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Acta Cryst. (2008). E64, o873    [ doi:10.1107/S1600536808010052 ]

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

G. Ramachandran, C. C. Kanakam and V. Manivannan

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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.

Refinement top

H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H, and with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of (I), viewed down the b axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.
2,4-Dinitro-1-naphthyl 4-toluenesulfonate top
Crystal data top
C17H12N2O7SF000 = 800
Mr = 388.35Dx = 1.512 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4023 reflections
a = 13.071 (2) Åθ = 1.8–25.2º
b = 7.8660 (13) ŵ = 0.24 mm−1
c = 16.595 (3) ÅT = 295 (2) K
β = 90.757 (3)ºBlock, colourless
V = 1706.0 (5) Å30.36 × 0.25 × 0.13 mm
Z = 4
Data collection top
Bruker Kappa APEXII
diffractometer		3116 independent reflections
Radiation source: fine-focus sealed tube2291 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 295(2) Kθmax = 25.4º
ω and φ scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→15
Tmin = 0.920, Tmax = 0.970k = −9→9
12222 measured reflectionsl = −19→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.104  w = 1/[σ2(Fo2) + (0.0486P)2 + 0.4765P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
3116 reflectionsΔρmax = 0.20 e Å−3
245 parametersΔρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C17H12N2O7SV = 1706.0 (5) Å3
Mr = 388.35Z = 4
Monoclinic, P21/cMo Kα
a = 13.071 (2) ŵ = 0.24 mm−1
b = 7.8660 (13) ÅT = 295 (2) K
c = 16.595 (3) Å0.36 × 0.25 × 0.13 mm
β = 90.757 (3)º
Data collection top
Bruker Kappa APEXII
diffractometer		3116 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2291 reflections with I > 2σ(I)
Tmin = 0.920, Tmax = 0.970Rint = 0.031
12222 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.044245 parameters
wR(F2) = 0.104H-atom parameters constrained
S = 1.02Δρmax = 0.20 e Å−3
3116 reflectionsΔρmin = −0.23 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.75961 (5)0.14928 (8)0.91732 (3)0.04636 (19)
N20.47400 (18)0.4441 (3)1.21402 (12)0.0509 (5)
N10.77051 (15)0.1383 (3)1.12836 (11)0.0511 (5)
C80.62399 (17)0.1694 (3)1.03092 (12)0.0379 (5)
C90.66905 (17)0.2018 (3)1.10432 (13)0.0396 (5)
C100.61838 (18)0.2985 (3)1.16206 (13)0.0418 (5)
H100.65050.32441.21090.050*
C110.52268 (18)0.3540 (3)1.14659 (12)0.0394 (5)
C120.47017 (17)0.3258 (3)1.07210 (12)0.0383 (5)
C130.52516 (16)0.2336 (3)1.01249 (12)0.0366 (5)
C140.37180 (18)0.3875 (3)1.05167 (14)0.0462 (6)
H140.33470.44761.08970.055*
C150.33082 (18)0.3603 (3)0.97732 (15)0.0502 (6)
H150.26580.40160.96510.060*
C160.38494 (19)0.2709 (3)0.91879 (15)0.0494 (6)
H160.35580.25420.86800.059*
C170.47966 (18)0.2082 (3)0.93546 (13)0.0421 (5)
H170.51480.14840.89620.051*
C10.82025 (17)−0.0380 (3)0.88993 (14)0.0467 (6)
C40.9179 (2)−0.3362 (4)0.84598 (18)0.0639 (7)
C20.8941 (2)−0.1075 (4)0.94025 (17)0.0660 (8)
H20.9113−0.05480.98880.079*
C30.9421 (2)−0.2557 (4)0.91778 (19)0.0744 (9)
H30.9918−0.30260.95160.089*
C60.7943 (2)−0.1167 (4)0.81845 (15)0.0583 (7)
H60.7439−0.07080.78480.070*
