A chalcogen-bonded complex H3N⋯S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy

Abstract

General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. Full terms of use are available: http://www.bristol.ac.uk/pure/userguides/explore-bristol-research/ebr-terms/ A chalcogen-bonded complex H3N⋯S=C=S formed by ammonia and carbon disulfide characterised by chirped-pulse, broadband microwave spectroscopy Abstract Ground-state rotational spectra were observed for ten symmetric-top isotopologues H3N⋯S=C=S, H3N⋯ 34 S=C=S, H3N⋯S=C= 34 S, H3N⋯S= 13 C=S, H3 15 N⋯S=C=S, H3 15 N⋯ 34 S=C=S, H3 15 N⋯S=C= 34 S, H3 15 N⋯S= 13 C=S, H3 15 N⋯ 33 S=C=S and H3 15 N⋯S=C= 33 S, the first five in their natural abundance in a mixture of ammonia and carbon disulphide in argon and the second group with enriched 15 NH3. The four asymmetric-rotor isotopomers H2DN⋯S=C=S, H2DN⋯ 34 S=C=S, H2DN⋯S=C= 34 S, and HD2N⋯S=C=S were investigated by using a sample composed of ND3 mixed with CS2. Rotational constants, centrifugal distortion constants and 33 S nuclear quadrupole coupling constants were determined from spectral analyses and were interpreted with the aid of models of the complex to determine its symmetry, geometry, one measure of the strength of the intermolecular binding, and information about the subunit dynamics. The complex has C3v symmetry, with nuclei in the order H3N⋯S=C=S, thereby establishing that the non-covalent interaction is a chalcogen bond involving the non-bonding electron pair of ammonia as the nucleophile and the axial region near one of the S atoms as the electrophile. The small intermolecular stretching force constant k = 3.97(5) N m -1 indicates a weak interaction and suggests the assumption of unperturbed component geometries on complex formation. A simple model used to account for the contribution of the subunit angular oscillations to the zero-point motion leads to the intermolecular bond length r(N⋯S) = 3.388(10) Å. * Corresponding authors: a.c.

Versatility of the Cyano Group in Intermolecular Interactions

“…Following many decades of study of the H-bond [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ], a great deal of research has turned to closely related interactions in which the bridging proton is replaced by any of a number of larger atoms, generally drawn from the right side of the periodic table. Depending upon the specific column of the table in which these atoms lie, the noncovalent bonds are typically referred to as halogen, chalcogen, and pnicogen bonds [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ]. Despite the diversity of the bridging atoms, these various interactions share a number of characteristics.…”

Effects of Halogen, Chalcogen, Pnicogen, and Tetrel Bonds on IR and NMR Spectra

“…Recent years have witnessed a growing recognition of a range of newly rediscovered noncovalent bonds. Similarly to their closely related H-bond cousin, this class of bonds [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25] are derived from a primary electrostatic attraction, supplemented by substantial amounts of charge transfer, polarization, and dispersion ingredients. In addition to their occurrence in small-model dimers, these sorts of interactions are a major factor in the structure and function of much larger supramolecular systems [26,27,28,29,30,31,32,33,34,35].…”

Theoretical Studies of IR and NMR Spectral Changes Induced by Sigma-Hole Hydrogen, Halogen, Chalcogen, Pnicogen, and Tetrel Bonds in a Model Protein Environment

“…Depending upon the column of the periodic table from which this bridging atom is drawn, the resulting noncovalent bond with a nucleophile is designated as a halogen (XB), chalcogen (YB), pnicogen (ZB), or tetrel (TB) bond. Like the HB, this class of bonds [10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36] are similarly derived from a primary electrostatic attraction, supplemented by substantial amounts of charge transfer, polarization, and dispersion components.…”