organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aCollege of Chemistry and Bioengineering, Changsha University of Science and Technology, Changsha 410076, People's Republic of China
*Correspondence e-mail: xiaozidan2009@126.com

(Received 13 May 2009; accepted 22 May 2009; online 6 June 2009)

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[Buu-Hoï, N. P. & Royer, R. (1950). J. Org. Chem. 15, 123-130.]); Caulfield et al. (2002[Caulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). Eur. Patent EP 1253141.]); Harfenist & Joyner (1983[Harfenist, M. & Joyner, C. T. (1983). US Patent No. 4 379 160.]); Harper et al. (2002[Harper, R. W., Lin, H. S. & Richett, M. E. (2002). World Patent WO2002079154.]). For bond-length data, see Allen et al. (1987[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.]). For synthetic procedures, see: Duan et al. (2005a[Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005a). Fine Chem. 22, 39-40.],b[Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005b). Fine Chem. 22, 52.]).

[Scheme 1]

Experimental

Crystal data
  • C19H13BrClN

  • Mr = 370.66

  • Orthorhombic, P n a 21

  • 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[Rigaku (2005). CrystalClear. Rigaku Americas Corporation, The Woodlands, Texas, USA.]) Tmin = 0.627, Tmax = 0.803

  • 10796 measured reflections

  • 2664 independent reflections

  • 2401 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.023

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1163 Friedel pairs

  • Flack parameter: 0.014 (9)

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Americas Corporation, The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 m3
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 mm1
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)
Confocal monochromatorRint = 0.031
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 1.8°
ω and ϕ scansh = 2019
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 1818
Tmin = 0.627, Tmax = 0.803l = 66
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 Å3
199 parametersΔρmin = 0.47 e Å3
1 restraintAbsolute structure: Flack (1983), 1163 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H-atom parameters constrained
wR(F2) = 0.056Δρmax = 0.38 e Å3
S = 1.04Δρmin = 0.47 e Å3
2664 reflectionsAbsolute structure: Flack (1983), 1163 Friedel pairs
199 parametersAbsolute structure 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)
H40.68480.01981.20380.028*
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, º) 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—C2178.2 (3)C9—C10—C11—C120.8 (4)
C13—N1—C1—C212.0 (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—C71.7 (3)
N1—C1—C2—C3179.4 (3)C13—N1—C12—C7168.4 (2)
C6—C1—C2—C30.4 (4)C10—C11—C12—N1179.6 (3)
C1—C2—C3—C40.1 (4)C10—C11—C12—C71.9 (4)
C2—C3—C4—C50.1 (4)C8—C7—C12—N1179.7 (2)
C3—C4—C5—C60.3 (4)C6—C7—C12—N11.2 (3)
C4—C5—C6—C10.6 (4)C8—C7—C12—C112.2 (4)
C4—C5—C6—C7178.3 (3)C6—C7—C12—C11177.0 (2)
N1—C1—C6—C5179.2 (2)C1—N1—C13—C1493.3 (3)
C2—C1—C6—C50.6 (4)C12—N1—C13—C1470.8 (3)
N1—C1—C6—C70.9 (3)N1—C13—C14—C19142.8 (3)
C2—C1—C6—C7178.9 (2)N1—C13—C14—C1539.3 (4)
C5—C6—C7—C81.2 (5)C19—C14—C15—C160.7 (4)
C1—C6—C7—C8179.1 (3)C13—C14—C15—C16177.2 (2)
C5—C6—C7—C12177.8 (3)C14—C15—C16—C170.6 (4)
C1—C6—C7—C120.1 (3)C15—C16—C17—C180.3 (4)
C12—C7—C8—C91.3 (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—Br1178.51 (19)C15—C14—C19—C180.6 (4)
C8—C9—C10—C110.0 (4)C13—C14—C19—C18177.4 (2)
Br1—C9—C10—C11178.8 (2)C17—C18—C19—C140.2 (4)

Experimental details

Crystal data
Chemical formulaC19H13BrClN
Mr370.66
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)113
a, b, c (Å)17.272 (4), 15.789 (3), 5.5948 (11)
V3)1525.7 (5)
Z4
Radiation typeMo Kα
µ (mm1)2.86
Crystal size (mm)0.18 × 0.16 × 0.08
Data collection
DiffractometerRigaku Saturn CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.627, 0.803
No. of measured, independent and
observed [I > 2σ(I)] reflections
10796, 2664, 2401
Rint0.031
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.056, 1.04
No. of reflections2664
No. of parameters199
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.47
Absolute structureFlack (1983), 1163 Friedel pairs
Absolute structure parameter0.014 (9)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

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

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First citationBuu-Hoï, N. P. & Royer, R. (1950). J. Org. Chem. 15, 123–130.  CrossRef CAS Google Scholar
First citationCaulfield, T., Cherrier, M. P., Combeau, C. & Mailliet, P. (2002). Eur. Patent EP 1253141.  Google Scholar
First citationDuan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005a). Fine Chem. 22, 39–40.  CAS Google Scholar
First citationDuan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005b). Fine Chem. 22, 52.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHarfenist, M. & Joyner, C. T. (1983). US Patent No. 4 379 160.  Google Scholar
First citationHarper, R. W., Lin, H. S. & Richett, M. E. (2002). World Patent WO2002079154.  Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Americas Corporation, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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