent interactions with different halide anions have been studied.…”

Relationships between Interaction Energy and Electron Density Properties for Homo Halogen Bonds of the [(A)nY–X···X–Z(B)m] Type (X = Cl, Br, I)

“…It was shown by Kozuch and Martin [95] for a set of 51 structures bearing XBs that the root-mean-square deviation, the mean signed error, and the maximum error of dissociation energy for M06-2X are 0.43, 0.01, and 1.58 kcal/mol, respectively, relative to the CCSD(T) method. Additionally, it was shown [92] that the E int (V b ) correlation for structures of the [(A) n Z–Y···F] − type (Y = F, Cl, Br) at the M06-2X level of theory has similar parameters as that for the MP4, CCSD, and CCSD(T) methods (see Figure 7A in [90]).…”

“…Since the publication of the EML formula, numerous but usually not justified attempts to apply this relationship to different types of non-covalent interactions were undertaken. However, it was shown that these equations may not be universal, and their validity may be restricted only to the type of interactions for which they were deduced [91,92]. Thus, there is a great practical need to establish the reliable E int (property) relationships for the most important types of non-covalent interactions others than the X–H···O, FH···FR, and Y–Hal···Z(B) m ones.…”

“…Recently, the author started the project aimed to establish the E int (property) relationships for various types of non-covalent interactions. In the first publication of this research cycle [92], the halogen bonds of the [(A) n Z–Y···X] − type (X, Y = F, Cl, Br; Z = F, Cl, Br, I, C, N, O, H, S, P, Si, B, totally 441 structure) formed upon interaction of the neutral fragment (A) n Z–Y and the halide anion X − were considered. It was shown that the E int (property) correlations are different for each particular type of the Y···X − interaction and they are also different from Equations (1)–(4).…”

Molecular Structures Polymorphism the Role of F…F Interactions in Crystal Packing of Fluorinated Tosylates

“…According to Reference [41] EML formula in most cases underestimated the energy of intermolecular interactions by substantial amount as compared to the method implemented to CrystalExplorer program (CE-B3LYP). Severe judgement about EML correlation were expressed in the paper by Kuznetsov [42]. On the other hand, according to other published articles the lattice energies calculated from EML correlation provided reasonable values that agreed with experimental sublimation heat [43][44][45].…”