Crystal structure of 3-bromo-9-ethyl-9H-carbazole

Mykola Bezuglyi; Gintare Grybauskaite; Gintautas Bagdziunas; Juozas Vidas Grazulevicius

doi:10.1107/S2056989015023907

. 2015 Dec 19;71(Pt 12):o1067–o1068. doi: 10.1107/S2056989015023907

Crystal structure of 3-bromo-9-ethyl-9H-carbazole

Mykola Bezuglyi ^a,^*, Gintare Grybauskaite ^b, Gintautas Bagdziunas ^b, Juozas Vidas Grazulevicius ^b

PMCID: PMC4719982 PMID: 26870501

Abstract

In the title compound, C₁₄H₁₂BrN, the tricyclic ring system is essentially planar (r.m.s. deviation 0.026 Å). The carbon atoms of the ethyl group deviate from the mean plane by 0.148 (9) (CH₂) and 1.59 (1) Å (CH₃). In the crystal, H⋯π contacts [2.698–2.898 Å] shorter than the van der Waals contact distance of 3.70 Å are observed. A scalable to gram quantities selective synthesis of mono-bromine-substituted carbazole derivatives was developed.

Keywords: crystal structure, carbazole, C—H⋯π interactions

Related literature

N-substituted carbazole derivatives are important for anti-cancer research (Caulfield et al., 2002 ▸) and as materials for opto-electronic devices (Niu et al., 2011 ▸; Miyazaki et al., 2014 ▸; Grigalevicius et al., 2002 ▸). The crystal structure of 1,3,6,8-tetrabromo-9-ethyl-9H-carbazole was reported by Bezuglyi et al. (2015 ▸). graphic file with name e-71-o1067-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₂BrN
M _r = 274.16
Orthorhombic,
a = 15.263 (16) Å
b = 7.745 (8) Å
c = 20.41 (2) Å
V = 2413 (5) Å³
Z = 8
Mo Kα radiation
μ = 3.39 mm⁻¹
T = 293 K
0.40 × 0.09 × 0.08 mm

Data collection

Rigaku XtaLAB mini diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▸) T _min = 0.450, T _max = 0.763
8316 measured reflections
2721 independent reflections
1383 reflections with F ² > 2.0σ(F ²)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.078
wR(F ²) = 0.236
S = 1.05
2721 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku, 2011 ▸); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; 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 ▸); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S2056989015023907/nk2233sup1.cif

e-71-o1067-sup1.cif^{(22KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023907/nk2233Isup2.hkl

e-71-o1067-Isup2.hkl^{(133.7KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015023907/nk2233Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015023907/nk2233fig1.tif

The molecular structure of the title molecule with displacement ellipsoids drawn at the 50% probability level.

CCDC reference: 1442215

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

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

Cg1 are the centroids of the N1/C1/C6/C7/C12 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯Cg1ⁱ	0.93	2.81	3.637 (7)	149
C11—H11⋯Cg2ⁱⁱ	0.93	3.01	3.922 (8)	167

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

Acknowledgments

This research was supported by FP7 REGPOT-2012–2013-1 ICT project CEOSeR under grant agreement No 316010. The authors are grateful to Dr Vasyl Kinzhybalo from the Institute of Low Temperature and Structure Research, Polish Academy of Sciences, for valuable recommendations.

supplementary crystallographic information

S1. Synthesis and crystallization

9-ethyl-carbazole (1.00 g, 5.12 mmol) was added to a solution of N-bromosuccinimide (0.911 g, 5.12 mmol) in 10 ml of DMF. The reaction mixture was refluxed at room temperature for 24 h. When the reaction was completed (monitored via TLC) the solution was poured into a large amount of water with ice and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate followed by solvent evaporation in rotary evaporator. The product was crystallized from methanol to afford a white needle-like crystals. Yield: 0.88 g (62%), melting point 58–60°C. ¹H NMR (700 MHz, CDCl₃) δ 8.10 (d, J = 7.7 Hz, 1H), 7.63 (d, J = 2.5 Hz, 1H), 7.49 (ddd, J = 8.2, 7.1, 1.1 Hz, 1H), 7.42 (d, J = 8.2 Hz, 1H), 7.35 (d, J = 8.7 Hz, 1H), 7.25 – 7.22 (m, 1H), 7.16 (dd, J = 8.8, 2.5 Hz, 1H), 4.37 (q, J = 7.3 Hz, 2H), 1.45 (t, J = 7.3 Hz, 4H).

S2. Refinement

All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.930 Å for aromatic C—H, with 0.969 Å for methylene C—H, 0.957 Å for methyl distances and U_iso(H) = 1.2 U_eq.