Rational Modification of the Hierarchy of Intermolecular Interactions in Molecular Crystal Structures by Using Tunable Halogen Bonds

被引：162

作者：

Espallargas, Guillermo Minguez ^{[1
]}

Zordan, Fiorenzo ^{[1
]}

Marin, Luis Arroyo ^{[1
]}

Adams, Harry ^{[1
]}

Shankland, Kenneth ^{[2
]}

van de Streek, Jacco ^{[3
]}

Brammer, Lee ^{[1
]}

机构：

[1] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England

[2] Univ Reading, Sch Pharm, Reading RG6 6AD, Berks, England

[3] Avant Garde Mat Simulat, D-79100 Freiburg, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2009年 / 15卷 / 31期

基金：

英国工程与自然科学研究理事会;

关键词：

crystal engineering; halogen bonds; hydrogen bonds; pi interactions; supramolecular chemistry; INORGANIC SUPRAMOLECULAR SYNTHONS; DOT-X'-C; POWDER DIFFRACTION DATA; HALIDE ION SYNTHON; HYDROGEN-BOND; SOLID-STATE; TETRAHALOCUPRATE(II) IONS; COORDINATION-COMPLEXES; PI STACKING; UNIT-CELL;

D O I：

10.1002/chem.200900410

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

引用

页码：7554 / 7568

页数：15

共 89 条

[1] Structural competition between hydrogen bonds and halogen bonds [J].