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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2009 Jun 6;65(Pt 7):o1476. doi: 10.1107/S1600536809019448

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

Zi-Dan Xiao a, Tong Pan a, Dao-Wu Yang a,*
PMCID: PMC2969400  PMID: 21582778

Abstract

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.

Related literature

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 bond-length data, see Allen et al. (1987 ▶). For synthetic procedures, see: Duan et al. (2005a ▶,b ▶).graphic file with name e-65-o1476-scheme1.jpg

Experimental

Crystal data

  • C19H13BrClN

  • M r = 370.66

  • Orthorhombic, Inline graphic

  • a = 17.272 (4) Å

  • b = 15.789 (3) Å

  • c = 5.5948 (11) Å

  • V = 1525.7 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.86 mm−1

  • T = 113 K

  • 0.18 × 0.16 × 0.08 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.627, T max = 0.803

  • 10796 measured reflections

  • 2664 independent reflections

  • 2401 reflections with I > 2σ(I)

  • R int = 0.031

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023

  • wR(F 2) = 0.056

  • S = 1.04

  • 2664 reflections

  • 199 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.47 e Å−3

  • Absolute structure: Flack (1983 ▶), 1163 Friedel pairs

  • Flack parameter: 0.014 (9)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019448/dn2457sup1.cif

e-65-o1476-sup1.cif (18.6KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019448/dn2457Isup2.hkl

e-65-o1476-Isup2.hkl (130.8KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

Fig. 1.

Fig. 1.

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A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for H atoms).

Crystal data

C19H13BrClN Dx = 1.614 Mg m−3
Mr = 370.66 Melting point: 432 K
Orthorhombic, Pna21 Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n Cell parameters from 5012 reflections
a = 17.272 (4) Å θ = 1.8–27.9°
b = 15.789 (3) Å µ = 2.86 mm−1
c = 5.5948 (11) Å T = 113 K
V = 1525.7 (5) Å3 Block, colorless
Z = 4 0.18 × 0.16 × 0.08 mm
F(000) = 744
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Data collection

Rigaku Saturn CCD area-detector diffractometer 2664 independent reflections
Radiation source: rotating anode 2401 reflections with I > 2σ(I)
confocal Rint = 0.031
Detector resolution: 7.31 pixels mm-1 θmax = 25.0°, θmin = 1.8°
ω and φ scans h = −20→19
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) k = −18→18
Tmin = 0.627, Tmax = 0.803 l = −6→6
10796 measured reflections
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Refinement

Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023 H-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 reflections Δρmax = 0.38 e Å−3
199 parameters Δρmin = −0.46 e Å−3
1 restraint Absolute structure: Flack (1983), 1163 Friedel pairs
Primary atom site location: structure-invariant direct methods Flack parameter: 0.014 (9)
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Special details

