TY - JOUR

T1 - Metal-Involving Halogen Bonding Confirmed Using DFT Calculations with Periodic Boundary Conditions

AU - Елисеева, Анастасия Александровна

AU - Иванов, Даниил Михайлович

AU - Алиярова, Ирина Сергеевна

AU - Хазанова, Марина Александровна

AU - Черанёва, Анна Михайловна

PY - 2023/4/22

Y1 - 2023/4/22

N2 - The cocrystallization of trans-[PtI2(NCN(CH2)5)2] and iodoform (CHI3) yields crystalline adduct trans-[PtI2(NCN(CH2)5)2]∙2CHI3, the structure of which was studied via single-crystal X-ray diffractometry (XRD). In the XRD structure of trans-[PtI2(NCN(CH2)5)2]∙2CHI3, 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 dz2-orbital) toward the σ-holes of I atoms of CHI3. 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.

AB - The cocrystallization of trans-[PtI2(NCN(CH2)5)2] and iodoform (CHI3) yields crystalline adduct trans-[PtI2(NCN(CH2)5)2]∙2CHI3, the structure of which was studied via single-crystal X-ray diffractometry (XRD). In the XRD structure of trans-[PtI2(NCN(CH2)5)2]∙2CHI3, 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 dz2-orbital) toward the σ-holes of I atoms of CHI3. 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.

KW - CP2K

KW - dialkylcyanamides

KW - halogen bonding

KW - iodoform

KW - periodic calculations

KW - platinum(II)

UR - https://www.mdpi.com/2073-4352/13/5/712

UR - https://www.mendeley.com/catalogue/893b3b56-86b3-331c-bc65-82e9957cb40a/

U2 - 10.3390/cryst13050712

DO - 10.3390/cryst13050712

M3 - Article

VL - 13

JO - Crystals

JF - Crystals

SN - 2073-4352

IS - 5

M1 - 712

ER -