2-(4,5-Di­chloro-2-nitro­phen­yl)-4-meth­oxy-3-methyl-9-phenyl­sulfon­yl-9H-carbazole

P Narayanan; K Sethusankar; Velu Saravanan; Arasambattu K Mohanakrishnan

doi:10.1107/S1600536814001342

. 2014 Jan 29;70(Pt 2):o212–o213. doi: 10.1107/S1600536814001342

2-(4,5-Dichloro-2-nitrophenyl)-4-methoxy-3-methyl-9-phenylsulfonyl-9H-carbazole

P Narayanan ^a, K Sethusankar ^a,^*, Velu Saravanan ^b, Arasambattu K Mohanakrishnan ^b

PMCID: PMC3998356 PMID: 24764917

Abstract

In the title compound, C₂₆H₁₈Cl₂N₂O₅S, the carbazole ring system is essentially planar with a maximum deviation of 0.0498 (16) Å for the N atom. The carbazole ring system is almost orthogonal to the phenylsulfonyl and dichloro-substituted nitrophenyl rings, making dihedral angles of 84.23 (7) and 85.46 (12)°, respectively. The molecular structure features intramolecular C—H⋯O interactions, which generate two S(6) ring motifs. In the crystal, molecules are linked by C—Cl⋯O halogen bonds [3.016 (3) Å, 166.63 (5)°], which generate infinite C(8) chains running parallel to [010].

Related literature

For the biological activity and uses of carbazole derivatives, see: Itoigawa et al. (2000 ▶); Ramsewak et al. (1999 ▶). For their electronic properties and applications, see: Friend et al. (1999 ▶); Zhang et al. (2004 ▶). For a related structure, see: Gopinath et al. (2013 ▶). For the Thorpe–Ingold effect, see: Bassindale et al. (1984 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). graphic file with name e-70-0o212-scheme1.jpg

Experimental

Crystal data

C₂₆H₁₈Cl₂N₂O₅S
M _r = 541.39
Monoclinic,
a = 18.6364 (7) Å
b = 12.1665 (4) Å
c = 21.1272 (7) Å
β = 91.461 (2)°
V = 4788.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 296 K
0.25 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.905, T _max = 0.923
23543 measured reflections
5218 independent reflections
4056 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.112
S = 1.03
5218 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814001342/rk2420sup1.cif

e-70-0o212-sup1.cif^{(31KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001342/rk2420Isup2.hkl

e-70-0o212-Isup2.hkl^{(250.4KB, hkl)}

Click here for additional data file.^{(8.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814001342/rk2420Isup3.cml

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=952293

Additional supporting information: 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⋯O2	0.93	2.33	2.915 (3)	121
C11—H11⋯O1	0.93	2.36	2.955 (2)	122

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Acknowledgments

The authors thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

1. Comment

Carbazole and its derivative have become quite attractive compounds owing to their applications in pharmacy and molecular electronics. It has been reported that carbazole derivatives exhibit various biological activities such as antitumor (Itoigawa et al., 2000), anti-inflammatory and antimutagenic (Ramsewak et al., 1999). Carbazole derivatives also exhibit electroactivity and luminenscence and are considered to be potential candidates for electronic applications such as colour displays, organic semiconductors, laser and solar cells (Friend et al., 1999; Zhang et al., 2004).

The title compound, C₂₆H₁₈Cl₂N₂O₅S, comprises a carbazole ring system which is attached to a phenylsulfonyl ring, a dichloro substituted nitrophenyl ring, a methoxy group and a methyl group. The carbazole ring system is essentially planar with maximum deviation of 0.0498 (16)Å for the nitrogen atom (N1). The methyl group carbon atom (C25) deviates from the carbazole ring by -0.0866 (22)Å. The carbazole ring system is almost orthogonal to phenyl ring attached to sulfonyl group and nitrophenyl ring with dihedral angles of 84.23 (7)° and 85.46 (12)°, respectively.

The atom S1 has a distorted tetrahedral configuration. The widening of angle O2—S1—O1 [120.21 (10)°] and narrowing of angle N1—S1—C19 [105.23 (9)°] from the ideal tetrahedral value are attributed to the Thorpe–Ingold effect (Bassindale et al., 1984). As a result of electron-withdrawing character of the phenylsulfonyl group, the bond lengths N1—C1 = 1.426 (2)Å and N1—C12 = 1.418 (2)Å in the molecule are longer than the mean value of 1.355 (14)Å (Allen et al. 1987). The sum of the bond angles around N1 [353.9°] indicate the sp² hybridization. The chlorine atoms Cl1 & Cl2 are significantly deviated by 0.1037 (6)Å and -0.0586 (5)Å, respectively from the phenyl ring (C13–C18).

The molecular structure is stabilized by C2—H2···O2, C11—H11···O1 intramolecular interactions, which generate two S(6) ring motifs (Fig. 1). In the crystal packing, molecules are linked by C15—Cl1···O5ⁱ intermolecular halogen bonding (XB), between the chlorine atom (Cl1) and methoxy group oxygen atom (O5) of the carbazole ring system [Cl1···O5ⁱ = 3.016 (3)Å and C15—Cl1···O5ⁱ angle of 166.63 (2)°], which generate C(8) infinite one dimensional chain running parallel to base vector [0 1 0] (Bernstein et al., 1995). The packing view of the title compound is shown in Fig. 2. Symmetry code: (i) 1/2-x, 1/2+y, 3/2-z.

2. Experimental

A mixture of (E)-1-(2-(4,5-dichloro-2-nitrostyryl)-1-(phenylsulfonyl)- 1H-indol-3-yl)-2-(phenylsulfonyl)propan-1-one (4.0 g, 6 mmol), dimethylsulfate (2.86 ml, 30 mmol) and K₂CO₃ (8.28 g, 60 mmol) in tetrahydrofuran (100 ml) was stirred at room temperature for 18 h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (100 g). The solid obtained was filtered and dried (CaCl₂) to give enol ether. Then, the crued enol ether was dissolved in xylenes (100 ml) and refluxed for 24 h. Removal of xylenes in vacuo followed by column chromatographic purification (silica gel; hexane–ethyl acetate, 8:2) gave 9-(phenylsulfonyl)-2-(4,5-dichloro-2-nitrophenyl)-4-methoxy-3-methyl- 9H-carbazole (2.17 g, 67%) as a colourless solid. Single crystal suitable for X–ray diffraction were prepared by slow evaporation of a solution of the title compound in chloroform (CHCl₃) at room temperature. M.p. 493–495 K.