Lu, Huangjie Wang, Yaxing Wang, Congzhi Chen, Lanhua Shi, Weiqun Diwu, Juan Chai, Zhifang Albrecht-Schmitt, Thomas E. Wang, Shuao Two-Dimensional Inorganic Cationic Network of Thorium Iodate Chloride with Unique Halogen–Halogen Bonds A unique two-dimensional inorganic cationic network with the formula [Th<sub>3</sub>O<sub>2</sub>(IO<sub>3</sub>)<sub>5</sub>(OH)<sub>2</sub>]Cl was synthesized hydrothermally. Its crystal structure can best be described as positively charged slabs built with hexanuclear thorium clusters connected by iodate trigonal pyramids. Additional chloride anions are present in the interlayer spaces but surprisingly are not exchangeable, as demonstrated by a series of CrO<sub>4</sub><sup>2–</sup> uptake experiments. This is because all chloride anions are trapped by multiple strong halogen–halogen interactions with short Cl–I bond lengths ranging from 3.134 to 3.333 Å, forming a special Cl-centered trigonal-pyramidal polyhedron as a newly observed coordination mode for halogen bonds. Density functional theory calculations clarified that electrons transformed from central Cl atoms to I atoms, generating a halogen–halogen interaction energy with a value of about −8.3 kcal mol<sup>–1</sup> per Cl···I pair as well as providing a total value of −57.9 kcal mol<sup>–1</sup> among delocalized halogen–halogen bonds, which is a new record value reported for a single halogen atom. Additional hydrogen-bonding interaction is also present between Cl and OH, and the interaction energy is predicted to be −8.1 kcal mol<sup>–1</sup>, confirming the strong total interaction to lock the interlayer Cl anions. Cationic Network;IO 3;halogen bonds;mol;OH;Cl atoms;halogen atom;theory calculations;record value;Additional hydrogen-bonding interaction;kcal;cationic network;Thorium Iodate Chloride;Additional chloride anions;interlayer Cl anions;coordination mode;Th 3 O 2;crystal structure;interlayer spaces;chloride anions;Cl-centered trigonal-pyramidal polyhedron;interaction energy;hexanuclear thorium clusters 2016-08-05
    https://acs.figshare.com/articles/dataset/Two-Dimensional_Inorganic_Cationic_Network_of_Thorium_Iodate_Chloride_with_Unique_Halogen_Halogen_Bonds/3544739
10.1021/acs.inorgchem.6b01110.s001