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Acta Cryst. (2009). E65, o215    [ doi:10.1107/S1600536808042815 ]

3,6-Dibromo-9-(4-chlorobenzyl)-9H-carbazole

J. Cui, M. Duan and L. Cai

Abstract top

The title compound, C19H12Br2ClN, was synthesized by N-alkylation of 1-chloro-4-(chloromethyl)benzene with 3,6-dibromo-9H-carbazole. The carbazole ring system is essentially planar (mean deviation of 0.028 Å) and makes a dihedral angle of 74.6 (3)° with the plane of the benzene ring.

Comment top

Carbazole derivatives substituted by N-alkylation possess valuable pharmaceutical properties (Buu-Hoï & Royer, 1950; Harfenist & Joyner, 1983; Caulfield et al., 2002; Harper et al., 2002). In this paper, we report the structure of 3,6-dibromo-9-(4-chlorobenzyl)-9H-carbazole (I), which was synthesized by N-alkylation of 1-chloro-4-(chloromethyl)benzene with 3,6-dibromo-9H-carbazole. The carbazole ring system is essentially planar with mean deviations of 0.0277Å. The carbazole plane is inclined to the benzene ring planes at dihedral angle of 74.6 (3)°. The C—Br distances fall in the range 1.883 (4) to 1.905 (5) Å, consistent with the literature (Allen et al., 1987).

Related literature top

For the pharmaceutical properties of carbazoles, see: Buu-Hoï & Royer (1950); Caulfield et al. (2002); Harfenist & Joyner (1983); Harper et al. (2002). For bond length data, see: Allen et al. (1987). For the synthesis of the title compound, see: Duan et al. (2005a,b); Smith et al. (1992). For related literature, see: Borzatta & Carrozza (1991). For a related compound, see: Cui & Cai (2009).

Experimental top

The title compound was prepared according to the procedure of Duan et al. (2005a,b) from 3,6-dibromo-carbazole (Smith et al. 1992) and 1-chloro-4-(chloromethyl)benzene. Compound (I) (40 mg) was dissolved in mixture of chloroform (10 ml) and ethanol (5 ml) and the solution was kept at room temperature for 18 d. Natural evaporation of the solution gave colourless crystals suitable for X-Ray analysis. (m.p. 451–452 K).

