The many flavours of halogen bonds - message from experimental electron density and Raman spectroscopy

被引:16
作者
Wang, Ruimin [1 ,2 ]
George, Janine [3 ]
Potts, Shannon Kimberly [1 ]
Kremer, Marius [1 ]
Dronskowski, Richard [1 ,4 ,5 ]
Englert, Ulli [1 ,2 ]
机构
[1] Rhein Westfal TH Aachen, Inst Inorgan Chem, Landoltweg 1, D-52056 Aachen, Germany
[2] Shanxi Univ, Inst Mol Sci, Taiyuan 030006, Shanxi, Peoples R China
[3] Inst Condensed Matter & Nanosci, Chemin Etoiles 8-L7-03-01, B-1348 Louvain La Neuve, Belgium
[4] Rhein Westfal TH Aachen, JARA, HPC, D-52056 Aachen, Germany
[5] Shenzhen Polytech, Hoffmann Inst Adv Mat, 7098 Liuxian Blvd, Shenzhen, Peoples R China
来源
ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY | 2019年 / 75卷
关键词
halogen bonds; experimental electron density; AIM analysis; crystal engineering; crystal structure; Raman spectroscopy; EXPERIMENTAL CHARGE-DENSITY; INITIO MOLECULAR-DYNAMICS; PLANE-WAVE; CRYSTAL-STRUCTURE; HYDROGEN-BONDS; X-RAY; SIGMA-HOLE; CL; DIFFRACTION; ABSORPTION;
D O I
10.1107/S205322961901132X
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Experimental electron-density studies based on high-resolution diffraction experiments allow halogen bonds between heavy halogens to be classified. The topological properties of the electron density in Cl center dot center dot center dot Cl contacts vary smoothly as a function of the interaction distance. The situation is less straightforward for halogen bonds between iodine and small electronegative nucleophiles, such as nitrogen or oxygen, where the electron density in the bond critical point does not simply increase for shorter distances. The number of successful charge-density studies involving iodine is small, but at least individual examples for three cases have been observed. (a) Very short halogen bonds between electron-rich nucleophiles and heavy halogen atoms resemble three-centre-four-electron bonds, with a rather symmetric heavy halogen and without an appreciable sigma hole. (b) For a narrow intermediate range of halogen bonds, the asymmetric electronic situation for the heavy halogen with a pronounced sigma hole leads to rather low electron density in the (3,-1) critical point of the halogen bond; the properties of this bond critical point cannot fully describe the nature of the associated interaction. (c) For longer and presumably weaker contacts, the electron density in the halogen bond critical point is only to a minor extent reduced by the presence of the sigma hole and hence may be higher than in the aforementioned case. In addition to the electron density and its derived properties, the halogen-carbon bond distance opposite to the sigma hole and the Raman frequency for the associated vibration emerge as alternative criteria to gauge the halogen-bond strength. We find exceptionally long C-I distances for tetrafluorodiiodobenzene molecules in cocrystals with short halogen bonds and a significant red shift for their Raman vibrations.
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页码:1190 / +
页数:16
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