supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, o1476    [ doi:10.1107/S1600536809019448 ]

3-Bromo-9-(4-chlorobenzyl)-9H-carbazole

Z.-D. Xiao, T. Pan and D.-W. Yang

Abstract top

The title compound, C19H13BrClN, was synthesized by N-alkylation of 4-chloro-1-(chloromethyl)benzene with 3-bromo-9H-carbazole. The carbazole ring system is essentially planar, with a mean deviation of 0.028 Å, and it makes a dihedral angle of 91.2 (3) Å 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, the structure of 3-bromo-9-(4-chlorobenzyl)-9H-carbazole (I), synthesized by N-alkylation of 1-(chloromethyl)-4-chloroobenzene with 3-bromo-9H-carbazole, is reported

The carbazole ring is essentially planar, with mean deviations of 0.0275 Å. The dihedral angle between the carbazole ring and the benzyl ring is 91.2° A. The C—Br distance is 1.909 (3) Å, consistent with the literature (Allen et al., 1987).

Related literature top

For the pharmaceutical properties of the title compound, see: Buu-Hoï & Royer (1950); Caulfield et al. (2002); Harfenist & Joyner (1983); Harper et al. (2002). For related structures, see Allen et al. (1987). For related synthesis, see: Duan et al. (2005a,b).

Experimental top

The title compound was prepared according to the procedure of Duan et al. (2005a,b). A solution of potassium hydroxide (0.67 g) in dimethylformamide (8 ml) was stirred at room temperature for 20 min. 3-Bromo-9H-carbazole (1.0 g, 4 mmol) was added and the mixture stirred for a further 40 min. A solution of 1-(chloromethyl)-4-chlorobenzene (0.97 g, 6 mmol) in dimethylformamide (5 ml) was added dropwise with stirring. The resulting mixture was then stirred at room temperature for 12 h and poured into water (100 ml), yielding a white precipitate. The solid product was filtered off, washed with cold water and recrystallized from EtOH, giving crystals of (I). Yield: 1.26 g (85.2%); m.p. 431 - 433 K. Compound (I) (40 mg) was dissolved in mixture of chloroform (5 ml) and ethanol (5 ml) and the solution was kept at room temperature for 14 d. Natural evaporation of the solution gave colourless crystals suitable for X-Ray analysis.