Refinement top

All H atoms were included in the riding model approximation with C—H distances = 0.93 (aromatic) and 0.97 (methylene) Å, and with Uiso(H) = 1.2xUeq(C).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A perspective view of (I) with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Crystal packing of (I), viewed down the a axis with H atoms omitted for clarity.
3,6-Dibromo-9-(4-chlorobenzyl)-9H-carbazole top
Crystal data top
C19H12Br2ClNDx = 1.887 Mg m−3
Mr = 449.57Melting point = 451–452 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5270 reflections
a = 8.7673 (18) Åθ = 2.4–27.9°
b = 16.732 (3) ŵ = 5.29 mm−1
c = 21.574 (4) ÅT = 113 K
V = 3164.8 (10) Å3Prism, colorless
Z = 80.06 × 0.02 × 0.02 mm
F(000) = 1760
Data collection top
Rigaku Saturn
diffractometer		2794 independent reflections
Radiation source: rotating anode2369 reflections with I > 2σ(I)
confocalRint = 0.090
ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		h = −10→10
Tmin = 0.742, Tmax = 0.902k = −19→13
18205 measured reflectionsl = −25→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0488P)2 + 2.2242P]
where P = (Fo2 + 2Fc2)/3
2794 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.54 e Å−3
0 restraintsΔρmin = −0.53 e Å−3
Crystal data top
C19H12Br2ClNV = 3164.8 (10) Å3
Mr = 449.57Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.7673 (18) ŵ = 5.29 mm−1
b = 16.732 (3) ÅT = 113 K
c = 21.574 (4) Å0.06 × 0.02 × 0.02 mm
Data collection top
Rigaku Saturn
diffractometer		2369 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		Rint = 0.090
Tmin = 0.742, Tmax = 0.902θmax = 25.0°
18205 measured reflectionsStandard reflections: 0
2794 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.54 e Å−3
S = 1.10Δρmin = −0.53 e Å−3
2794 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.22114 (6)0.09041 (3)0.56121 (2)0.02566 (18)
Br20.65417 (6)−0.19402 (3)0.84401 (2)0.02964 (19)
Cl10.54034 (14)0.40983 (8)0.94634 (5)0.0248 (3)
N10.2015 (4)0.0764 (3)0.83555 (17)0.0200 (9)
C10.1896 (5)0.0868 (3)0.7726 (2)0.0181 (10)
C20.1017 (5)0.1422 (3)0.7406 (2)0.0205 (11)
H20.03880.17830.76110.025*
C30.1123 (5)0.1410 (3)0.6772 (2)0.0208 (11)
H30.05620.17710.65360.025*
C40.2067 (5)0.0860 (3)0.6482 (2)0.0193 (11)
C50.2911 (5)0.0299 (3)0.6790 (2)0.0193 (11)
H50.3511−0.00710.65800.023*
C60.2827 (5)0.0308 (3)0.7433 (2)0.0163 (10)
C70.3559 (5)−0.0160 (3)0.7902 (2)0.0170 (10)
C80.4580 (5)−0.0795 (3)0.7888 (2)0.0198 (11)
H80.4890−0.10200.75150.024*
C90.5117 (6)−0.1080 (3)0.8443 (2)0.0236 (12)
C100.4625 (5)−0.0769 (3)0.9006 (2)0.0240 (12)
H100.4999−0.09770.93750.029*
C110.3590 (5)−0.0155 (3)0.9018 (2)0.0224 (11)
H110.32590.00520.93950.027*
C120.3041 (5)0.0154 (3)0.8466 (2)0.0182 (11)
C130.1391 (6)0.1292 (3)0.8828 (2)0.0230 (12)
H13A0.11940.09850.92010.028*
