Crystal structure of 1,3,6,8-tetra­bromo-9-ethyl-9H-carbazole

Bezuglyi, M.; Grybauskaite, G.; Bagdziunas, G.; Grazulevicius, J.V.

doi:10.1107/S2056989015010117

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 6| June 2015| Page o373

doi:10.1107/S2056989015010117

Open

access

Crystal structure of 1,3,6,8-tetrabromo-9-ethyl-9H-carbazole

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

^aDepartment of Chemistry, National Taras Shevchenko University, 62a Volodymirska st., Kyiv, Ukraine, and ^bDepartment of Polymer Chemistry and Technology, Kaunas University of Technology, Radvilenu Road 19, LT-50254, Kaunas, Lithuania
^*Correspondence e-mail: nikolay_bezugliy@ukr.net

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 16 May 2015; accepted 25 May 2015; online 30 May 2015)

In the title compound, C₁₄H₉Br₄N, the tricyclic ring system is almost planar (r.m.s. deviation for the 13 non-H atoms = 0.017 Å) and the methyl C atom deviates from the mean plane of the ring system by 1.072 (17) Å. In the crystal, Br⋯Br contacts [3.636 (3) and 3.660 (3) Å] slightly shorter than the van der Waals contact distance of 3.70 Å are seen.

Keywords: crystal structure; carbazole; halogen–halogen contact.

CCDC reference: 1402621

1. Related literature

For applications of N-substituted carbazole derivatives in anticancer research, see: Caulfield et al. (2002 ). For their use in optoelectronic devices, see: Niu et al. (2011 ); Miyazaki et al. (2014 ); Grigalevicius et al. (2002 ).

2. Experimental

2.1. Crystal data

C₁₄H₉Br₄N
M_r = 510.85
Monoclinic, P 2₁
a = 4.202 (2) Å
b = 14.654 (6) Å
c = 12.245 (6) Å
β = 92.758 (18)°
V = 753.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 10.70 mm⁻¹
T = 293 K
0.40 × 0.13 × 0.12 mm

2.2. Data collection

Rigaku XtaLAB mini diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ) T_min = 0.115, T_max = 0.277
2755 measured reflections
2599 independent reflections
2071 reflections with F² > 2.0σ(F²)
R_int = 0.021

2.3. Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.130
S = 1.01
2600 reflections
172 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.66 e Å⁻³
Absolute structure: Flack (1983 ), 868 Friedel Pairs
Absolute structure parameter: 0.05 (4)

Data collection: CrystalClear-SM Expert (Rigaku, 2011 ); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalStructure (Rigaku, 2010 ); software used to prepare material for publication: CrystalStructure.

Supporting information

CCDC reference: 1402621

Crystal structure: contains datablocks General, I. DOI: 10.1107/S2056989015010117/hb7428sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010117/hb7428Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015010117/hb7428Isup3.cml

checkCIF report

Synthesis and crystallization top

9-Ethyl-9H-carbazole (0.904 g, 4.63 mmol) was added to the solution of N-bromosuccinimide (NBS) (3.708 g, 20.83 mmol) in 30 ml of DMF. The reaction mixture was heated at 60°C for 24 hours. When the reaction completed (monitored via TLC) the solution was poured into a large amount of water with ice. The precipitate was filtered off and crystallized from the mixture of isopropanol and DMF (volume ratio about 5:1) to isolate the product as needles. The bulk sample appears yellowish, but individual crystals are colourless. Yield 1.80 g (76 %), m.p. 155–156°C. ¹H NMR (700 MHz, CDCl₃) δ 7.92 (d, J = 1.8 Hz, 2H), 7.69 (d, J = 1.8 Hz, 2H), 5.10 (q, J = 7.1 Hz, 2H), 1.33 (t, J = 7.1 Hz, 3H).

Refinement top

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.

Related literature top

For applications of N-substituted carbazole derivatives in anticancer research, see: Caulfield et al. (2002). For their use in optoelectronic devices, see: Niu et al. (2011); Miyazaki et al. (2014); Grigalevicius et al. (2002).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. The molecular structure of the title molecule with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound.
	Fig. 3. C—Br···Br and Br···π intermolecular contacts.