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

x y z Uiso*/Ueq
Br1 0.258680 (12) 0.185476 (15) 1.32912 (10) 0.02288 (9)
Cl1 0.65120 (4) 0.59416 (4) 0.8259 (2) 0.02847 (16)
N1 0.53701 (13) 0.18736 (14) 0.6844 (4) 0.0167 (5)
C1 0.58534 (13) 0.13162 (15) 0.8041 (6) 0.0152 (6)
C2 0.66094 (15) 0.10636 (17) 0.7491 (5) 0.0209 (7)
H2 0.6862 0.1270 0.6143 0.025*
C3 0.69681 (15) 0.04979 (18) 0.9013 (5) 0.0224 (7)
H3 0.7471 0.0322 0.8682 0.027*
C4 0.65932 (16) 0.01831 (19) 1.1042 (6) 0.0233 (7)
H4 0.6848 −0.0198 1.2038 0.028*
C5 0.58446 (15) 0.04349 (18) 1.1579 (5) 0.0186 (7)
H5 0.5597 0.0227 1.2934 0.022*
C6 0.54667 (15) 0.10001 (16) 1.0080 (5) 0.0167 (6)
C7 0.47140 (14) 0.13996 (16) 1.0130 (5) 0.0135 (6)
C8 0.40812 (14) 0.13595 (18) 1.1675 (5) 0.0160 (6)
H8 0.4082 0.1001 1.2993 0.019*
C9 0.34553 (15) 0.18694 (17) 1.1181 (5) 0.0174 (6)
C10 0.34293 (15) 0.24129 (18) 0.9223 (5) 0.0210 (7)
H10 0.2993 0.2746 0.8960 0.025*
C11 0.40475 (15) 0.24581 (18) 0.7676 (5) 0.0202 (7)
H11 0.4040 0.2824 0.6373 0.024*
C12 0.46844 (13) 0.19405 (14) 0.8117 (6) 0.0147 (5)
C13 0.55872 (15) 0.24502 (16) 0.4941 (5) 0.0193 (7)
H13A 0.5160 0.2495 0.3822 0.023*
H13B 0.6026 0.2214 0.4087 0.023*
C14 0.57980 (15) 0.33317 (17) 0.5812 (5) 0.0151 (6)
C15 0.62228 (15) 0.34401 (18) 0.7921 (6) 0.0227 (7)
H15 0.6358 0.2971 0.8835 0.027*
C16 0.64432 (14) 0.42472 (17) 0.8658 (6) 0.0215 (7)
H16 0.6729 0.4319 1.0052 0.026*
C17 0.62343 (16) 0.49356 (17) 0.7311 (5) 0.0187 (6)
C18 0.58085 (15) 0.48457 (18) 0.5212 (6) 0.0223 (7)
H18 0.5671 0.5318 0.4313 0.027*
C19 0.55924 (15) 0.40353 (17) 0.4486 (5) 0.0192 (7)
H19 0.5306 0.3967 0.3091 0.023*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Br1 0.01586 (13) 0.02907 (15) 0.02370 (15) 0.00028 (9) 0.0041 (2) −0.0042 (2)
Cl1 0.0313 (3) 0.0172 (3) 0.0370 (4) −0.0025 (2) 0.0062 (6) −0.0066 (5)
N1 0.0162 (12) 0.0175 (14) 0.0164 (13) −0.0024 (9) 0.0028 (10) 0.0012 (10)
C1 0.0157 (11) 0.0141 (13) 0.0159 (16) −0.0043 (9) −0.0006 (15) −0.0046 (15)
C2 0.0167 (14) 0.0249 (17) 0.0210 (17) −0.0076 (12) 0.0033 (11) −0.0064 (12)
C3 0.0131 (14) 0.0229 (17) 0.031 (2) 0.0027 (11) −0.0004 (12) −0.0099 (13)
C4 0.0196 (16) 0.0219 (17) 0.0283 (18) 0.0007 (13) −0.0074 (13) −0.0015 (14)
C5 0.0187 (16) 0.0179 (16) 0.0193 (16) −0.0019 (12) −0.0037 (13) −0.0021 (12)
C6 0.0161 (14) 0.0147 (16) 0.0192 (16) −0.0050 (11) −0.0006 (12) −0.0059 (13)
C7 0.0121 (13) 0.0118 (15) 0.0166 (15) −0.0036 (10) −0.0011 (12) −0.0024 (12)
C8 0.0184 (15) 0.0137 (16) 0.0159 (16) −0.0045 (11) −0.0051 (12) −0.0018 (12)
C9 0.0128 (13) 0.0187 (16) 0.0208 (17) −0.0032 (12) 0.0023 (12) −0.0078 (13)
C10 0.0161 (15) 0.0222 (17) 0.0248 (17) 0.0011 (11) −0.0055 (12) −0.0029 (13)
C11 0.0232 (14) 0.0199 (15) 0.017 (2) −0.0010 (11) −0.0014 (12) 0.0006 (12)
C12 0.0155 (11) 0.0150 (13) 0.0137 (14) −0.0051 (9) 0.0017 (18) −0.0022 (16)
C13 0.0193 (15) 0.0235 (17) 0.0151 (15) −0.0050 (12) 0.0030 (13) −0.0026 (14)
C14 0.0138 (14) 0.0174 (15) 0.0142 (15) −0.0024 (11) 0.0050 (12) 0.0002 (12)
C15 0.0235 (13) 0.0193 (14) 0.025 (2) −0.0009 (10) −0.0009 (16) 0.0049 (15)
C16 0.0220 (13) 0.0251 (16) 0.017 (2) −0.0035 (10) 0.0012 (14) −0.0007 (14)
C17 0.0181 (14) 0.0149 (16) 0.0229 (16) −0.0008 (11) 0.0056 (12) −0.0012 (12)
C18 0.0201 (15) 0.0194 (17) 0.0273 (18) 0.0039 (12) 0.0024 (14) 0.0017 (14)
C19 0.0145 (14) 0.0261 (18) 0.0172 (16) 0.0001 (11) 0.0007 (12) 0.0013 (13)
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Geometric parameters (Å, °)