C50.8437 (2)−0.2639 (4)0.79741 (18)0.0671 (8)
H50.8264−0.31630.74890.081*
C70.9719 (2)−0.4974 (4)0.8216 (2)0.0947 (11)
H7A1.0222−0.47150.78180.142*
H7B0.9230−0.57620.79950.142*
H7C1.0049−0.54700.86800.142*
O10.70983 (14)0.2246 (2)0.84979 (9)0.0613 (5)
O20.82266 (13)0.2523 (2)0.96766 (10)0.0584 (5)
O30.67103 (11)0.06829 (18)0.97377 (8)0.0431 (4)
O40.82359 (15)0.2326 (3)1.16921 (12)0.0810 (6)
O50.79512 (14)−0.0046 (3)1.10830 (11)0.0644 (5)
O60.53013 (16)0.5300 (3)1.25734 (11)0.0738 (6)
O70.38300 (16)0.4246 (3)1.22514 (11)0.0713 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0527 (4)0.0503 (4)0.0362 (3)−0.0065 (3)0.0072 (3)−0.0017 (3)
N20.0698 (15)0.0451 (12)0.0382 (11)0.0054 (11)0.0093 (11)0.0005 (9)
N10.0516 (13)0.0644 (15)0.0372 (11)−0.0010 (12)−0.0001 (9)0.0005 (11)
C80.0473 (13)0.0341 (12)0.0324 (11)−0.0068 (10)0.0055 (10)0.0000 (9)
C90.0447 (13)0.0384 (12)0.0358 (12)−0.0044 (10)0.0001 (10)0.0041 (10)
C100.0582 (15)0.0389 (12)0.0285 (11)−0.0081 (11)0.0000 (10)0.0002 (10)
C110.0532 (14)0.0313 (11)0.0338 (11)−0.0022 (10)0.0087 (10)0.0017 (9)
C120.0485 (13)0.0300 (11)0.0364 (12)−0.0069 (10)0.0043 (10)0.0048 (9)
C130.0446 (13)0.0309 (11)0.0344 (11)−0.0090 (10)0.0013 (10)0.0028 (9)
C140.0521 (14)0.0383 (13)0.0485 (14)−0.0017 (11)0.0078 (11)0.0060 (11)
C150.0448 (14)0.0490 (14)0.0566 (15)−0.0038 (11)−0.0045 (12)0.0106 (13)
C160.0564 (15)0.0488 (14)0.0427 (13)−0.0126 (12)−0.0088 (12)0.0061 (11)
C170.0517 (14)0.0394 (12)0.0352 (12)−0.0088 (11)0.0001 (10)0.0011 (10)
C10.0405 (13)0.0579 (15)0.0420 (13)−0.0071 (11)0.0076 (11)−0.0057 (11)
C40.0484 (15)0.0653 (18)0.078 (2)−0.0063 (14)0.0158 (14)−0.0175 (16)
C20.0531 (16)0.087 (2)0.0578 (16)0.0052 (15)−0.0036 (13)−0.0213 (15)
C30.0555 (17)0.089 (2)0.079 (2)0.0164 (16)−0.0041 (15)−0.0103 (18)
C60.0564 (16)0.0690 (18)0.0496 (15)0.0026 (14)0.0009 (12)−0.0111 (13)
C50.0612 (17)0.076 (2)0.0641 (18)−0.0081 (15)0.0040 (14)−0.0264 (16)
C70.075 (2)0.077 (2)0.133 (3)0.0067 (18)0.022 (2)−0.028 (2)
O10.0794 (12)0.0660 (12)0.0387 (9)0.0039 (9)0.0059 (9)0.0086 (8)
O20.0630 (11)0.0584 (11)0.0539 (10)−0.0189 (9)0.0080 (8)−0.0100 (9)
O30.0514 (9)0.0404 (9)0.0377 (8)−0.0031 (7)0.0076 (7)−0.0054 (7)
O40.0617 (12)0.1075 (17)0.0734 (13)−0.0049 (11)−0.0180 (11)−0.0267 (12)
O50.0660 (12)0.0632 (12)0.0640 (12)0.0149 (10)−0.0005 (9)0.0042 (10)
O60.0898 (15)0.0723 (13)0.0593 (12)0.0021 (11)0.0009 (11)−0.0308 (10)
O70.0664 (13)0.0885 (15)0.0596 (12)0.0031 (11)0.0229 (10)−0.0065 (10)
Geometric parameters (Å, °) top
S1—O11.4179 (17)C14—H140.9300
S1—O21.4196 (16)C15—C161.399 (3)
S1—O31.6287 (16)C15—H150.9300
S1—C11.736 (3)C16—C171.358 (3)
N2—O71.216 (3)C16—H160.9300
N2—O61.224 (3)C17—H170.9300
N2—C111.476 (3)C1—C61.377 (3)
N1—O41.216 (3)C1—C21.381 (3)
N1—O51.216 (3)C4—C51.376 (4)
N1—C91.467 (3)C4—C31.382 (4)
C8—C91.370 (3)C4—C71.509 (4)
C8—O31.388 (2)C2—C31.378 (4)
C8—C131.416 (3)C2—H20.9300
C9—C101.397 (3)C3—H30.9300
C10—C111.346 (3)C6—C51.373 (4)
C10—H100.9300C6—H60.9300
C11—C121.423 (3)C5—H50.9300
C12—C141.411 (3)C7—H7A0.9600
C12—C131.429 (3)C7—H7B0.9600
C13—C171.417 (3)C7—H7C0.9600
C14—C151.356 (3)
O1—S1—O2118.91 (11)C14—C15—H15119.5
O1—S1—O3107.20 (10)C16—C15—H15119.5
