3-Bromo­methyl-4-meth­oxy-2-(2-nitro­phen­yl)-9-phenyl­sulfonyl-9H-carbazole

S Gopinath; K Sethusankar; Velu Saravanan; Arasambattu K Mohanakrishnan

doi:10.1107/S160053681401143X

. 2014 May 24;70(Pt 6):o707–o708. doi: 10.1107/S160053681401143X

3-Bromomethyl-4-methoxy-2-(2-nitrophenyl)-9-phenylsulfonyl-9H-carbazole

S Gopinath ^a, K Sethusankar ^a,^*, Velu Saravanan ^b, Arasambattu K Mohanakrishnan ^b

PMCID: PMC4050995 PMID: 24940279

Abstract

In the title compound, C₂₆H₁₉BrN₂O₅S, the carbazole tricycle is essentially planar, with the largest deviation being 0.126 (3) Å for the C atom connected to the nitrophenyl group. The carbazole moiety is almost orthogonal to the benzene rings of the adjacent phenylsulfonyl and nitrophenyl groups, making dihedral angles of 85.43 (15) and 88.62 (12)°, respectively. The molecular conformation is stabilized by two C—H⋯O hydrogen bonds involving the sulfone group, which form similar six-membered rings. In the crystal, molecules symmetrically related by a glide plane are linked in C(6) chains parallel to [001] by C—H⋯O hydrogen bonds formed with the participation of the nitro group. The chains are reinforced by additional C—H⋯π interactions.

Related literature

For the uses and biological importance of carbazoles, see: Itoigawa et al. (2000 ▶); Ramsewak et al. (1999 ▶). For electronic properties and applications, see: Friend et al. (1999 ▶); Zhang et al. (2004 ▶). For related structures, see: Narayanan et al. (2014 ▶); Gopinath et al. (2014 ▶). For the Thorpe–Ingold effect, see: Bassindale (1984 ▶). For bond-length distortions, see: Allen et al. (1987 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₆H₁₉BrN₂O₅S
M _r = 551.40
Monoclinic,
a = 10.3176 (4) Å
b = 14.4431 (6) Å
c = 15.4901 (6) Å
β = 92.329 (2)°
V = 2306.40 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.92 mm⁻¹
T = 296 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.901, T _max = 0.905
28756 measured reflections
6652 independent reflections
3939 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.161
S = 1.03
6652 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.74 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/S160053681401143X/ld2127sup1.cif

e-70-0o707-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401143X/ld2127Isup2.hkl

e-70-0o707-Isup2.hkl^{(325.6KB, hkl)}

Click here for additional data file.^{(8.5KB, cml)}

Supporting information file. DOI: 10.1107/S160053681401143X/ld2127Isup3.cml

CCDC reference: 1003645

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3	0.93	2.34	2.941 (4)	122
C9—H9⋯O4	0.93	2.32	2.925 (4)	122
C23—H23⋯O1ⁱ	0.93	2.53	3.264 (4)	136
C22—H22⋯Cg1ⁱⁱ	0.93	2.95	3.810 (4)	155

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

Acknowledgments

SG and KS thank Dr Babu Varghese, Senior Scientific Officer, SAIF, IIT, Madras, India for the data collection.

supplementary crystallographic information

1. Comment

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

The title compound, Fig. 1, comprises a carbazole ring system which is attached to a phenylsulfonyl group, a nitrophenyl, a methoxy and a bromomethyl group. The carbazole ring system is essentially planar with maximum deviation of -0.126 (3) Å for the carbon atom C10. The oxygen atom O5 significantly deviates from the carbazole ring by 0.1560 (22) Å. The carbazole ring is almost orthagonal to phenyl ring attached to sulfonyl group and nitrophenyl ring with dihedral angles of 85.43 (15)° and 88.62 (12)°, respectively.

As a result of electron-withdrawing character of phenysulfonyl group, the bond lengths N1–C1 = 1.424 (4) Å and N1–C8 = 1.430 (3) Å in the molecule are longer than the mean value of 1.355 (14) Å (Allen, et al. 1987). The atom S1 has a distorted tetrahedral configuration. The widening of angle O3—S1—O4 [120.22 (15)°] and narrowing angle N1—S1—C14 [104.44 (13)°] from the ideal tetrahedral value are attributed to the Thorpe-Ingold effect (Bassindale, et al. 1984).

The sum of the bond angles around N1 [353.6°] indicate the sp² hybridization. The nitrogen atom N2 is almost in the plane of phenyl ring with the torsional angle of C21–C20–C25–N2 = -179.6 (3)°. The bromine atom forms the torsional angle of C10– C11–C26–Br1 = 88.1 (3)°.

The molecular structure is stabilized by C—H···O hydrogen bonds (Table 1 Fig. 1), which generate two S(6) ring motifs. In the crystal packing, molecules are linked via C23—H23···O1ⁱ intermolecular hydrogen bonding, which generate C(6) infinite chains running parallel to the base vector [0 0 1]. The crystal packing is further stabilized by C22—H22···Cg1ⁱⁱ intermolecular interaction, where the Cg1 is the centre of gravity of the benzene ring(C7–C12) (Bernstein, et al. 1995). The packing view of the title compound shown in the Fig-2 and Fig-3. The symmetry codes are: (i) x, -y + 1/2 + 1, +z - 1/2 (ii) x, 3/2 - y, -1/2 + z

2. Experimental

A mixture of 4-methoxy-3-methyl-2-(2-nitrophenyl)-9- (phenylsulfonyl)-9H-carbazole(1.65 g, 3.5 mmol) and NBS(0.93 g, 5.25 mmol) in dry CCl4(100 ml) containing a catalytic amount of AIBN(50 mg) was refluxed for 1 h. Then, it was cooled to room temperature and the additional equivalent of NBS(0.93 g, 5.25 mmol) and AIBN(50 mg) were added and allowed to reflux for 1 h. Then the reaction mixture was cooled to room temperature and the floated succinimide was filtered off through Na2So4 pad and washed with hot CCl4 (20 ml). The subsequent removal of solvent in vacuo followed by tituration of the crude product with MeOH(10 ml) afforded 3-(bromomethyl)-4-methoxy-2-(2-nitrophenyl)-9-(phenylsulfonyl) -9Hcarbazole(1.71 g, 89%) as a dull white solid. Single crystals suitable for X-ray diffraction was prepared by slow evapouration of a solution of the title compound in methanol at room temperature.

m.p. = 483 K–485 K.