H13B0.04250.15050.86830.028*
C140.2447 (5)0.1977 (3)0.8982 (2)0.0190 (11)
C150.2722 (5)0.2589 (3)0.8562 (2)0.0208 (11)
H150.22640.25680.81740.025*
C160.3654 (5)0.3226 (3)0.8703 (2)0.0198 (11)
H160.38250.36280.84140.024*
C170.4333 (5)0.3259 (3)0.9281 (2)0.0220 (11)
C180.4101 (6)0.2650 (3)0.9700 (2)0.0237 (11)
H180.45790.26661.00840.028*
C190.3168 (5)0.2020 (3)0.9553 (2)0.0214 (11)
H190.30180.16140.98410.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0279 (3)0.0322 (4)0.0169 (3)−0.0001 (2)0.00008 (19)0.0030 (2)
Br20.0277 (3)0.0238 (4)0.0375 (3)0.0038 (2)−0.0060 (2)0.0027 (2)
Cl10.0296 (7)0.0222 (8)0.0225 (6)−0.0055 (5)−0.0011 (5)−0.0009 (5)
N10.025 (2)0.018 (3)0.0176 (19)−0.0014 (18)0.0005 (16)−0.0021 (18)
C10.023 (2)0.013 (3)0.018 (2)−0.003 (2)−0.0011 (19)−0.005 (2)
C20.019 (2)0.016 (3)0.027 (3)−0.003 (2)−0.003 (2)−0.005 (2)
C30.021 (3)0.020 (3)0.021 (2)−0.004 (2)−0.004 (2)0.001 (2)
C40.017 (2)0.023 (3)0.017 (2)−0.004 (2)−0.0016 (19)0.000 (2)
C50.021 (2)0.016 (3)0.021 (2)−0.001 (2)0.0007 (19)0.000 (2)
C60.016 (2)0.016 (3)0.017 (2)−0.003 (2)0.0019 (18)−0.002 (2)
C70.017 (2)0.015 (3)0.019 (2)−0.006 (2)0.0002 (18)−0.001 (2)
C80.018 (2)0.022 (3)0.020 (2)−0.003 (2)0.0014 (19)0.001 (2)
C90.021 (3)0.020 (3)0.030 (3)−0.003 (2)−0.004 (2)0.004 (2)
C100.027 (3)0.023 (3)0.022 (2)−0.007 (2)−0.006 (2)0.004 (2)
C110.028 (3)0.021 (3)0.019 (2)−0.005 (2)−0.001 (2)−0.003 (2)
C120.017 (2)0.018 (3)0.019 (2)−0.008 (2)−0.0026 (18)0.003 (2)
C130.025 (3)0.026 (3)0.018 (2)0.000 (2)0.008 (2)−0.007 (2)
C140.019 (2)0.020 (3)0.018 (2)0.001 (2)0.0044 (19)−0.008 (2)
C150.017 (2)0.028 (3)0.017 (2)0.003 (2)0.0022 (19)−0.002 (2)
C160.019 (2)0.020 (3)0.020 (2)0.006 (2)0.0042 (19)0.002 (2)
C170.023 (3)0.024 (3)0.020 (2)−0.001 (2)0.000 (2)−0.001 (2)
C180.032 (3)0.024 (3)0.015 (2)0.003 (2)−0.002 (2)0.001 (2)
C190.027 (3)0.016 (3)0.021 (2)−0.002 (2)0.008 (2)0.004 (2)
Geometric parameters (Å, °) top
Br1—C41.883 (4)C8—H80.9300
Br2—C91.905 (5)C9—C101.390 (7)
Cl1—C171.734 (5)C10—C111.370 (7)
N1—C11.373 (6)C10—H100.9300
N1—C121.382 (6)C11—C121.384 (6)
N1—C131.455 (6)C11—H110.9300
C1—C21.390 (7)C13—C141.510 (7)
C1—C61.393 (7)C13—H13A0.9700
C2—C31.370 (6)C13—H13B0.9700
C2—H20.9300C14—C191.386 (7)
C3—C41.387 (7)C14—C151.389 (7)
C3—H30.9300C15—C161.377 (7)
C4—C51.368 (7)C15—H150.9300
C5—C61.389 (6)C16—C171.383 (6)
C5—H50.9300C16—H160.9300
C6—C71.431 (7)C17—C181.376 (7)
C7—C81.390 (7)C18—C191.372 (7)
C7—C121.402 (6)C18—H180.9300
C8—C91.371 (6)C19—H190.9300
C1—N1—C12108.3 (4)C9—C10—H10119.9
C1—N1—C13126.0 (4)C10—C11—C12119.6 (5)
C12—N1—C13124.9 (4)C10—C11—H11120.2
N1—C1—C2128.2 (4)C12—C11—H11120.2
N1—C1—C6108.6 (4)N1—C12—C11130.7 (4)
C2—C1—C6123.2 (4)N1—C12—C7109.7 (4)
C3—C2—C1116.7 (5)C11—C12—C7119.6 (5)
C3—C2—H2121.7N1—C13—C14112.6 (4)
C1—C2—H2121.7N1—C13—H13A109.1