1,3,6,8-Tetrabromo-9-ethyl-9H-carbazole top

Crystal data top

C₁₄H₉Br₄N	F(000) = 480.00
M_r = 510.85	D_x = 2.253 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2yb	Cell parameters from 2306 reflections
a = 4.202 (2) Å	θ = 3.2–27.5°
b = 14.654 (6) Å	µ = 10.70 mm⁻¹
c = 12.245 (6) Å	T = 293 K
β = 92.758 (18)°	Chip, colorless
V = 753.1 (6) Å³	0.40 × 0.13 × 0.12 mm
Z = 2

Data collection top

Rigaku XtaLAB mini diffractometer	2071 reflections with F² > 2.0σ(F²)
Detector resolution: 6.827 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 27.5°
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	h = −5→5
T_min = 0.115, T_max = 0.277	k = −18→18
2755 measured reflections	l = −15→4
2599 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0517P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
2600 reflections	Δρ_max = 0.74 e Å⁻³
172 parameters	Δρ_min = −0.66 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 868 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (4)
Secondary atom site location: difference Fourier map

Crystal data top

C₁₄H₉Br₄N	V = 753.1 (6) Å³
M_r = 510.85	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.202 (2) Å	µ = 10.70 mm⁻¹
b = 14.654 (6) Å	T = 293 K
c = 12.245 (6) Å	0.40 × 0.13 × 0.12 mm
β = 92.758 (18)°

Data collection top

Rigaku XtaLAB mini diffractometer	2599 independent reflections
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	2071 reflections with F² > 2.0σ(F²)
T_min = 0.115, T_max = 0.277	R_int = 0.021
2755 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	H-atom parameters constrained
wR(F²) = 0.130	Δρ_max = 0.74 e Å⁻³
S = 1.01	Δρ_min = −0.66 e Å⁻³
2600 reflections	Absolute structure: Flack (1983), 868 Friedel Pairs
172 parameters	Absolute structure parameter: 0.05 (4)
1 restraint

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	1.0896 (3)	0.54414 (9)	0.00371 (12)	0.0652 (4)
Br2	0.4335 (4)	0.80930 (10)	−0.24666 (11)	0.0710 (4)
Br3	0.3881 (3)	1.05176 (9)	0.38945 (12)	0.0657 (4)
Br4	1.0717 (3)	0.73324 (10)	0.49105 (11)	0.0654 (4)
N1	0.9560 (19)	0.7062 (6)	0.2062 (8)	0.041 (2)
C1	0.854 (3)	0.7148 (7)	0.0995 (9)	0.037 (3)
C2	0.893 (3)	0.6617 (8)	0.0045 (10)	0.046 (3)
C3	0.768 (3)	0.6924 (8)	−0.0998 (10)	0.051 (3)
C4	0.598 (3)	0.7757 (8)	−0.1069 (10)	0.048 (3)
C5	0.556 (3)	0.8265 (7)	−0.0176 (9)	0.042 (3)
C6	0.682 (3)	0.7978 (7)	0.0871 (9)	0.039 (3)
C7	0.671 (3)	0.8383 (7)	0.1907 (9)	0.039 (3)
C8	0.533 (3)	0.9191 (7)	0.2281 (10)	0.044 (3)
C9	0.566 (3)	0.9430 (8)	0.3353 (9)	0.047 (3)
C10	0.729 (3)	0.8854 (8)	0.4117 (10)	0.048 (3)
C11	0.869 (3)	0.8032 (8)	0.3764 (9)	0.046 (3)
C12	0.845 (3)	0.7785 (8)	0.2676 (9)	0.041 (3)
C13	1.178 (3)	0.6333 (8)	0.2518 (11)	0.051 (3)
C14	1.008 (3)	0.5530 (9)	0.2926 (12)	0.067 (4)
H3	0.7995	0.6581	−0.1623	0.0616*
H5	0.4442	0.8811	−0.0240	0.0498*
H8	0.4181	0.9565	0.1791	0.0524*
H10	0.7444	0.9015	0.4852	0.0581*
H13A	1.3166	0.6139	0.1951	0.0616*
H13B	1.3104	0.6590	0.3111	0.0616*
H14A	0.8767	0.5270	0.2342	0.0802*
H14B	0.8768	0.5712	0.3508	0.0802*
H14C	1.1601	0.5084	0.3193	0.0802*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0604 (7)	0.0431 (7)	0.0918 (11)	0.0099 (7)	0.0024 (7)	−0.0126 (7)
Br2	0.0871 (9)	0.0752 (10)	0.0491 (7)	0.0044 (9)	−0.0140 (7)	−0.0013 (7)
Br3	0.0759 (8)	0.0475 (7)	0.0738 (9)	0.0015 (8)	0.0042 (7)	−0.0187 (7)
Br4	0.0710 (9)	0.0678 (9)	0.0557 (8)	−0.0063 (8)	−0.0143 (7)	0.0171 (6)
N1	0.039 (5)	0.037 (5)	0.047 (5)	−0.009 (4)	−0.002 (4)	0.000 (4)
C1	0.034 (5)	0.026 (5)	0.051 (6)	0.003 (5)	0.004 (5)	−0.004 (5)
C2	0.031 (5)	0.040 (6)	0.066 (8)	−0.010 (5)	−0.001 (5)	0.003 (5)
C3	0.052 (6)	0.048 (7)	0.055 (7)	−0.009 (6)	0.007 (5)	−0.017 (6)
C4	0.050 (6)	0.040 (6)	0.054 (7)	−0.013 (6)	0.004 (6)	−0.006 (5)
C5	0.049 (6)	0.020 (5)	0.054 (7)	−0.003 (5)	−0.011 (5)	0.002 (4)
C6	0.037 (5)	0.033 (6)	0.046 (6)	−0.001 (5)	0.005 (4)	−0.002 (5)
C7	0.038 (5)	0.030 (5)	0.048 (6)	−0.017 (5)	0.002 (5)	0.002 (4)
C8	0.049 (6)	0.032 (6)	0.051 (7)	−0.007 (5)	0.001 (5)	0.002 (5)
C9	0.057 (7)	0.048 (6)	0.037 (6)	−0.015 (6)	0.002 (5)	−0.004 (5)
C10	0.054 (6)	0.042 (6)	0.049 (7)	−0.008 (6)	0.002 (6)	−0.007 (5)
C11	0.047 (6)	0.047 (7)	0.043 (6)	−0.012 (6)	−0.009 (5)	0.007 (5)
C12	0.036 (5)	0.041 (6)	0.047 (6)	−0.020 (5)	−0.002 (5)	0.004 (5)
C13	0.039 (6)	0.037 (6)	0.076 (9)	0.002 (5)	−0.019 (6)	0.007 (6)
C14	0.066 (7)	0.030 (6)	0.106 (11)	−0.004 (7)	0.013 (7)	0.018 (7)

