Kryukova Mariya A, Kostareva Margarita B, Cheranyova Anna M, Khazanova Marina A, Rozhkov Anton V, Ivanov Daniil M
Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., Saint Petersburg 199034, Russia.
Int J Mol Sci. 2025 May 9;26(10):4555. doi: 10.3390/ijms26104555.
The cocrystallization of -[PtI(NCR)] (R = NMe, NEt, Ph , o-ClCH) with iodine and iodoform gave the crystalline adducts ∙4I, ∙2CHI, ∙2CHI, and ∙4I, whose structures were studied by single-crystal X-ray diffractometry (XRD). In the structures, apart from the rather predictable C-H⋯I hydrogen bonds (HBs) and I-I⋯I or C-I⋯I halogen bonds (XBs) with the iodide ligands, we identified bifurcated I-I⋯(I-Pt) and C-I⋯(I-Pt) metal-involving XBs, where the platinum center and iodide ligands function as simultaneous XB acceptors toward σ-holes of I atoms in I or CHI. Appropriate density functional theory (DFT) calculations (PBE-D3/jorge-DZP-DKH with plane waves in the GAPW method) performed with periodic boundary conditions confirmed the existence of the bifurcated metal-involving I-I⋯(I-Pt) and C-I⋯(I-Pt) interactions and their noncovalent nature.
-[PtI(NCR)]（R = NMe、NEt、Ph、o-ClCH）与碘和碘仿的共结晶得到了晶体加合物∙4I、∙2CHI、∙2CHI和∙4I，其结构通过单晶X射线衍射法（XRD）进行了研究。在这些结构中，除了与碘化物配体形成的相当可预测的C-H⋯I氢键（HBs）和I-I⋯I或C-I⋯I卤键（XBs）外，我们还确定了分叉的I-I⋯(I-Pt)和C-I⋯(I-Pt)涉及金属的XBs，其中铂中心和碘化物配体同时作为XBs受体，朝向I或CHI中I原子的σ-空穴。在周期性边界条件下进行的适当密度泛函理论（DFT）计算（采用GAPW方法中的平面波的PBE-D3/jorge-DZP-DKH）证实了分叉的涉及金属的I-I⋯(I-Pt)和C-I⋯(I-Pt)相互作用的存在及其非共价性质。
