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

Abstract

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.

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 ▸).

Experimental  

Crystal data  

• C₁₄H₉Br₄N

• M _r = 510.85

• Monoclinic,

• a = 4.202 (2) Å

• b = 14.654 (6) Å

• c = 12.245 (6) Å

• β = 92.758 (18)°

• V = 753.1 (6) ų

• Z = 2

• Mo Kα radiation

• μ = 10.70 mm⁻¹

• T = 293 K

• 0.40 × 0.13 × 0.12 mm

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 F ² > 2.0σ(F ²)

• R _int = 0.021

Refinement  

• R[F ² > 2σ(F ²)] = 0.056

• wR(F ²) = 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.

Supplementary Material

CCDC reference: 1402621

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

supplementary crystallographic information

S1. Synthesis and crystallization

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).

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.

Figures

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.

Crystal data

C14H9Br4N	F(000) = 480.00
Mr = 510.85	Dx = 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

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

Refinement

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(Fo2) + (0.0517P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
2600 reflections	Δρmax = 0.74 e Å−3
172 parameters	Δρmin = −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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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.