Refinement top

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

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for H atoms).
3-Bromo-9-(4-chlorobenzyl)-9H-carbazole top
Crystal data top
C19H13BrClNDx = 1.614 Mg m−3
Mr = 370.66Melting point: 432 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 5012 reflections
a = 17.272 (4) Åθ = 1.8–27.9°
b = 15.789 (3) ŵ = 2.86 mm−1
c = 5.5948 (11) ÅT = 113 K
V = 1525.7 (5) Å3Block, colorless
Z = 40.18 × 0.16 × 0.08 mm
F(000) = 744
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2664 independent reflections
Radiation source: rotating anode2401 reflections with I > 2σ(I)
confocalRint = 0.031
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 1.8°
ω and φ scansh = −20→19
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		k = −18→18
Tmin = 0.627, Tmax = 0.803l = −6→6
10796 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.056 w = 1/[σ2(Fo2) + (0.0295P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2664 reflectionsΔρmax = 0.38 e Å−3
199 parametersΔρmin = −0.46 e Å−3
1 restraintAbsolute structure: Flack (1983), 1163 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.014 (9)
Crystal data top
C19H13BrClNV = 1525.7 (5) Å3
Mr = 370.66Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 17.272 (4) ŵ = 2.86 mm−1
b = 15.789 (3) ÅT = 113 K
c = 5.5948 (11) Å0.18 × 0.16 × 0.08 mm
Data collection top
Rigaku Saturn CCD area-detector
diffractometer		2664 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		2401 reflections with I > 2σ(I)
Tmin = 0.627, Tmax = 0.803Rint = 0.031
10796 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.056Δρmax = 0.38 e Å−3
S = 1.04Δρmin = −0.46 e Å−3
2664 reflectionsAbsolute structure: Flack (1983), 1163 Friedel pairs
199 parametersFlack parameter: 0.014 (9)
1 restraint
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
Br10.258680 (12)0.185476 (15)1.32912 (10)0.02288 (9)
Cl10.65120 (4)0.59416 (4)0.8259 (2)0.02847 (16)
N10.53701 (13)0.18736 (14)0.6844 (4)0.0167 (5)
C10.58534 (13)0.13162 (15)0.8041 (6)0.0152 (6)
C20.66094 (15)0.10636 (17)0.7491 (5)0.0209 (7)
H20.68620.12700.61430.025*
C30.69681 (15)0.04979 (18)0.9013 (5)0.0224 (7)
H30.74710.03220.86820.027*
C40.65932 (16)0.01831 (19)1.1042 (6)0.0233 (7)
H40.6848−0.01981.20380.028*
C50.58446 (15)0.04349 (18)1.1579 (5)0.0186 (7)
H50.55970.02271.29340.022*
C60.54667 (15)0.10001 (16)1.0080 (5)0.0167 (6)
C70.47140 (14)0.13996 (16)1.0130 (5)0.0135 (6)
C80.40812 (14)0.13595 (18)1.1675 (5)0.0160 (6)
H80.40820.10011.29930.019*
C90.34553 (15)0.18694 (17)1.1181 (5)0.0174 (6)
C100.34293 (15)0.24129 (18)0.9223 (5)0.0210 (7)
H100.29930.27460.89600.025*
C110.40475 (15)0.24581 (18)0.7676 (5)0.0202 (7)
H110.40400.28240.63730.024*
C120.46844 (13)0.19405 (14)0.8117 (6)0.0147 (5)
C130.55872 (15)0.24502 (16)0.4941 (5)0.0193 (7)
