Crystal Structure of the 1:1 Addition Compound Dithiane-Iodoform.

Bjorvatten, T.; Hassel, O.; Buchardt, Ole; Olsen, Gert E.; Pedersen, Christian; Toft, Jens

doi:10.3891/acta.chem.scand.15-1429

Cited by 22 publications

(11 citation statements)

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“…Reference Since many halogen atoms have regions of both positive and negative electrostatic potential on their surfaces, it should be possible for such a halogen atom in one molecule to interact attractively with the same atom in another, identical molecule, that is, "like attracting like." It would be highly directional; the positive s hole on one halogen atom interacting with a negative side of the other (6). This is indeed exactly what is found in the crystal lattice of molecular chlorine, Cl 2 (7).…”

Section: Moleculesupporting

confidence: 66%

“…These molecules were involved in some of the early instances of halogen bonding to be characterized crystallographically. CHI 3 interacts with 1,4-dithiane as shown in 1, [6] O=PBr 3 has Br···O close contacts in its crystal lattice, [12] and ClÀC(O)ÀC(O)ÀCl forms a complex with 1,4-dioxane. [9] Halogen bonding can now be explained in a very straightforward manner.…”

Section: The S Holementioning

confidence: 99%

“…A number of complexes between halides and oxygen/nitrogen Lewis bases were reported and characterized crystallographically in the 1960s, much of this being done by Hassel and his colleagues. Some examples are as follows: SbI 3 ···1,4-dithiane, [4] IÀCCÀI···1,4-dioxane, [5] CHI 3 ···1,4-dithiane (1), [6] CHI 3 ···quinoline, [7] I 2 C=CI 2 ···1,4-diselenane, [8] ClÀC(O)ÀC(O)À Cl···1,4-dioxane, [9] BrÀC(O)ÀC(O)ÀBr···1,4-dioxane (2), [9] and Br 2 C=CBr 2 ···pyrazine (3). [10] These form chain-like structures in the crystal held together by weak X···B bonds, for example, compounds 1-3.…”

Section: The Enigma Of Halogen Bonding: Early Experimental Observationsmentioning

confidence: 99%

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Halogen Bonding: An Interim Discussion

2013

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Halogen bonding is a noncovalent interaction that is receiving rapidly increasing attention because of its significance in biological systems and its importance in the design of new materials in a variety of areas, for example, electronics, nonlinear optical activity, and pharmaceuticals. The interactions can be understood in terms of electrostatics/polarization and dispersion; they involve a region of positive electrostatic potential on a covalently bonded halogen and a negative site, such as the lone pair of a Lewis base. The positive potential, labeled a σ hole, is on the extension of the covalent bond to the halogen, which accounts for the characteristic near-linearity of halogen bonding. In many instances, the lateral sides of the halogen have negative electrostatic potentials, allowing it to also interact favorably with positive sites. In this discussion, after looking at some of the experimental observations of halogen bonding, we address the origins of σ holes, the factors that govern the magnitudes of their electrostatic potentials, and the properties of the resulting complexes with negative sites. The relationship of halogen and hydrogen bonding is examined. We also point out that σ-hole interactions are not limited to halogens, but can also involve covalently bonded atoms of Groups IV-VI. Examples of applications in biological/medicinal chemistry and in crystal engineering are mentioned, taking note that halogen bonding can be "tuned" to fit various requirements, that is, strength of interaction, steric factors, and so forth.

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Section: Moleculesupporting

confidence: 66%

Section: The S Holementioning

confidence: 99%

Section: The Enigma Of Halogen Bonding: Early Experimental Observationsmentioning

confidence: 99%

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Halogen Bonding: An Interim Discussion

2013

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“…-RT In (/Obld -/g)/(/t -/obsd) = -rRT In fcrate + C or (4) log (/obsd -/g)/(/t -/obsd) = r'Es + C" Here it is convenient to use the doubly corrected Es parameters in place of the rate constants, again redefining the constant C.…”

Section: ¡Q>-no2mentioning

confidence: 99%

Conformational preferences in acylic chloro sulfides. Semiquantitative approach

Underwood¹,

Chan²,

Green³

et al. 1973

J. Org. Chem.

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The erythro isomers in alkyl-substituted l-chloro-l-phenyl-2-ethyl 2,4-dinitrophenyl sulfides increasingly favor the conformer having trans hydrogens as the size of R increases. The rates of solvolysis in 95% ethanol show evidence of anchimeric assistance by sulfur and give products of retained configuration. The rates are correlated with Taft's Eg values and corrected Es values are taken. These Es values are correlated with the nmr chemical shift of the 2' hydrogen in the dinitrophenyl ring, and the Es values are adjusted again. A linear freeenergy correlation is made between the corrected Es values and the equilibrium constant (gauche -trans conformers) {Jobsd -Jq)/(Jt -Jobad). Unique values of the limiting coupling constants Jt and Ja cannot be obtained by this procedure. Reasons are given for choosing one solution of the correlation procedure, Jt = 13.5 Hz and Ja = 2.5 ± 1 Hz. The percentage of the trans conformer in several compounds is roughly calculated. The conformations of the solvolysis products (sulfide ethers and sulfide alcohols) are briefly discussed.

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“…The iodoform octasulfur (CHI 3 Á Á Á S 8 ) is an example of such type of charge-transfer complex and the nature of charge-transfer (IÁ Á ÁS) interaction has been investigated by experimental charge density analysis based on its crystal structure [33]. Besides iodoform octasulfur, the charge-transfer complexes of iodoform with dioxane, dithiane, and diselenane were also found in their crystal forms [34][35][36]. Despite the fact that these CT complexes are very typical and representative, the CT interactions are not fully understood in terms of their strength, geometrical preference, and fundamental physical nature.…”

Section: Introductionmentioning

confidence: 98%