Geometric parameters (Å, º) top

Br1—C2	1.912 (11)	C7—C12	1.458 (15)
Br2—C4	1.880 (12)	C8—C9	1.359 (16)
Br3—C9	1.894 (12)	C9—C10	1.412 (16)
Br4—C11	1.906 (11)	C10—C11	1.418 (16)
N1—C1	1.361 (14)	C11—C12	1.379 (15)
N1—C12	1.393 (14)	C13—C14	1.476 (17)
N1—C13	1.507 (14)	C3—H3	0.930
C1—C2	1.415 (16)	C5—H5	0.930
C1—C6	1.418 (14)	C8—H8	0.930
C2—C3	1.429 (17)	C10—H10	0.930
C3—C4	1.417 (16)	C13—H13A	0.970
C4—C5	1.340 (16)	C13—H13B	0.970
C5—C6	1.426 (15)	C14—H14A	0.960
C6—C7	1.404 (15)	C14—H14B	0.960
C7—C8	1.403 (15)	C14—H14C	0.960

Br2···Br4ⁱ	3.660 (3)	Br3···Br4ⁱⁱ	3.636 (3)

C1—N1—C12	110.4 (8)	Br4—C11—C12	125.5 (9)
C1—N1—C13	125.6 (9)	C10—C11—C12	120.3 (10)
C12—N1—C13	123.8 (9)	N1—C12—C7	106.2 (9)
N1—C1—C2	134.0 (9)	N1—C12—C11	135.2 (10)
N1—C1—C6	108.5 (9)	C7—C12—C11	118.5 (10)
C2—C1—C6	117.5 (10)	N1—C13—C14	113.0 (9)
Br1—C2—C1	124.5 (8)	C2—C3—H3	120.413
Br1—C2—C3	114.7 (9)	C4—C3—H3	120.407
C1—C2—C3	120.7 (10)	C4—C5—H5	119.576
C2—C3—C4	119.2 (11)	C6—C5—H5	119.568
Br2—C4—C3	116.3 (9)	C7—C8—H8	119.725
Br2—C4—C5	122.8 (9)	C9—C8—H8	119.729
C3—C4—C5	120.9 (11)	C9—C10—H10	119.964
C4—C5—C6	120.9 (10)	C11—C10—H10	119.962
C1—C6—C5	120.9 (10)	N1—C13—H13A	108.986
C1—C6—C7	107.8 (9)	N1—C13—H13B	108.988
C5—C6—C7	131.3 (9)	C14—C13—H13A	108.984
C6—C7—C8	133.2 (10)	C14—C13—H13B	108.981
C6—C7—C12	106.9 (9)	H13A—C13—H13B	107.779
C8—C7—C12	119.9 (10)	C13—C14—H14A	109.473
C7—C8—C9	120.5 (10)	C13—C14—H14B	109.466
Br3—C9—C8	122.1 (9)	C13—C14—H14C	109.472
Br3—C9—C10	117.2 (9)	H14A—C14—H14B	109.470
C8—C9—C10	120.6 (11)	H14A—C14—H14C	109.470
C9—C10—C11	120.1 (11)	H14B—C14—H14C	109.476
Br4—C11—C10	114.2 (8)