O2—S1—O3107.24 (9)C17—C16—C15120.6 (2)
O1—S1—C1110.71 (11)C17—C16—H16119.7
O2—S1—C1112.01 (11)C15—C16—H16119.7
O3—S1—C198.58 (10)C16—C17—C13120.2 (2)
O7—N2—O6124.1 (2)C16—C17—H17119.9
O7—N2—C11119.1 (2)C13—C17—H17119.9
O6—N2—C11116.7 (2)C6—C1—C2120.4 (2)
O4—N1—O5124.4 (2)C6—C1—S1119.9 (2)
O4—N1—C9116.8 (2)C2—C1—S1119.70 (19)
O5—N1—C9118.8 (2)C5—C4—C3117.8 (3)
C9—C8—O3121.7 (2)C5—C4—C7121.3 (3)
C9—C8—C13120.4 (2)C3—C4—C7120.9 (3)
O3—C8—C13117.89 (18)C3—C2—C1119.2 (3)
C8—C9—C10120.6 (2)C3—C2—H2120.4
C8—C9—N1123.7 (2)C1—C2—H2120.4
C10—C9—N1115.71 (19)C2—C3—C4121.4 (3)
C11—C10—C9119.6 (2)C2—C3—H3119.3
C11—C10—H10120.2C4—C3—H3119.3
C9—C10—H10120.2C5—C6—C1119.2 (3)
C10—C11—C12123.4 (2)C5—C6—H6120.4
C10—C11—N2114.8 (2)C1—C6—H6120.4
C12—C11—N2121.7 (2)C6—C5—C4122.0 (3)
C14—C12—C11125.6 (2)C6—C5—H5119.0
C14—C12—C13118.3 (2)C4—C5—H5119.0
C11—C12—C13116.1 (2)C4—C7—H7A109.5
C8—C13—C17121.0 (2)C4—C7—H7B109.5
C8—C13—C12119.83 (19)H7A—C7—H7B109.5
C17—C13—C12119.1 (2)C4—C7—H7C109.5
C15—C14—C12120.8 (2)H7A—C7—H7C109.5
C15—C14—H14119.6H7B—C7—H7C109.5
C12—C14—H14119.6C8—O3—S1119.58 (13)
C14—C15—C16120.9 (2)
O3—C8—C9—C10−177.46 (19)C11—C12—C14—C15176.7 (2)
C13—C8—C9—C100.0 (3)C13—C12—C14—C15−0.2 (3)
O3—C8—C9—N11.8 (3)C12—C14—C15—C16−0.2 (3)
C13—C8—C9—N1179.21 (19)C14—C15—C16—C170.5 (3)
O4—N1—C9—C8143.2 (2)C15—C16—C17—C13−0.3 (3)
O5—N1—C9—C8−38.6 (3)C8—C13—C17—C16−179.9 (2)
O4—N1—C9—C10−37.5 (3)C12—C13—C17—C16−0.1 (3)
O5—N1—C9—C10140.7 (2)O1—S1—C1—C6−17.0 (2)
C8—C9—C10—C112.9 (3)O2—S1—C1—C6−152.30 (19)
N1—C9—C10—C11−176.4 (2)O3—S1—C1—C695.1 (2)
C9—C10—C11—C12−2.8 (3)O1—S1—C1—C2163.2 (2)
C9—C10—C11—N2175.77 (19)O2—S1—C1—C227.9 (2)
O7—N2—C11—C10−143.1 (2)O3—S1—C1—C2−84.7 (2)
O6—N2—C11—C1034.3 (3)C6—C1—C2—C30.5 (4)
O7—N2—C11—C1235.5 (3)S1—C1—C2—C3−179.7 (2)
O6—N2—C11—C12−147.1 (2)C1—C2—C3—C40.0 (5)
C10—C11—C12—C14−177.1 (2)C5—C4—C3—C2−0.3 (4)
N2—C11—C12—C144.5 (3)C7—C4—C3—C2179.2 (3)
C10—C11—C12—C13−0.1 (3)C2—C1—C6—C5−0.8 (4)
N2—C11—C12—C13−178.59 (19)S1—C1—C6—C5179.4 (2)
C9—C8—C13—C17176.87 (19)C1—C6—C5—C40.6 (4)
O3—C8—C13—C17−5.6 (3)C3—C4—C5—C60.0 (4)
C9—C8—C13—C12−2.9 (3)C7—C4—C5—C6−179.5 (3)
O3—C8—C13—C12174.60 (17)C9—C8—O3—S1−80.6 (2)
C14—C12—C13—C8−179.86 (19)C13—C8—O3—S1101.93 (19)
C11—C12—C13—C83.0 (3)O1—S1—O3—C8−86.68 (17)
C14—C12—C13—C170.3 (3)O2—S1—O3—C842.07 (17)
C11—C12—C13—C17−176.83 (19)C1—S1—O3—C8158.41 (16)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O50.932.553.194 (3)127
C14—H14···O70.932.332.895 (3)119
C17—H17···O30.932.482.798 (3)100
C10—H10···O1i0.932.453.327 (3)157
Symmetry codes: (i) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O50.932.553.194 (3)127
C14—H14···O70.932.332.895 (3)119
C17—H17···O30.932.482.798 (3)100
C10—H10···O1i0.932.453.327 (3)157
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

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

references
References top

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Manivannan, V., Vembu, N., Nallu, M., Sivakumar, K. & Fronczek, F. R. (2005b). Acta Cryst. E61, o242–o244.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Yachi, K., Sugiyama, Y., Sawada, Y., Iga, T., Ikeda, Y., Toda, G. & Hananon, M. (1989). Biochim. Biophys. Acta, 978, 1–7.