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Crystal structure of 2,4-di-nitro-phenyl 4-methyl-benzene-sulfonate: a new polymorph.

Cooley TA, Riley S, Biros SM, Staples RJ, Ngassa FN - Acta Crystallogr E Crystallogr Commun (2015)

Bottom Line: The title compound, C13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-di-nitro-phenol and p-toluene-sulfonyl chloride.Acta Cryst, E59, o378-380].The aromatic substituents on the sulfonate group are oriented gauche to one another with a C-O-S-C torsion angle of -62.0 (3)°.

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Affiliation: Department of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA.

ABSTRACT
The title compound, C13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-di-nitro-phenol and p-toluene-sulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH [Vembu et al. (2003). Acta Cryst, E59, o378-380]. The aromatic substituents on the sulfonate group are oriented gauche to one another with a C-O-S-C torsion angle of -62.0 (3)°. The supra-molecular features that contribute to the crystal stability are offset π-π [centroid-centroid distance = 3.729 (2) Å] and multiple C-H⋯O inter-actions.

No MeSH data available.


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(a) The asymmetric unit of the title compound along with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level; (b) the structure and atom-numbering scheme of a polymorph of the title compound WUVYUH (Vembu, et al., 2003a ▸). All hydrogen atoms have been omitted for clarity.
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fig2: (a) The asymmetric unit of the title compound along with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level; (b) the structure and atom-numbering scheme of a polymorph of the title compound WUVYUH (Vembu, et al., 2003a ▸). All hydrogen atoms have been omitted for clarity.

Mentions: A review of the current literature lends credence to both a concerted mechanism and a non-concerted mechanism (Guthrie, 1991 ▸; Colthurst & Williams, 1997 ▸; Spillane et al., 2001 ▸; Um et al., 2003 ▸, 2004 ▸, 2013 ▸). Using primary and secondary amines as nucleophiles, the factors influencing regioselectivity of nucleophilic substitution reactions at the sulfonyl group have been reported (Um et al., 2004 ▸). It has been demonstrated that the regioselectivity and S—O bond-fission mechanism depends on the basicity of the amine and the electronic nature of the sulfonyl substituent. Based on the current state of knowledge in the field, we have sought to capitalize on the chemistry learned on the mechanistic insight of S—O vs C—O bond fission by investigating the effect of different substituents on the reactivity of sulfonates. In our work, we are inter­ested in using various sulfonate analogues (Fig. 1 ▸) as electrophilic substrates in nucleophilic aromatic substitution (SNAr) reactions similar to those reported by others (Qrareya et al., 2014 ▸). As the title compound is of inter­est in our ongoing effort on probing the mechanism of SNAr reactions with sulfonate derivatives, we report here on the synthesis and crystal structure of a new polymorph of 2,4-di­nitro­phenyl 4-methyl­benzene­sulfonate (Fig. 2 ▸).


Crystal structure of 2,4-di-nitro-phenyl 4-methyl-benzene-sulfonate: a new polymorph.

Cooley TA, Riley S, Biros SM, Staples RJ, Ngassa FN - Acta Crystallogr E Crystallogr Commun (2015)

(a) The asymmetric unit of the title compound along with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level; (b) the structure and atom-numbering scheme of a polymorph of the title compound WUVYUH (Vembu, et al., 2003a ▸). All hydrogen atoms have been omitted for clarity.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4555369&req=5

fig2: (a) The asymmetric unit of the title compound along with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level; (b) the structure and atom-numbering scheme of a polymorph of the title compound WUVYUH (Vembu, et al., 2003a ▸). All hydrogen atoms have been omitted for clarity.
Mentions: A review of the current literature lends credence to both a concerted mechanism and a non-concerted mechanism (Guthrie, 1991 ▸; Colthurst & Williams, 1997 ▸; Spillane et al., 2001 ▸; Um et al., 2003 ▸, 2004 ▸, 2013 ▸). Using primary and secondary amines as nucleophiles, the factors influencing regioselectivity of nucleophilic substitution reactions at the sulfonyl group have been reported (Um et al., 2004 ▸). It has been demonstrated that the regioselectivity and S—O bond-fission mechanism depends on the basicity of the amine and the electronic nature of the sulfonyl substituent. Based on the current state of knowledge in the field, we have sought to capitalize on the chemistry learned on the mechanistic insight of S—O vs C—O bond fission by investigating the effect of different substituents on the reactivity of sulfonates. In our work, we are inter­ested in using various sulfonate analogues (Fig. 1 ▸) as electrophilic substrates in nucleophilic aromatic substitution (SNAr) reactions similar to those reported by others (Qrareya et al., 2014 ▸). As the title compound is of inter­est in our ongoing effort on probing the mechanism of SNAr reactions with sulfonate derivatives, we report here on the synthesis and crystal structure of a new polymorph of 2,4-di­nitro­phenyl 4-methyl­benzene­sulfonate (Fig. 2 ▸).

Bottom Line: The title compound, C13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-di-nitro-phenol and p-toluene-sulfonyl chloride.Acta Cryst, E59, o378-380].The aromatic substituents on the sulfonate group are oriented gauche to one another with a C-O-S-C torsion angle of -62.0 (3)°.

View Article: PubMed Central - HTML - PubMed

Affiliation: Department of Chemistry, Grand Valley State University, 1 Campus Dr., Allendale, MI 49401, USA.

ABSTRACT
The title compound, C13H10N2O7S, was synthesized via a nucleophilic substitution reaction between 2,4-di-nitro-phenol and p-toluene-sulfonyl chloride. This crystal structure is a polymorph of CSD entry WUVYUH [Vembu et al. (2003). Acta Cryst, E59, o378-380]. The aromatic substituents on the sulfonate group are oriented gauche to one another with a C-O-S-C torsion angle of -62.0 (3)°. The supra-molecular features that contribute to the crystal stability are offset π-π [centroid-centroid distance = 3.729 (2) Å] and multiple C-H⋯O inter-actions.

No MeSH data available.


Related in: MedlinePlus