Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, and Institute of Molecular Biology, University of Oregon, Eugene, Oregon, 97403-1253, USA.
Chem Soc Rev. 2022 Feb 21;51(4):1454-1469. doi: 10.1039/d1cs00838b.
The short C-H⋯S contacts found in available structural data for both small molecules and larger biomolecular systems suggest that such contacts are an often overlooked yet important stabilizing interaction. Moreover, many of these short C-H⋯S contacts meet the definition of a hydrogen bonding interaction. Using available structural data from the Cambridge Structural Database (CSD), as well as selected examples from the literature in which important C-H⋯S contacts may have been overlooked, we highlight the generality of C-H⋯S hydrogen bonding as an important stabilizing interaction. To uncover and establish the generality of these interactions, we compare C-H⋯S contacts with other traditional hydrogen bond donors and acceptors as well as investigate how coordination number and metal bonding affect the preferred geometry of interactions in the solid state. This work establishes that the C-H⋯S bond meets the definition of a hydrogen bond and serves as a guide to identify C-H⋯S hydrogen bonds in diverse systems.
在小分子和更大生物分子体系的现有结构数据中发现的短 C-H⋯S 接触表明，此类接触是一种经常被忽视但却很重要的稳定相互作用。此外，这些短的 C-H⋯S 接触中有许多符合氢键相互作用的定义。我们利用剑桥结构数据库（CSD）中的现有结构数据，以及文献中选择的一些可能被忽视的重要 C-H⋯S 接触的例子，强调了 C-H⋯S 氢键作为一种重要的稳定相互作用的普遍性。为了揭示和确立这些相互作用的普遍性，我们将 C-H⋯S 接触与其他传统的氢键供体和受体进行了比较，并研究了配位数和金属键合如何影响固态中相互作用的优选几何形状。这项工作证实 C-H⋯S 键符合氢键的定义，并可作为在不同体系中识别 C-H⋯S 氢键的指南。
