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. 2021 May 23;26(11):3119.
doi: 10.3390/molecules26113119.

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

Sergey V Baykov  1 , Artem V Semenov  2   3 , Eugene A Katlenok  1 , Anton A Shetnev  4 , Nadezhda A Bokach  1
Affiliations

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

Sergey V Baykov et al. Molecules. .

Abstract

Structures of three tetrahalophthalic anhydrides (TXPA: halogen = Cl (TCPA), Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair···π-hole (lp···πh) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X···O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the π system (π-hole) of the anhydride ring (further lp(O)···πh) were observed. Computational studies by a number of theoretical methods (molecular electrostatic potentials, the quantum theory of atoms in molecules, the independent gradient model, natural bond orbital analyses, the electron density difference, and symmetry-adapted perturbation theory) demonstrated that the X···O(anhydride) contacts in TCPA and TBPA and lp(O)···πh in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X···O(acyl) and X···X HaBs, and, for TIPA, the main contribution provided I···I HaBs.

Keywords: X-ray diffraction studies; computational studies; halogen bond; noncovalent interactions; tetrahalophthalic anhydrides.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
Structures of tetrahalophthalic anhydrides.
Figure 2
Figure 2
Types of X···O contacts in the structures of TXPA.
Figure 3
Figure 3
HaB in crystals of (a) TCPA and (b) TBPA.
Figure 4
Figure 4
Noncovalent interactions in a crystal of TIPA.
Figure 5
Figure 5
MEP surface in tetrahalophthalic anhydrides at the PBE0-D3BJ/ZORA-def2-TZVP level of theory-optimized structures (isosurface 0.001 a.u.; kcal/mol). The color scheme was taken from Politzer’s work [47,48].
Figure 6
Figure 6
The sign(λ2)ρb(r) function mapped on the δginter isosurface for the TCPA and TIPA (δginter = 0.006 a.u. and blue-cyan-green-yellow-red color scale −0.05 < sign(λ2)ρb(r) < 0.05). QTAIM distribution of bond critical points (red) and bond paths.
Figure 7
Figure 7
EDD maps for tetrahalophthalic anhydrides. Electrons transfer from the electron density decreased regions (blue) to increased regions (red). The isovalues EDD maps: TCPAF1 and TBPAF1 0.00015; TCPAF2, TBPAF2 TIPAF1, TIPAF2 0.0005; TCPAF3, TBPAF3, TIPAF3 0.0003.
Figure 8
Figure 8
Decomposition interaction energies of bimolecular fragments tetrahalophthalic anhydrides. Bar color corresponds to the percentage of each stabilizing contribution (Eelst + Eind + Edis = 100%). R is the interatomic distance to ΣRvdW ratio. Eint represents the interaction energies (kcal/mol).
Figure 9
Figure 9
X-ray and optimized structures.
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