9-(4-Nitro­phenyl­sulfon­yl)-9H-carbazole

Nesimi Uludağ; Murat Ateş; Barış Tercan; Tuncer Hökelek

doi:10.1107/S1600536811017818

. 2011 May 14;67(Pt 6):o1428–o1429. doi: 10.1107/S1600536811017818

9-(4-Nitrophenylsulfonyl)-9H-carbazole

Nesimi Uludağ ^a, Murat Ateş ^a, Barış Tercan ^b, Tuncer Hökelek ^c,^*

PMCID: PMC3120556 PMID: 21754808

Abstract

In the title molecule, C₁₈H₁₂N₂O₄S, the carbazole skeleton is nearly planar [maximum deviation = 0.037 (1) Å] and is oriented at a dihedral angle of 73.73 (5)° with respect to the benzene ring. An intramolecular C—H⋯O hydrogen bond links a nitro O atom to the carbazole skeleton. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between inversion-related benzene rings [centroid–centroid distance = 3.7828 (8) Å] and two weak C—H⋯π interactions may also stabilize the structure.

Related literature

For tetrahydrocarbazole systems present in the framework of a number of indole-type alkaloids of biological interest, see: Saxton (1983 ▶). For related structures, see: Hökelek et al. (1994 ▶, 1998, ▶ 1999) ▶; Patır et al. (1997 ▶); Hökelek & Patır (1999 ▶). For the role of carbazole-based compounds in electroactive materials, see: Morin et al. (2004 ▶); Pasquali et al. (1993 ▶). For applications of chemically or electrochemically polymerized carbazole-based heterocyclic polymer systems, see: Sacak (1999 ▶); Santhanam & Sundaresan (1986 ▶).

Experimental

Crystal data

C₁₈H₁₂N₂O₄S
M _r = 352.37
Monoclinic,
a = 7.4877 (2) Å
b = 11.7612 (3) Å
c = 17.3744 (4) Å
β = 90.119 (2)°
V = 1530.06 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.921, T _max = 0.943
26862 measured reflections
3824 independent reflections
3269 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.06
3824 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017818/su2273sup1.cif

e-67-o1428-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017818/su2273Isup2.hkl

e-67-o1428-Isup2.hkl^{(183.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017818/su2273Isup3.cml

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

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

Cg2 and Cg3 are the centroids of the C1–C4/C4A/C9A and C5A/C5–C8/C8A rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1	0.95	2.43	3.0210 (18)	121
C6—H6⋯O2ⁱ	0.95	2.57	3.4085 (19)	147
C14—H14⋯O2ⁱⁱ	0.95	2.46	3.2731 (18)	143
C1—H1⋯Cg3ⁱⁱⁱ	0.95	2.94	3.7368 (15)	142
C12—H12⋯Cg2^iv	0.95	2.71	3.4376 (15)	134

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the X-ray diffractometer. This work was supported financially by the Scientific & Technological Research Council of Turkey (grant No. TUBITAK-110T516).

supplementary crystallographic information

Comment

Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Saxton, 1983). The structures of tricyclic, tetracyclic and pentacyclic ring systems with dithiolane and other substituents of the tetrahydrocarbazole core, have been reported previously (Hökelek et al., 1994; Patır et al., 1997; Hökelek et al., 1998; Hökelek et al., 1999; Hökelek & Patır, 1999). Carbazole-based compounds play a very important role in electroactive materials (Morin et al., 2004; Pasquali et al., 1993). Carbazole-based heterocyclic polymer systems can be chemically or electrochemically polymerized to give products with a number of applications, such as rechargable batteries (Sacak, 1999) and electrochromic displays (Santhanam & Sundaresan, 1986). The title compound may be considered as a synthetic precursor of tetracyclic indole alkaloids of biological interests. The present study was undertaken to ascertain its crystal structure.

The title compound consists of a carbazole skeleton with a nitrophenylsulfonyl group (Fig. 1), where the bond lengths and angles are within normal ranges, and generally agree with those in the previously reported compounds mentioned above. In all structures atom N9 is substituted.

An examination of the deviations from the least-squares planes through individual rings shows that rings A (C1—C4/C4a/C9a), B (C4a/C5a/C8a/N9/C9a), C (C5a/C5—C8/C8a) and D (C10—C15) are planar. The carbazole skeleton, containing the rings A, B and C is also nearly coplanar [maximum deviation 0.037 (1) Å for atom C5] with dihedral angles of A/B = 1.10 (7), A/C = 1.94 (7) and B/C = 1.85 (7) °. The phenyl ring is oriented with respect to the carbazole skeleton at a dihedral angle of 73.73 (5)°. Atoms S1 and N10 are displaced by 0.095 (1) and 0.026 (1) Å, respectively, from the phenyl ring mean plane. The intramolecular C—H···O hydrogen bond (Table 1) links the nitro oxygen (O1) to the carbazole skeleton.

In the crystal intermolecular C—H···O hydrogen bonds link the molecules into a three dimensional network (Table 1 and Fig. 2). The π–π contacts between the phenyl rings, Cg4—Cg4ⁱ [symmetry code: (i) 1 - x, 1 - y, -z, where Cg4 is the centroid of ring D (C10—C15)] may stabilize the structure, with a centroid-centroid distance of 3.7828 (8) Å, with perpendicular separation of 3.5543 (5) Å and a slipage of 1.295 Å. There also exist two weak C—H···π interactions involving rings A [Cg2 centroid of ring (C1—C4/C4a/C9a)] and C [Cg3 centroid of ring (C5a/C5—C8/C8a)], see Table 1.

Experimental

For the preparation of the title compound, carbazole (3.0 g, 19.45 mmol) and 4-nitrobenzene-1-sulfonyl chloride (8.6 g, 38.91 mmol) were dissolved in dichloromethane (300 ml), and then tetramethyl ammonium hydrogen sulphate (0.3 g) and sodium hydroxide (40 ml, 50%) were added. The resulting mixture was stirred at room temperature for 24 h. It was then poured into water (200 ml) and dichloromethane (200 ml). The solvent was evaporated and the residue was purified by column chromatograpy using silica gel, and the product was crystallized from ethylacetate (yield; 4.2 g, 75.12%, m.p. 466 K).