Br1—C9 1.909 (3) C8—H8 0.9300
Cl1—C17 1.742 (3) C9—C10 1.392 (4)
N1—C1 1.385 (3) C10—C11 1.376 (4)
N1—C12 1.386 (3) C10—H10 0.9300
N1—C13 1.450 (3) C11—C12 1.393 (4)
C1—C2 1.399 (3) C11—H11 0.9300
C1—C6 1.413 (4) C13—C14 1.519 (4)
C2—C3 1.381 (4) C13—H13A 0.9700
C2—H2 0.9300 C13—H13B 0.9700
C3—C4 1.398 (4) C14—C19 1.382 (4)
C3—H3 0.9300 C14—C15 1.400 (4)
C4—C5 1.386 (4) C15—C16 1.392 (4)
C4—H4 0.9300 C15—H15 0.9300
C5—C6 1.388 (4) C16—C17 1.371 (4)
C5—H5 0.9300 C16—H16 0.9300
C6—C7 1.445 (3) C17—C18 1.393 (4)
C7—C8 1.395 (4) C18—C19 1.393 (4)
C7—C12 1.415 (4) C18—H18 0.9300
C8—C9 1.376 (4) C19—H19 0.9300
C1—N1—C12 108.4 (2) C9—C10—H10 119.9
C1—N1—C13 126.7 (2) C10—C11—C12 118.1 (3)
C12—N1—C13 123.4 (2) C10—C11—H11 121.0
N1—C1—C2 129.6 (3) C12—C11—H11 121.0
N1—C1—C6 109.2 (2) N1—C12—C11 129.0 (3)
C2—C1—C6 121.2 (3) N1—C12—C7 109.4 (2)
C3—C2—C1 117.9 (3) C11—C12—C7 121.6 (3)
C3—C2—H2 121.1 N1—C13—C14 113.7 (2)
C1—C2—H2 121.1 N1—C13—H13A 108.8
C2—C3—C4 121.5 (3) C14—C13—H13A 108.8
C2—C3—H3 119.2 N1—C13—H13B 108.8
C4—C3—H3 119.2 C14—C13—H13B 108.8
C5—C4—C3 120.4 (3) H13A—C13—H13B 107.7
C5—C4—H4 119.8 C19—C14—C15 119.3 (3)
C3—C4—H4 119.8 C19—C14—C13 120.2 (3)
C4—C5—C6 119.5 (3) C15—C14—C13 120.5 (3)
C4—C5—H5 120.3 C16—C15—C14 120.3 (3)
C6—C5—H5 120.3 C16—C15—H15 119.8
C5—C6—C1 119.5 (2) C14—C15—H15 119.8
C5—C6—C7 133.8 (3) C17—C16—C15 119.4 (3)
C1—C6—C7 106.7 (2) C17—C16—H16 120.3
C8—C7—C12 119.5 (2) C15—C16—H16 120.3
C8—C7—C6 134.2 (3) C16—C17—C18 121.4 (3)
C12—C7—C6 106.3 (2) C16—C17—Cl1 118.9 (2)
C9—C8—C7 117.7 (3) C18—C17—Cl1 119.7 (2)
C9—C8—H8 121.2 C17—C18—C19 118.8 (3)
C7—C8—H8 121.2 C17—C18—H18 120.6
C8—C9—C10 123.0 (3) C19—C18—H18 120.6
C8—C9—Br1 119.1 (2) C14—C19—C18 120.8 (3)
C10—C9—Br1 117.9 (2) C14—C19—H19 119.6
C11—C10—C9 120.1 (3) C18—C19—H19 119.6
C11—C10—H10 119.9
C12—N1—C1—C2 −178.2 (3) C9—C10—C11—C12 0.8 (4)
C13—N1—C1—C2 −12.0 (4) C1—N1—C12—C11 176.2 (3)
C12—N1—C1—C6 1.6 (3) C13—N1—C12—C11 9.5 (4)
C13—N1—C1—C6 167.8 (2) C1—N1—C12—C7 −1.7 (3)
N1—C1—C2—C3 179.4 (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—C4 0.1 (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—C6 0.3 (4) C6—C7—C12—N1 1.2 (3)
C4—C5—C6—C1 −0.6 (4) C8—C7—C12—C11 2.2 (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—C5 0.6 (4) C12—N1—C13—C14 70.8 (3)
N1—C1—C6—C7 −0.9 (3) N1—C13—C14—C19 −142.8 (3)
C2—C1—C6—C7 178.9 (2) N1—C13—C14—C15 39.3 (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—C16 177.2 (2)
C5—C6—C7—C12 177.8 (3) C14—C15—C16—C17 0.6 (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—Cl1 179.8 (2)
C6—C7—C8—C9 177.6 (3) C16—C17—C18—C19 0.1 (4)
C7—C8—C9—C10 0.2 (4) Cl1—C17—C18—C19 180.0 (2)
C7—C8—C9—Br1 −178.51 (19) C15—C14—C19—C18 0.6 (4)
C8—C9—C10—C11 0.0 (4) C13—C14—C19—C18 −177.4 (2)
Br1—C9—C10—C11 178.8 (2) C17—C18—C19—C14 −0.2 (4)
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2457).

References

  1. 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.
  2. Buu-Hoï, N. P. & Royer, R. (1950). J. Org. Chem.15, 123–130.
  3. Caulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). Eur. Patent EP 1253141.
  4. Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005a). Fine Chem.22, 39–40.
  5. Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005b). Fine Chem.22, 52.
  6. Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  7. Harfenist, M. & Joyner, C. T. (1983). US Patent No. 4 379 160.
  8. Harper, R. W., Lin, H. S. & Richett, M. E. (2002). World Patent WO2002079154.
  9. Rigaku (2005). CrystalClear Rigaku Americas Corporation, The Woodlands, Texas, USA.
  10. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019448/dn2457sup1.cif

e-65-o1476-sup1.cif (18.6KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019448/dn2457Isup2.hkl

e-65-o1476-Isup2.hkl (130.8KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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