Metal-Involving Halogen Bonding Confirmed Using DFT Calculations with Periodic Boundary Conditions
oleh: Anastasiya A. Eliseeva, Marina A. Khazanova, Anna M. Cheranyova, Irina S. Aliyarova, Roman I. Kravchuk, Evfpraksiia S. Oganesyan, Andrey V. Ryabykh, Olga A. Maslova, Daniil M. Ivanov, Serge A. Beznosyuk
| Format: | Article |
|---|---|
| Diterbitkan: | MDPI AG 2023-04-01 |
Deskripsi
The cocrystallization of <i>trans</i>-[PtI<sub>2</sub>(NCN(CH<sub>2</sub>)<sub>5</sub>)<sub>2</sub>] and iodoform (CHI<sub>3</sub>) yields crystalline adduct <i>trans</i>-[PtI<sub>2</sub>(NCN(CH<sub>2</sub>)<sub>5</sub>)<sub>2</sub>]∙2CHI<sub>3</sub>, the structure of which was studied via single-crystal X-ray diffractometry (XRD). In the XRD structure of <i>trans</i>-[PtI<sub>2</sub>(NCN(CH<sub>2</sub>)<sub>5</sub>)<sub>2</sub>]∙2CHI<sub>3</sub>, apart from rather predictable C–H∙∙∙I hydrogen bonds (HBs) and C−I∙∙∙I halogen bonds (XBs) with the iodide ligands, we identified C–I∙∙∙Pt metal-involving XBs, where the platinum center functions as an XB acceptor (that includes a metal <i>d</i><sub>z</sub><sup>2</sup>-orbital) toward the σ-holes of I atoms of CHI<sub>3</sub>. DFT calculations (PBE-D3/jorge-TZP-DKH with plane waves in the GAPW method) were carried out in the CP2K program for isolated molecules, complex–iodoform clusters, and crystal models with periodic boundary conditions, where the noncovalent nature and the existence of the interactions were confirmed using charge analysis, Wiberg bond indexes, and QTAIM topology analysis of electron density, whereas the philicities of the noncovalent partners were proved using charge analysis, electron localization function, electron density deformation, and one-electron potential projections, as well as electron density/electrostatic potential profiles for cluster models and electrostatic potential surfaces (ρ = 0.001 a.u.) for isolated molecules.