Complementary halogen and hydrogen bonding: sulfur⋯iodine interactions and thioamide ribbons

Arman, Hadi D.; Gieseking, Rebecca L.; Hanks, Timothy W.; Pennington, William T.

doi:10.1039/b925710a

Cited by 81 publications

(79 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This ability of the thione sulfur atoms to interact with more than one XB donor has been mentioned in a few examples with organic XB donors 18,19,30 while it is essentially unknown with the thione adducts with I 2 , Br 2 , IBr or ICl (see below). This ability of the thione sulfur atoms to interact with more than one XB donor has been mentioned in a few examples with organic XB donors 18,19,30 while it is essentially unknown with the thione adducts with I 2 , Br 2 , IBr or ICl (see below).…”

Section: Scheme 2 Investigated Iodinated Dithiole-2-thiones and Thiazmentioning

confidence: 97%

“…Most of the reported examples involved either sp 3 sulfur atoms in thioethers or sp 2 sulfur atoms in thiones and thioureas, interacting with I 2 , IBr or ICl. One can essentially mention (Scheme 1) the co-crystals of thiourea, ethylenethiourea, 18 2-mercapto-1methyl-imidazole 19 or primary thioamides, 20 with strongly activated halogen bond donors such as 1,2-and 1,4diiodotetrafluorobenzene. 5 In this context, it is quite surprising that this wide pool of sulfurbased XB acceptors has not been engaged extensively in XB systems with other XB donor molecules than the dihalogens and interhalogens.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

et al. 2016

View full text Add to dashboard Cite

The propensity of the sp 2 sulfur atom in thiones to act as a halogen bond (XB) acceptor is well established with dihalides (I 2 , IBr or ICl) as XB donors, but has been more rarely explored with organic XB donors. The crystal structures of four iodinated heterocycles, namely, the mono-and diiodo derivatives of 1,3-dithiole-2-thione and N-ethylthiazole-2-thione, offer an opportunity to evaluate the strength and directionality of such C-I⋯S interactions. We describe here the original synthesis of 3-ethyl-5-iodothiazole-2Ĳ3H)-thione and 3-ethyl-4,5-diiodothiazole-2Ĳ3H)-thione and the solid state structures of the four compounds, with specific attention to the halogen bonds (C-I⋯SC) and hydrogen bonds (C-H⋯I,S) taking place in the crystals, in connection with the peculiarities of the calculated electrostatic surface potential (ESP) of the four molecules. The thione sulfur atoms in thiazole-2-thiones appear as better XB acceptors than in dithiole-2-thiones, with a notable deformation of the charge concentration area. The mono-iodinated derivatives, 4-iodo-1,3-dithiole-2-thione and 3-ethyl-5-iodothiazole-2-thione, are characterized by hydrogen atoms with positive extremum of the electrostatic surface potential comparable to those of the neighboring iodine atoms, illustrating the parallelism between C-I⋯S halogen bonds and the so-called weak C-H⋯I,S hydrogen bonds. CrystEngCommThis journal is

show abstract

Section: Scheme 2 Investigated Iodinated Dithiole-2-thiones and Thiazmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

et al. 2016

View full text Add to dashboard Cite

show abstract

“…However, it might be much more interesting to contrast the behavior of XB donors 2-4 with A and D to that with A and C. Especially with 2, the isolation of two stoichiometric variations, A·D·2 2 Initially, A·D·2 2 is formed as the kinetic product, with A and D assembling into motif I and 2 only serving as a monotopic halogen bond donor, not utilizing its full potential (Figure 3a). 33 The system evolves, however, resulting in the formation of A·D 2 ·2 2 with the re-emerging motif II, and the formation of chains through N−H···S hydrogen bonds supported by C−I···S and C−I···O halogen bonding with 2 again acting as a ditopic donor (Figure 3b). Next, the structure of A·D 2 ·3 2 , featuring thiourea D in the more stable cis conformation 40 still exhibits motif II, with A·D 2 moieties connected into chains through C−I···S halogen bonds with XB donor 3 (Figure 4a).…”