H13A0.51600.24950.38220.023*
H13B0.60260.22140.40870.023*
C140.57980 (15)0.33317 (17)0.5812 (5)0.0151 (6)
C150.62228 (15)0.34401 (18)0.7921 (6)0.0227 (7)
H150.63580.29710.88350.027*
C160.64432 (14)0.42472 (17)0.8658 (6)0.0215 (7)
H160.67290.43191.00520.026*
C170.62343 (16)0.49356 (17)0.7311 (5)0.0187 (6)
C180.58085 (15)0.48457 (18)0.5212 (6)0.0223 (7)
H180.56710.53180.43130.027*
C190.55924 (15)0.40353 (17)0.4486 (5)0.0192 (7)
H190.53060.39670.30910.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01586 (13)0.02907 (15)0.02370 (15)0.00028 (9)0.0041 (2)−0.0042 (2)
Cl10.0313 (3)0.0172 (3)0.0370 (4)−0.0025 (2)0.0062 (6)−0.0066 (5)
N10.0162 (12)0.0175 (14)0.0164 (13)−0.0024 (9)0.0028 (10)0.0012 (10)
C10.0157 (11)0.0141 (13)0.0159 (16)−0.0043 (9)−0.0006 (15)−0.0046 (15)
C20.0167 (14)0.0249 (17)0.0210 (17)−0.0076 (12)0.0033 (11)−0.0064 (12)
C30.0131 (14)0.0229 (17)0.031 (2)0.0027 (11)−0.0004 (12)−0.0099 (13)
C40.0196 (16)0.0219 (17)0.0283 (18)0.0007 (13)−0.0074 (13)−0.0015 (14)
C50.0187 (16)0.0179 (16)0.0193 (16)−0.0019 (12)−0.0037 (13)−0.0021 (12)
C60.0161 (14)0.0147 (16)0.0192 (16)−0.0050 (11)−0.0006 (12)−0.0059 (13)
C70.0121 (13)0.0118 (15)0.0166 (15)−0.0036 (10)−0.0011 (12)−0.0024 (12)
C80.0184 (15)0.0137 (16)0.0159 (16)−0.0045 (11)−0.0051 (12)−0.0018 (12)
C90.0128 (13)0.0187 (16)0.0208 (17)−0.0032 (12)0.0023 (12)−0.0078 (13)
C100.0161 (15)0.0222 (17)0.0248 (17)0.0011 (11)−0.0055 (12)−0.0029 (13)
C110.0232 (14)0.0199 (15)0.017 (2)−0.0010 (11)−0.0014 (12)0.0006 (12)
C120.0155 (11)0.0150 (13)0.0137 (14)−0.0051 (9)0.0017 (18)−0.0022 (16)
C130.0193 (15)0.0235 (17)0.0151 (15)−0.0050 (12)0.0030 (13)−0.0026 (14)
C140.0138 (14)0.0174 (15)0.0142 (15)−0.0024 (11)0.0050 (12)0.0002 (12)
C150.0235 (13)0.0193 (14)0.025 (2)−0.0009 (10)−0.0009 (16)0.0049 (15)
C160.0220 (13)0.0251 (16)0.017 (2)−0.0035 (10)0.0012 (14)−0.0007 (14)
C170.0181 (14)0.0149 (16)0.0229 (16)−0.0008 (11)0.0056 (12)−0.0012 (12)
C180.0201 (15)0.0194 (17)0.0273 (18)0.0039 (12)0.0024 (14)0.0017 (14)
C190.0145 (14)0.0261 (18)0.0172 (16)0.0001 (11)0.0007 (12)0.0013 (13)
Geometric parameters (Å, °) top
Br1—C91.909 (3)C8—H80.9300
Cl1—C171.742 (3)C9—C101.392 (4)
N1—C11.385 (3)C10—C111.376 (4)
N1—C121.386 (3)C10—H100.9300
N1—C131.450 (3)C11—C121.393 (4)
C1—C21.399 (3)C11—H110.9300
C1—C61.413 (4)C13—C141.519 (4)
C2—C31.381 (4)C13—H13A0.9700
C2—H20.9300C13—H13B0.9700
C3—C41.398 (4)C14—C191.382 (4)
C3—H30.9300C14—C151.400 (4)
C4—C51.386 (4)C15—C161.392 (4)
C4—H40.9300C15—H150.9300
C5—C61.388 (4)C16—C171.371 (4)
C5—H50.9300C16—H160.9300
C6—C71.445 (3)C17—C181.393 (4)
C7—C81.395 (4)C18—C191.393 (4)
C7—C121.415 (4)C18—H180.9300
C8—C91.376 (4)C19—H190.9300
C1—N1—C12108.4 (2)C9—C10—H10119.9
C1—N1—C13126.7 (2)C10—C11—C12118.1 (3)
C12—N1—C13123.4 (2)C10—C11—H11121.0
N1—C1—C2129.6 (3)C12—C11—H11121.0
