Preferred Geometries and Energies of Sulfur–Sulfur Interactions in Crystal Structures

Abstract

It has been demonstrated that sulfur-sulfur interactions can exist in various molecular systems. In this work we investigated sulfur-sulfur interactions in crystal structures of small molecules by analyzing geometric data from the Cambridge Structural Database (CSD) and by quantum chemical calculations. The analysis of cysteine residues (R-CH 2 SH) in the crystal structures from the CSD indicates that in the sulfur-sulfur interactions the preferred is parallel orientation of two C-S-H planes. Quantum chemical calculations were performed on model systems of methanethiol dimers. The most stable geometry of methanethiol dimer with parallel orientation of C-S-H planes is significantly strong; the interaction energy is -1.80 kcal/mol calculated at the very accurate CCSD(T)/CBS level. However, the strongest sulfur-sulfur Author Contributions: I.S.A. performed quantum chemical calculations, interpreted the data, and prepared the manuscript.; G.V.J. proposed topic and performed CSD search.; M.K.M. has done SAPT, QTAIM and NCI index method calculations and analyzed data.; S.D.Z. analyzed the results, supervised, wrote and edited the manuscript.

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

“…In contrast to [M(μ 3 ‐Cl)Cl(HL · S)] 4 , in the crystal structure of 1 there are close intermolecular S ··· S contacts of 3.771 Å that organize the complexes into pseudo‐chains (Figure and Figure ). This is in line with literature reports on the importance of parallel S ··· S interactions for the packing of S‐containing molecules in crystal lattices , …”

Supramolecular insight into the substitution of sulfur by selenium, based on crystal structures, quantum-chemical calculations and biosystem recognition

“…6), enabling electrostatic attraction between Se atoms. Similar behaviour is observed with S atoms (Antonijević et al, 2016). Red areas in the electrostatic potential maps indicate an increase in the electron density, while a positive potential is denoted by blue regions.…”

“…The analysis of the interactions of cysteine residues (R-CH 2 SH) in the crystal structures from the CSD showed that SÁ Á ÁS interactions with a parallel orientation of the C-S-H planes are the most numerous (Antonijević et al, 2016). Quantum-chemical calculations at the CCSD(T)/CBS level were performed on model systems of methanethiol dimers with parallel orientations and with starting geometries similar to the geometries presented here.…”

Triptycene End-Capped Quinoxalinophenanthrophenazines with Aromatic Substituents – Synthesis, Characterization, and Single-Crystal Structure Analysis

“…As mentioned already in the introduction, we were interested in understanding whether the preferred tight cofacial packing of the QPP π planes observed previously for various structures is "robust" even for QPP with additional aromatic substituents, which not only have a higher steric demand but are also able to additionally interact with the backbone or themselves, e.g., by competing π-stacking, [9][10][11] London dispersion, 12 or S-S interactions. 37,38 Single crystals were either grown by slow evaporation of the solvent of a concentrated QPP solution in chloroform or by vapor diffusion into such a solution. All solvates crystallized in the triclinic space group P-1.…”