2-Azido­methyl-3-methyl-1-phenyl­sulfonyl-1H-indole

S Karthikeyan; K Sethusankar; Ganesan Gobi Rajeswaran; Arasambattu K Mohanakrishnan

doi:10.1107/S1600536811030601

. 2011 Aug 6;67(Pt 9):o2245–o2246. doi: 10.1107/S1600536811030601

2-Azidomethyl-3-methyl-1-phenylsulfonyl-1H-indole

S Karthikeyan ^a, K Sethusankar ^a,^*, Ganesan Gobi Rajeswaran ^b, Arasambattu K Mohanakrishnan ^b

PMCID: PMC3200696 PMID: 22065043

Abstract

In the title compound, C₁₆H₁₄N₄O₂S, the plane of the indole ring is twisted by 70.4 (2)° with respect to the plane of the azidomethyl substituent. As a result of the electron-withdrawing character of the phenylsulfonyl groups, the N—C bond lengths are slightly longer than the anticipated value of approximately 1.355 Å for an N atom with a planar configuration. The indole ring is essentially planar, with a maximum deviation of 0.0296 Å. The azide group is almost linear, the N—N—N angle being 171.4 (3)°. The methyl group on the azide-substituted C atom is in a flagpole position. The phenyl ring of the sulfonyl substituent makes a dihedral angle of 87.07 (10)° with the best plane of the indole moiety. The crystal packing is stabilized by intermolecular C—H⋯O interactions, which link the molecules into infinite chains running parallel to the b axis. The crystal packing is further stabilized by C—H⋯π interactions.

Related literature

For the biological activity of compounds containing an indole ring system, sulfur and azides, see: Williams et al. (1993 ▶); Amblard et al. (2009 ▶); De-Benedetti et al. (1985 ▶). For related structures, see: Fernandes et al. (2005 ▶). For comparison of molecular dimensions, see: Bassindale (1984 ▶); Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₄N₄O₂S
M _r = 326.38
Orthorhombic,
a = 11.0337 (4) Å
b = 12.1424 (4) Å
c = 23.2234 (9) Å
V = 3111.37 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 295 K
0.30 × 0.25 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
37510 measured reflections
4231 independent reflections
2776 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.166
S = 0.99
4231 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811030601/rk2287sup1.cif

e-67-o2245-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030601/rk2287Isup2.hkl

e-67-o2245-Isup2.hkl^{(203.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811030601/rk2287Isup3.cml

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

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

Cg3 is the centroid of the C11–C16 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O1ⁱ	0.93	2.46	3.322 (3)	154
C5—H5⋯Cg3ⁱⁱ	0.93	2.89	3.714 (3)	148

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

SK and KS thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X–ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, RKM Vivekananda College, for providing facilities in the department for carrying out this work.

supplementary crystallographic information

Comment

The phenylsulfonyl indole compounds inhibit the HIV–1 RT enzyme in vitro and HTLVIIIb viral spread in MT–4 human T–lymphoid cells (Williams, et al., 1993). The Cu(I)–catalyzed 1,3–dipolar cycloaddition reaction between alkynes and azides has been suitable for the synthesis of a large number of modified nucleosides, nucleotides and oligonucleotides with a broad range of applications (Amblard et al., 2009). A lot of sulfur containing compounds, exhibit insecticidal, germicidal, antimicrobial and antibacterial activities (De-Benedetti et al., 1985).

In the title compound C₁₆H₁₄N₄O₂S, the molecular conformation (Fig. 1) is preferred with the plane of indole ring twisted by 70.4 (2)° with respect to the plane of the azido group bound to the methyl substituent. The indole ring is essentially planar with a maximum deviation 0.0296 (17)Å for the atom N1. The bond angle around N3, in the chain of atom N2–N3–N4, is 171.4 (3)° and thus the azidomethyl side chain is almost linear. The methyl group on the azide substituted C atom is in a flag pole position.

The phenyl ring of the sulfonyl substituent makes a dihedral angle of 87.07 (10)° with the indole moiety. The deviation of atoms S1 and C10 from the indole mean plane is 0.453 (5)Å and -0.0618 (24)Å, respectively. As a result of electron–withdrawing character of the phenylsulfonyl group, the bond lengths N1—C8 = 1.432 (2)Å and N1—C1 = 1.416 (2)Å in the molecule are longer than the mean value of 1.355 (14)Å (Allen et al., 1987). Due to Thorpe–Ingold effect (Bassindale, 1984), bond angles around atom S1 show significant deviations from the ideal tetrahedral value, with significant deviations, widening of angle O1═S1═O2 = 119.71 (10)° and narrowing of angle N1—S1—C11 = 105.36 (8)°. The title molecule exhibits structural similarities with the already reported related structure (Fernandes et al., 2005).

In crystal packing, the molecule is stabilized by intermolecular C—H···O interactions which link the molecules into infinite chains running parallel to b axis. The crystal packing is further stabilized by C—H···π interaction, where Cg3 is centroid of C11–C16. The symmetry codes: (i) -1/2-x, 1/2+y, z; (ii) -x, 1-y, 1-z. The packing view of the title compound is shown in the Fig. 2.

Experimental

To a solution of 2–(bromomethyl)–3–methyl–1–phenylsulfonyl–indole (1 mmol) in DMF (3 ml) was added sodium azide (2 mmol) and stirred for 2 h at room temperature. After consumption of the 2–(bromomethyl)–3–methyl–1–phenylsulfonyl–indole (monitored by TLC), reaction mass was poured into ice water (20 ml). The solid obtained was filtered and dried (CaSO₄). Then the crude product was recrystalized with MeOH (5 ml) afforded the 2–(azidomethyl)–3–methyl–1–phenylsulfonyl–indole as a colourless solid. Yield: 0.28 g (92%).