2,4-Dinitro-1-naphthyl 4-toluene­sulfonate

G Ramachandran; Charles Christopher Kanakam; V Manivannan

doi:10.1107/S1600536808010052

. 2008 Apr 18;64(Pt 5):o873. doi: 10.1107/S1600536808010052

2,4-Dinitro-1-naphthyl 4-toluenesulfonate

G Ramachandran ^a, Charles Christopher Kanakam ^a, V Manivannan ^b,^*

PMCID: PMC2961114 PMID: 21202359

Abstract

In the title compound, C₁₇H₁₂N₂O₇S, the dihedral angle between the benzene ring and the naphthyl plane is 26.34 (6)°. The nitro groups make dihedral angles of 40.09 (4) and 37.05 (3)° with the naphthyl plane. In the crystal structure, weak intra- and intermolecular C—H⋯O interactions are observed.

Related literature

For biological activity, see: Yachi et al. (1989 ▶). For the structure of closely related compounds, see: Manivannan et al. (2005a ▶,b ▶).

Experimental

Crystal data

C₁₇H₁₂N₂O₇S
M _r = 388.35
Monoclinic,
a = 13.071 (2) Å
b = 7.8660 (13) Å
c = 16.595 (3) Å
β = 90.757 (3)°
V = 1706.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 (2) K
0.36 × 0.25 × 0.13 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.920, T _max = 0.970
12222 measured reflections
3116 independent reflections
2291 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.104
S = 1.02
3116 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808010052/is2287sup1.cif

e-64-0o873-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010052/is2287Isup2.hkl

e-64-0o873-Isup2.hkl^{(149.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O5	0.93	2.55	3.194 (3)	127
C14—H14⋯O7	0.93	2.33	2.895 (3)	119
C17—H17⋯O3	0.93	2.48	2.798 (3)	100
C10—H10⋯O1ⁱ	0.93	2.45	3.327 (3)	157

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge Professor T. N. Guru Row and Dr Vijay Thiruvenkatam, Indian Institute of Science, Bangalore, India, for the data collection.

supplementary crystallographic information

Comment

Aromatic sulfonates are used in monitoring the merging of lipids (Yachi et al., 1989). The geometric parameters in the title compound agree with the reported values of similar structures (Manivannan et al., 2005a,b). The dihedral angle between the mean planes of phenyl and naphthyl rings is 26.34 (6)°. The planes N1/O5/O4 and N2/O6/O7 make the dihedral angles of 40.09 (4) and 37.05 (3)°, respectively, with the naphthyl ring. The torsion angles [O1—S1—C1—C6 = -17.0 (2)° and O2—S1—C1—C2 = 27.9 (2)°] indicate a syn conformation of the sulfonyl moiety.

In addition to this, because of the presence of highly electron attracting nitro groups, there are strong dipole-dipole attractions between different molecules in the lattice arrangement. The nitro group substituted naphthylring, which is electron deficient is found to be lying over the electron rich tolyl benzene ring of another molecule in the lattice. This leads to a sort of charge transfer complex.

The enhanced stability of this compound and larger stability of the lattice when compared to other sulfonates reported already, is supported by thermoanalytic studies. This compound is having higher density, melting point and higher lattice energy when compared to others. Another interesting property of this compound is that it possesses antibacterial activity almost equivalent to those of antibiotics. This is attributed to the elongation of the S—O (S1—O3) bond in –S—O–naphthyl ring such that the dissociation to naphthoxy moiety is facilitated. The facile formation of the naphthoxy radical is further supported by the high intensity peak for this specy in the Mass spectra. Kinetic studies also indicate that the rate of hydrolysis (rate of cleavage of the –S—O– bond) is very high when compared to other toluene sulfonates reported already.

The molecular structure is stabilized by weak intramolecular C—H···O interactions and the crystal packing of (I) (Fig. 2) is stabilized by weak intermolecular C—H···O interactions.

Experimental

Calculated quantity of (10 mmol) of alpha naphthol was dissolved in hot con. sulfuric acid (10 ml) and heated for 10 minutes over a water bath to get disulfonic acid. To this was added (10 ml) of fuming nitric acid in small quantity at a time with stirring. After the addition was over the reaction mixture was kept aside for an hour. It was poured into crushed ice with stirring. The precipitate was filtered, washed with cold water, dried and recrystallized from rectified spirit.

A solution of the above 2,4-dinitronaphthol and triethylamine in acetone was treated with sulfonyl chloride in acetone. This was left as such overnight. The solvent was evaporated and the residue was washed with triethylamine solution. The crude product was recrystallized from ethanol to get diffraction quality crystal of 2,4-dintro-1-naphthyl-4-toluene sulfonate.