N1—C1—C6109.2 (2)N1—C12—C11129.0 (3)
C2—C1—C6121.2 (3)N1—C12—C7109.4 (2)
C3—C2—C1117.9 (3)C11—C12—C7121.6 (3)
C3—C2—H2121.1N1—C13—C14113.7 (2)
C1—C2—H2121.1N1—C13—H13A108.8
C2—C3—C4121.5 (3)C14—C13—H13A108.8
C2—C3—H3119.2N1—C13—H13B108.8
C4—C3—H3119.2C14—C13—H13B108.8
C5—C4—C3120.4 (3)H13A—C13—H13B107.7
C5—C4—H4119.8C19—C14—C15119.3 (3)
C3—C4—H4119.8C19—C14—C13120.2 (3)
C4—C5—C6119.5 (3)C15—C14—C13120.5 (3)
C4—C5—H5120.3C16—C15—C14120.3 (3)
C6—C5—H5120.3C16—C15—H15119.8
C5—C6—C1119.5 (2)C14—C15—H15119.8
C5—C6—C7133.8 (3)C17—C16—C15119.4 (3)
C1—C6—C7106.7 (2)C17—C16—H16120.3
C8—C7—C12119.5 (2)C15—C16—H16120.3
C8—C7—C6134.2 (3)C16—C17—C18121.4 (3)
C12—C7—C6106.3 (2)C16—C17—Cl1118.9 (2)
C9—C8—C7117.7 (3)C18—C17—Cl1119.7 (2)
C9—C8—H8121.2C17—C18—C19118.8 (3)
C7—C8—H8121.2C17—C18—H18120.6
C8—C9—C10123.0 (3)C19—C18—H18120.6
C8—C9—Br1119.1 (2)C14—C19—C18120.8 (3)
C10—C9—Br1117.9 (2)C14—C19—H19119.6
C11—C10—C9120.1 (3)C18—C19—H19119.6
C11—C10—H10119.9
C12—N1—C1—C2−178.2 (3)C9—C10—C11—C120.8 (4)
C13—N1—C1—C2−12.0 (4)C1—N1—C12—C11176.2 (3)
C12—N1—C1—C61.6 (3)C13—N1—C12—C119.5 (4)
C13—N1—C1—C6167.8 (2)C1—N1—C12—C7−1.7 (3)
N1—C1—C2—C3179.4 (3)C13—N1—C12—C7−168.4 (2)
C6—C1—C2—C3−0.4 (4)C10—C11—C12—N1−179.6 (3)
C1—C2—C3—C40.1 (4)C10—C11—C12—C7−1.9 (4)
C2—C3—C4—C5−0.1 (4)C8—C7—C12—N1−179.7 (2)
C3—C4—C5—C60.3 (4)C6—C7—C12—N11.2 (3)
C4—C5—C6—C1−0.6 (4)C8—C7—C12—C112.2 (4)
C4—C5—C6—C7−178.3 (3)C6—C7—C12—C11−177.0 (2)
N1—C1—C6—C5−179.2 (2)C1—N1—C13—C14−93.3 (3)
C2—C1—C6—C50.6 (4)C12—N1—C13—C1470.8 (3)
N1—C1—C6—C7−0.9 (3)N1—C13—C14—C19−142.8 (3)
C2—C1—C6—C7178.9 (2)N1—C13—C14—C1539.3 (4)
C5—C6—C7—C8−1.2 (5)C19—C14—C15—C16−0.7 (4)
C1—C6—C7—C8−179.1 (3)C13—C14—C15—C16177.2 (2)
C5—C6—C7—C12177.8 (3)C14—C15—C16—C170.6 (4)
C1—C6—C7—C12−0.1 (3)C15—C16—C17—C18−0.3 (4)
C12—C7—C8—C9−1.3 (4)C15—C16—C17—Cl1179.8 (2)
C6—C7—C8—C9177.6 (3)C16—C17—C18—C190.1 (4)
C7—C8—C9—C100.2 (4)Cl1—C17—C18—C19180.0 (2)
C7—C8—C9—Br1−178.51 (19)C15—C14—C19—C180.6 (4)
C8—C9—C10—C110.0 (4)C13—C14—C19—C18−177.4 (2)
Br1—C9—C10—C11178.8 (2)C17—C18—C19—C14−0.2 (4)
Acknowledgements top

This work was supported by the Hunan Natural Science Foundation (05 J J30198) and the Scientific Research Foundation of Hunan Province (2008 GK-037).

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.

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

Caulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). Eur. Patent EP 1253141.

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.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

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

Harper, R. W., Lin, H. S. & Richett, M. E. (2002). World Patent WO2002079154.

Rigaku (2005). CrystalClear. Rigaku Americas Corporation, The Woodlands, Texas, USA.

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