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Crystals 2017, 7(7), 225;

The Interplay between Various σ- and π-Hole Interactions of Trigonal Boron and Trigonal Pyramidal Arsenic Triiodides

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nam. 2, 166 10 Prague 6, Czech Republic
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice, Czech Republic
Institute of Inorganic Chemistry of the Czech Academy of Sciences, v.v.i. 250 68 Husinec-Řež, Czech Republic
Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Palacký University, Olomouc, 771 46 Olomouc, Czech Republic
These authors contributed equally to this work.
Authors to whom correspondence should be addressed.
Academic Editors: Peter Politzer and Jane S. Murray
Received: 26 June 2017 / Revised: 17 July 2017 / Accepted: 17 July 2017 / Published: 19 July 2017
(This article belongs to the Special Issue Analysis of Halogen and Other σ-Hole Bonds in Crystals)
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Boron and arsenic triiodides (BI3 and AsI3, respectively) are similar molecules that differ mainly in their geometries. BI3 is a planar trigonal molecule with D3h symmetry, while AsI3 exhibits a trigonal pyramidal shape with C3v symmetry. Consequently, the As atom of the AsI3 molecule has three σ-holes, whereas the B atom of the BI3 molecule has two symmetrical π-holes. Additionally, there are σ-holes on the iodine atoms in the molecules studied. In the first step, we have studied σ-hole and π-hole interactions in the known monocrystals of BI3 and AsI3. Quantum mechanical calculations have revealed that the crystal packing of BI3 is dominated by π-hole interactions. In the case of AsI3, the overall contribution of dihalogen bonding is comparable to that of pnictogen bonding. Additionally, we have prepared the [Na(THF)6]+[I(AsI3)6](AsI3)2 complex, which can be described as the inverse coordination compound where the iodine anion is the center of the aggregate surrounded by six AsI3 molecules in the close octahedral environment and adjacent two molecules in remote distances. This complex is, besides expected dihalogen and pnictogen bonds, also stabilized by systematically attractive dispersion interactions. View Full-Text
Keywords: dihalogen bond; pnictogen bond; pi-back donation; dispersion; inverse coordination dihalogen bond; pnictogen bond; pi-back donation; dispersion; inverse coordination

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Fanfrlík, J.; Švec, P.; Růžičková, Z.; Hnyk, D.; Růžička, A.; Hobza, P. The Interplay between Various σ- and π-Hole Interactions of Trigonal Boron and Trigonal Pyramidal Arsenic Triiodides. Crystals 2017, 7, 225.

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