C2—C3—C4119.9 (5)C14—C13—H13A109.1
C2—C3—H3120.0N1—C13—H13B109.1
C4—C3—H3120.0C14—C13—H13B109.1
C5—C4—C3124.1 (4)H13A—C13—H13B107.8
C5—C4—Br1118.3 (4)C19—C14—C15117.5 (5)
C3—C4—Br1117.6 (4)C19—C14—C13121.0 (5)
C4—C5—C6116.6 (5)C15—C14—C13121.5 (4)
C4—C5—H5121.7C16—C15—C14122.0 (4)
C6—C5—H5121.7C16—C15—H15119.0
C5—C6—C1119.5 (4)C14—C15—H15119.0
C5—C6—C7132.5 (5)C15—C16—C17119.1 (5)
C1—C6—C7108.1 (4)C15—C16—H16120.5
C8—C7—C12120.9 (4)C17—C16—H16120.5
C8—C7—C6133.9 (4)C18—C17—C16119.9 (5)
C12—C7—C6105.3 (4)C18—C17—Cl1122.1 (4)
C9—C8—C7118.0 (5)C16—C17—Cl1118.0 (4)
C9—C8—H8121.0C19—C18—C17120.4 (5)
C7—C8—H8121.0C19—C18—H18119.8
C8—C9—C10121.7 (5)C17—C18—H18119.8
C8—C9—Br2119.0 (4)C18—C19—C14121.2 (5)
C10—C9—Br2119.3 (4)C18—C19—H19119.4
C11—C10—C9120.2 (5)C14—C19—H19119.4
C11—C10—H10119.9
C12—N1—C1—C2−178.9 (5)Br2—C9—C10—C11−179.4 (4)
C13—N1—C1—C2−8.9 (8)C9—C10—C11—C12−0.1 (7)
C12—N1—C1—C61.3 (5)C1—N1—C12—C11177.3 (5)
C13—N1—C1—C6171.2 (4)C13—N1—C12—C117.2 (8)
N1—C1—C2—C3178.8 (5)C1—N1—C12—C7−1.8 (5)
C6—C1—C2—C3−1.3 (7)C13—N1—C12—C7−171.9 (4)
C1—C2—C3—C40.4 (7)C10—C11—C12—N1−179.6 (5)
C2—C3—C4—C51.2 (8)C10—C11—C12—C7−0.5 (7)
C2—C3—C4—Br1−177.8 (4)C8—C7—C12—N1−178.6 (4)
C3—C4—C5—C6−1.8 (7)C6—C7—C12—N11.7 (5)
Br1—C4—C5—C6177.2 (3)C8—C7—C12—C112.1 (7)
C4—C5—C6—C10.8 (7)C6—C7—C12—C11−177.6 (4)
C4—C5—C6—C7−178.1 (5)C1—N1—C13—C14−85.7 (6)
N1—C1—C6—C5−179.4 (4)C12—N1—C13—C1482.7 (6)
C2—C1—C6—C50.7 (7)N1—C13—C14—C19−111.0 (5)
N1—C1—C6—C7−0.2 (5)N1—C13—C14—C1569.5 (6)
C2—C1—C6—C7179.9 (4)C19—C14—C15—C16−1.0 (7)
C5—C6—C7—C8−1.5 (9)C13—C14—C15—C16178.4 (4)
C1—C6—C7—C8179.5 (5)C14—C15—C16—C17−0.2 (7)
C5—C6—C7—C12178.2 (5)C15—C16—C17—C181.6 (7)
C1—C6—C7—C12−0.9 (5)C15—C16—C17—Cl1−176.0 (4)
C12—C7—C8—C9−2.9 (7)C16—C17—C18—C19−1.7 (8)
C6—C7—C8—C9176.7 (5)Cl1—C17—C18—C19175.8 (4)
C7—C8—C9—C102.3 (7)C17—C18—C19—C140.4 (8)
C7—C8—C9—Br2−179.1 (4)C15—C14—C19—C181.0 (7)
C8—C9—C10—C11−0.8 (8)C13—C14—C19—C18−178.5 (5)
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Borzatta, V. & Carrozza, P. (1991). European Patent EP 0 462 069.

Buu-Hoï, N. P. & Royer, R. (1950). J. Org. Chem. 15, 123–130.

Caulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). European Patent No. 1 253 141.

Cui, J. & Cai, L. (2009). Acta Cryst. E65, o??? [SJ2564].

Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005a). Fine Chem. 22, 39–40.

Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005b). Fine Chem. 22, 52.

Harfenist, M. & Joyner, C. T. (1983). US Patent No. 4 379 160.

Harper, R. W., Lin, H. S. & Richett, M. E. (2002). World Patent No. 02 079 154.

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas,

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smith, K., James, D. M., Mistry, A. G., Bye, M. R. & Faulkner, D. J. (1992). Tetrahedron, 48, 7479–7488.