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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. [ABSTRACT FROM AUTHOR]

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.

The reaction in the system CuII/sacNa(H)/NCNR2 (sacNa(H) = sodium saccharinate (saccharin); R = Me, Et) results in the formation of the complexes [Cu(sac)2(NCNR2)(H2O)2] (R = Me 1, Et 2) instead of the expected products derived from the saccharin–cyanamide coupling. Complexes 1, 2, and hydrate 1·2H2O were characterized by IR, AAS (Cu%), TGA, and also by single-crystal X-ray diffraction for 1 and 1·2H2O. An integrated computational study of model structure 1 in the gas phase demonstrates that the Cu–Ncyanamide and Cu–Nsac coordination bonds exhibited a single bond character, polarized toward the N atom and almost purely electrostatic, with the calculated vertical total energies for the Cu–Ncyanamide and Cu–Nsac of 43.6 and 156.4 kcal/mol, respectively. These data confirmed that the copper(II) completely blocks the nucleophilic centers of ligands via coordination, thus preventing the saccharin–cyanamide coupling.

The complexes trans-[PtBr2(NCNR2)2] (R2 = Me21, (CH2)52) were cocrystallized with 1,1,2,2-tetrabromoethane (tbe) in CH2Cl2 forming solvates 1·tbe and 2·tbe, respectively. In both solvates, tbe involved halogen bonding, viz. the C–Br···Br–Pt interactions, were detected by single-crystal X-ray diffractions experiments. Appropriate density functional theory calculations (M06/def2-TZVP) performed for isolated molecules and complex-tbe clusters, where the existence of the interactions and their noncovalent nature were confirmed by electrostatic potential surfaces (ρ = 0.001 a.u.) for isolated molecules, topology analysis of electron density, electron localization function and HOMO-LUMO overlap projections for clusters.

The reaction in the system CuII/sacNa(H)/NCNR2 (sacNa(H) = sodium saccharinate (saccharin); R = Me, Et) results in the formation of the complexes [Cu(sac)2(NCNR2)(H2O)2] (R = Me 1, Et 2) instead of the expected products derived from the saccharin–cyanamide coupling. Complexes 1, 2, and hydrate 1·2H2O were characterized by IR, AAS (Cu%), TGA, and also by single-crystal X-ray diffraction for 1 and 1·2H2O. An integrated computational study of model structure 1 in the gas phase demonstrates that the Cu–Ncyanamide and Cu–Nsac coordination bonds exhibited a single bond character, polarized toward the N atom and almost purely electrostatic, with the calculated vertical total energies for the Cu–Ncyanamide and Cu–Nsac of 43.6 and 156.4 kcal/mol, respectively. These data confirmed that the copper(II) completely blocks the nucleophilic centers of ligands via coordination, thus preventing the saccharin–cyanamide coupling. [ABSTRACT FROM AUTHOR]

The complexes trans-[PtBr2(NCNR2)2] (R2 = Me21, (CH2)52) were cocrystallized with 1,1,2,2-tetrabromoethane (tbe) in CH2Cl2 forming solvates 1·tbe and 2·tbe, respectively. In both solvates, tbe involved halogen bonding, viz. the C–Br···Br–Pt interactions, were detected by single-crystal X-ray diffractions experiments. Appropriate density functional theory calculations (M06/def2-TZVP) performed for isolated molecules and complex-tbe clusters, where the existence of the interactions and their noncovalent nature were confirmed by electrostatic potential surfaces (ρ = 0.001 a.u.) for isolated molecules, topology analysis of electron density, electron localization function and HOMO-LUMO overlap projections for clusters. [ABSTRACT FROM AUTHOR]