Non-bonded O⋯S contacts and O–H⋯S hydrogen bonds in isomeric hydroxyphenyl-1,3-dithianes

O−H···O versus O−H···S Hydrogen Bonding I: Experimental and Computational Studies on thep-Cresol·H2O andp-Cresol·H2S Complexes

“…Sulfur also happens to be a biologically abundant element (amino acids, disulfide bridges, etc. ), and the existence of the X−H···S (X = N, O) HB is well established from the crystallographic data on proteins and organic molecules. − Despite this, the experimental investigations have been very scant on the X−H···S hydrogen-bonded systems. A large number of computational studies have been devoted, however, to investigate either the H−S···π or S−H···π interaction in the case of H 2 S and aromatic hydrocarbon complexes. − The authors’ first report on the experimental observation of O−H···S HB in simple model compounds of two naturally occurring amino acids, tyrosine and methionine ( p -CResol was taken for tyrosine and dimethyl sulfide (DMS) for methionine), indicated that the O−H stretch red shift in these systems was almost the same as that for the O−H···O HB in the case of the p -cresol-(H 2 O) 1 complex.…”

“…), and the existence of the X-H • • • S (X ) N, O) HB is well established from the crystallographic data on proteins and organic molecules. [4][5][6][7][8][9][10][11][12][13][14][15] Despite this, the experimental investigations have been very scant on the X-H • • • S hydrogen-bonded systems. A large number of computational studies have been devoted, however, to investigate either the H-S • • • π or S-H • • • π interaction in the case of H 2 S and aromatic hydrocarbon complexes.…”

Synthesis, crystal structures and non-bonded S···S contacts with O‒H···O/O‒H···S hydrogen bonds in isomeric hydroxyphenyl-1,3-dithianes

“…We reported earlier in our publication (15) that contacts in crystals between divalent sulfur and other atoms X can be divided into two general types, depending on the nature of the second atom as described by Rosenfield et al (17). The two types are distinguished by the direction of the S· · ·X vector relative to the C−S−C plane ( Figure 1).…”

“…A comprehensive database study by Allen et al (18) has demonstrated that divalent sulfur, particularly as part of a C−S−C unit, is a poor but adequate acceptor for conventional hydrogen bond donors such as O−H and N−H. We previously reported the crystal structures of three isomeric hydroxyphenyl-1,3-dithianes, ortho-, meta-and para-HO−C 6 H 4 −C 4 H 7 S 2 , where both non-bonded O· · ·S contacts and O−H· · ·S hydrogen bonds play an important role in the packing within their crystals (15). …”

“…We reported the use of sulfur of dithiane rings in isomeric hydroxyphenyl-1,3-dithianes to generate different engineered solids based on non-bonded O· · ·S contacts and O−H· · ·S hydrogen bonds (15). In continuation of this work, we describe in this paper how the systematic variation of the number of phenolic hydroxyl groups and dithiane rings influences the hydrogen bonding interactions and packing of the molecules in the solid state.…”