C1—N1—C12—C7	−2.6 (10)	C3—C4—C5—C6	−0.3 (16)
C1—N1—C12—C11	178.7 (10)	C4—C5—C6—C1	−0.2 (15)
C12—N1—C1—C2	−179.2 (9)	C4—C5—C6—C7	−179.9 (9)
C12—N1—C1—C6	3.2 (10)	C1—C6—C7—C8	−179.3 (9)
C1—N1—C13—C14	−92.7 (12)	C1—C6—C7—C12	0.9 (10)
C13—N1—C1—C2	4.9 (16)	C5—C6—C7—C8	0.4 (18)
C13—N1—C1—C6	−172.6 (8)	C5—C6—C7—C12	−179.4 (9)
C12—N1—C13—C14	91.9 (11)	C6—C7—C8—C9	−178.4 (10)
C13—N1—C12—C7	173.4 (8)	C6—C7—C12—N1	1.0 (10)
C13—N1—C12—C11	−5.3 (17)	C6—C7—C12—C11	179.9 (8)
N1—C1—C2—Br1	6.9 (16)	C8—C7—C12—N1	−178.9 (8)
N1—C1—C2—C3	−176.1 (9)	C8—C7—C12—C11	0.1 (14)
N1—C1—C6—C5	177.7 (8)	C12—C7—C8—C9	1.4 (15)
N1—C1—C6—C7	−2.5 (10)	C7—C8—C9—Br3	179.4 (8)
C2—C1—C6—C5	−0.3 (13)	C7—C8—C9—C10	−2.4 (16)
C2—C1—C6—C7	179.4 (8)	Br3—C9—C10—C11	−179.7 (7)
C6—C1—C2—Br1	−175.7 (7)	C8—C9—C10—C11	2.0 (16)
C6—C1—C2—C3	1.3 (13)	C9—C10—C11—Br4	−178.9 (9)
Br1—C2—C3—C4	175.5 (7)	C9—C10—C11—C12	−0.5 (16)
C1—C2—C3—C4	−1.7 (15)	Br4—C11—C12—N1	−3.7 (17)
C2—C3—C4—Br2	−178.4 (8)	Br4—C11—C12—C7	177.7 (6)
C2—C3—C4—C5	1.2 (16)	C10—C11—C12—N1	178.1 (10)
Br2—C4—C5—C6	179.4 (6)	C10—C11—C12—C7	−0.5 (15)

Symmetry codes: (i) x−1, y, z−1; (ii) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₉Br₄N
M_r	510.85
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	4.202 (2), 14.654 (6), 12.245 (6)
β (°)	92.758 (18)
V (Å³)	753.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	10.70
Crystal size (mm)	0.40 × 0.13 × 0.12

Data collection
Diffractometer	Rigaku XtaLAB mini diffractometer
Absorption correction	Multi-scan (REQAB; Rigaku, 1998)
T_min, T_max	0.115, 0.277
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	2755, 2599, 2071
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.130, 1.01
No. of reflections	2600
No. of parameters	172
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.66
Absolute structure	Flack (1983), 868 Friedel Pairs
Absolute structure parameter	0.05 (4)

Computer programs: CrystalClear-SM Expert (Rigaku, 2011), CrystalClear-SM Expert (Rigaku, 2011), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010).

Acknowledgements

This research was supported by FP7 REGPOT-2012–2013-1 ICT project CEOSeR under grant agreement No. 316010.

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Caulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). Eur. Patent No. 1253141. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Grigalevicius, S., Ostrauskaite, J., Grazulevicius, J. V., Gaidelis, V., Jankauskas, V. & Sidaravicius, J. (2002). Mat. Chem. Phys. 77, 281–284. CrossRef Google Scholar
Miyazaki, T., Shibahara, M., Fujishige, J., Watanabe, M., Goto, K. & Shinmyozu, T. (2014). J. Org. Chem. 79, 11440–11453. CrossRef CAS PubMed Google Scholar
Niu, F., Niu, H., Liu, Y., Lian, J. & Zeng, P. (2011). RSC Adv. 1, 415–423. CAS Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear-SM Expert . Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 6| June 2015| Page o373

doi:10.1107/S2056989015010117

Open

access