Section: Scheme 3 Hydrogen Bond-mediated Binding Motifs Between Crowmentioning

confidence: 99%

“…Arman et al reported that the N−H···S type hydrogen bonding between thiourea-type molecules is preserved in the structures of their C−I···S halogen bonded co-crystals. 33 Moreover, the set of cocrystals described consisted of three different thioureas and three different halogen bond donors, suggesting that the orthogonality of hydrogen and halogen bonding could be a general property of such systems. Later, Robertson et al showed the halogen bonds between diiodine as the donor and tetramethylthiourea as the acceptor to be particularly robust in solution, which was ascribed to their pronounced charge-transfer character.…”

Section: Introductionmentioning

confidence: 99%

Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

2016

View full text Add to dashboard Cite

ABSTRACT:A carefully designed strategy is presented for construction of ternary co-crystals, based on the orthogonality of two supramolecular interaction modes: hydrogen bonding between crown ethers and thioureas and the halogen bonding between thioureas and perfluorohalocarbons. Tested on a set comprising two crown ethers, two thioureas and five halogen bond donors, the strategy resulted in a high, 75% success rate, with 15/20 component combinations yielding at least one co-crystal. Crystal structure analysis revealed the interplay between the hydrogen and halogen bonding motifs, also shedding light on the variables affecting their formation.

show abstract

“…The interplay between hydrogen and halogen bonding in sulfur-containing systems has potential relevance for thyroid chemistry [115,116] and as such a study of the cooperative effects between these and other non-covalent interactions in model systems may provide a better understanding of the structure and properties of related biomolecular complexes, especially those that may govern important biological activities in living systems. structures that these dimers adopt.…”

Section: Thiirane Xf/beh 2 Dimersmentioning

confidence: 99%

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

McDowell

Joseph

2015

Challenges and Advances in Computational Chemistry and Physics

View full text Add to dashboard Cite

Hydrogen, halogen, lithium and beryllium bonding are briefly surveyed as a prelude to a report of a computational study of the interplay between these various non-covalent interactions. Our study used model dimers and trimers involving the thiirane molecule, (CH 2 ) 2 S, complexed with small molecules like HF, ClF, BrF, LiF and BeH 2 to assess and investigate the interplay between the different noncovalent interactions. The model trimer systems show positive cooperative effects when thiirane is one of the terminal molecules, whereas a negative cooperative effect is evident when it is at the center of the trimer. The changes in selected molecular properties, including the redistribution of charge densities obtained by the natural population analysis (NPA), implemented in the natural bond orbital (NBO) procedure, and an Atoms in Molecules (AIM) topological analysis, were useful in understanding these cooperative effects. Introduction Overview of Non-Covalent InteractionsNon-covalent interactions in molecular systems is a topic of much scientific interest as it spans a number of scientific subdisciplines. They are responsible for the existence of condensed phases, for which the forces operative between interacting neutral molecules are strong enough to limit the volume of samples of a particular material but weak enough to ensure the fluidity of such materials in bulk.Such interactions are usually dominated by classical electrostatic forces, through the interaction between the permanent multipole moments of the interacting molecular species. These electrostatic forces are usually augmented by classical polarization and quantum-mechanical dispersion forces, and their long-range behavior dependent on some inverse power of their molecular separation (usually measured by the distance between the center of masses of the interacting molecules). At equilibrium

show abstract

Complementary halogen and hydrogen bonding: sulfur⋯iodine interactions and thioamide ribbons

Abstract: Complementary halogen bonding and hydrogen bonding coexist in co-crystals of organoiodines with molecules containing the thioamide functionality. Thiourea.organoiodine co-crystals are shown to exhibit a remarkably reliable synthon with complementary N-H...S ribbons and S...I interactions.

Cited by 81 publications

References 34 publications

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

Interplay of Hydrogen, Halogen, Lithium and Beryllium Bonds in Complexes of Thiirane

Contact Info

Product

Resources

About