C–H⋯S hydrogen bonding interactions

Abstract

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.

C–H▪▪▪S Hydrogen Bonds in Ampicillin and Amoxicillin Crystals Investigated by Sulfur K-Edge X-Ray Absorption Near-Edge Structure Spectroscopy and Single-Crystal X-Ray Structure Analysis

“…The distances and angles of the C-H▪▪▪S contacts in both the AMP and AMX crystals fell within the previously reported ranges of 2.9-3.3 Å and 126-180°, respectively, which were determined based on a survey of published crystal structures. 15) When the atomic coordinates of the hydrogen atoms participating in the C-H▪▪▪S contacts were freely refined, the geometries of the contacts remained within the reported ranges (Supplementary Table S1). This indicates that the contacts can be regarded as the C-H▪▪▪S hydrogen bonds.…”

“…The most notable non-covalent bonding interaction is the hydrogen bond that is formed between donor atoms with high electronegativity and acceptor atoms with lone pairs, such as oxygen and nitrogen. In addition to these conventional strong hydrogen bonds, non-conventional weak hydrogen bonds, such as C-H▪▪▪O, 1) C-H▪▪▪N, 2) C-H▪▪▪π 3) and C-H▪▪▪S, 4) have also been recognized as important specific intermolecular interactions. 5,6) Non-conventional weak hydrogen bonds have often been investigated using crystal structure analysis.…”

Synthesis and reactivity of a tris(carbene) zinc chloride complex

“…25 We recently reported the commonality of C-H⋯S interactions across many types of molecules, and upon further inspection of the structure of complex 3 we find multiple short C-H⋯S contacts that meet the definition of a hydrogen bond. 26 Multiple contacts between the C-H groups of the flanking t Bu of the Ph B ( t BuIm) 2 ( t BuImH) ligand point directly at the sulfur atoms of the S 4 2− chain, and some contacts are as short as 2.730 Å with a C-H⋯S bond angle near 160°, which is significantly shorter than the sum of the van der Waals radii of the H and S atoms (3.0 Å). In addition to crystallographic evidence for C-H⋯S interactions in complex 3, we also performed variable temperature 1 H NMR experiments (233-323 K) and observed a downfield shift of the flanking t Bu and imidazolium hydrogens at lower temperatures and an upfield shift of these resonances at elevated temperatures (see ESI Fig.…”

Hydrogen bonding with polonium

“…10,11 However, the past decade has witnessed the importance of polarizability in sulfur-and selenium-centered H-bonds (S/Se H-bonds). 6,[12][13][14][15][16] Some of the recent studies establish that sulfur and selenium can form equally strong H-bonds as oxygen. [17][18][19][20] Recent reports suggest that sulfur can not only behave as a H-bond acceptor, but also as a H-bond donor.…”