PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1589.
Published online 2009 June 17. doi:  10.1107/S160053680901976X
PMCID: PMC2969443

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

Abstract

The title compound, C19H13BrFN, was synthesized by N-alkyl­ation of 1-chloro­methyl-4-fluoro­benzene with 3-bromo-9H-carbazole. The carbazole ring system is essentially planar (r.m.s. deviation of 0.024 Å for the non-H atoms) and forms a dihedral angle of 88.2 (3)° with the benzene ring.

Related literature

For a similar structure, see: Huang et al. (2007 [triangle]). For the synthetic procedure, see: Duan et al. (2005a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1589-scheme1.jpg

Experimental

Crystal data

  • C19H13BrFN
  • M r = 354.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1589-efi1.jpg
  • a = 17.407 (4) Å
  • b = 15.068 (3) Å
  • c = 5.5865 (11) Å
  • V = 1465.3 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.81 mm−1
  • T = 113 K
  • 0.18 × 0.12 × 0.08 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.632, T max = 0.806
  • 9581 measured reflections
  • 2577 independent reflections
  • 2294 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.070
  • S = 0.99
  • 2577 reflections
  • 199 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.43 e Å−3
  • Δρmin = −0.69 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1139 Friedel pairs
  • Flack parameter: 0.004 (12)

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901976X/gk2211sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901976X/gk2211Isup2.hkl

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

supplementary crystallographic information

Comment

N-Alkyl carbazoles possess valuable pharmaceutical properties. In this paper, synthesis and the crystal structure of 3-bromo-9-(4-fluorobenzyl)-9H-carbazole is reported

The carbazole ring is essentially planar, with a r.m.s. deviation from the mean plane of 0.024 Å for the non-hydrogen atoms. The dihedral angle formed between the carbazole unit and the benzene ring is 88.2 (3) Å.

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-fluorobenzene (0.87 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 the title compound. Yield: 1.27 g (89.5%); m.p. 420–422 K. The title compound (40 mg) was dissolved in a mixture of chloroform (5 ml) and ethanol (5 ml) and the solution was kept at room temperature for 13 days. Evaporation of the solution gave colourless crystals suitable for X-ray analysis.

Refinement

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

Figures

Fig. 1.
Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are presented as spheres of arbitrary radius.

Crystal data

C19H13BrFNDx = 1.606 Mg m3
Mr = 354.21Melting point = 420–422 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 4959 reflections
a = 17.407 (4) Åθ = 1.8–27.9°
b = 15.068 (3) ŵ = 2.81 mm1
c = 5.5865 (11) ÅT = 113 K
V = 1465.3 (5) Å3Prism, colorless
Z = 40.18 × 0.12 × 0.08 mm
F(000) = 712

Data collection

Rigaku Saturn diffractometer2577 independent reflections
Radiation source: rotating anode2294 reflections with I > 2σ(I)
confocal multilayer X-ray opticRint = 0.050
Detector resolution: 7.31 pixels mm-1θmax = 25.0°, θmin = 1.8°
ω and [var phi] scansh = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −11→17
Tmin = 0.632, Tmax = 0.806l = −6→6
9581 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.070w = 1/[σ2(Fo2) + (0.0325P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.002
2577 reflectionsΔρmax = 0.43 e Å3
199 parametersΔρmin = −0.69 e Å3
1 restraintAbsolute structure: Flack (1983), 1139 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.004 (12)

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.

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

xyzUiso*/Ueq
Br10.257719 (15)0.68839 (2)1.21455 (15)0.02390 (12)
F10.64152 (11)1.09557 (12)0.7028 (5)0.0424 (5)
N10.53809 (16)0.69284 (17)0.5849 (5)0.0157 (7)
C10.58579 (15)0.63539 (19)0.7103 (7)0.0154 (6)
C20.66123 (18)0.6094 (2)0.6612 (6)0.0195 (8)
H20.68710.63040.52700.023*
C30.69613 (18)0.5514 (2)0.8188 (6)0.0224 (9)
H30.74610.53280.78820.027*
C40.6585 (2)0.5198 (2)1.0230 (7)0.0240 (9)
H40.68370.48151.12730.029*
C50.58356 (18)0.5459 (2)1.0697 (6)0.0187 (8)
H50.55820.52471.20460.022*
C60.54659 (18)0.6037 (2)0.9140 (6)0.0156 (8)
C70.47175 (18)0.6440 (2)0.9118 (6)0.0137 (7)
C80.40789 (17)0.6400 (2)1.0641 (5)0.0163 (8)
H80.40780.60341.19820.020*
C90.34574 (19)0.6916 (2)1.0091 (6)0.0165 (8)
C100.34296 (18)0.7470 (2)0.8090 (6)0.0183 (8)
H100.29910.78040.77780.022*
C110.40517 (18)0.7520 (2)0.6580 (6)0.0199 (8)
H110.40440.78960.52600.024*
C120.46916 (15)0.70008 (18)0.7062 (8)0.0144 (6)
C130.56110 (19)0.7523 (2)0.3949 (6)0.0188 (8)
H13A0.51930.75720.28080.023*
H13B0.60470.72680.31190.023*
C140.58251 (18)0.8443 (2)0.4797 (6)0.0136 (7)
C150.62396 (17)0.8572 (2)0.6911 (8)0.0210 (7)
H150.63820.80840.78330.025*
C160.64408 (18)0.9420 (2)0.7646 (6)0.0253 (10)
H160.67200.95040.90470.030*
C170.6225 (2)1.0122 (2)0.6294 (6)0.0258 (9)
C180.5814 (2)1.0036 (2)0.4166 (7)0.0280 (9)
H180.56771.05280.32570.034*
C190.56160 (18)0.9178 (2)0.3464 (6)0.0211 (8)
H190.53360.90970.20620.025*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.01522 (18)0.0313 (2)0.02516 (18)0.00202 (13)0.0037 (3)−0.0041 (2)
F10.0644 (14)0.0163 (10)0.0464 (12)−0.0111 (9)0.0121 (17)−0.0079 (14)
N10.0132 (16)0.0153 (16)0.0187 (16)−0.0052 (12)0.0024 (12)−0.0004 (13)
C10.0149 (15)0.0133 (15)0.0180 (15)−0.0033 (12)−0.003 (2)−0.004 (2)
C20.0160 (17)0.0242 (19)0.018 (2)−0.0069 (15)0.0010 (14)−0.0034 (16)
C30.0119 (19)0.020 (2)0.035 (2)0.0037 (15)−0.0007 (16)−0.0073 (17)
C40.023 (2)0.017 (2)0.032 (2)0.0003 (17)−0.0037 (17)−0.0009 (18)
C50.018 (2)0.0174 (19)0.0203 (18)0.0009 (16)−0.0073 (16)−0.0043 (16)
C60.0133 (18)0.0165 (19)0.0170 (18)−0.0070 (15)0.0033 (15)−0.0080 (16)
C70.0151 (18)0.0103 (18)0.0158 (17)0.0010 (15)−0.0042 (14)−0.0019 (16)
C80.0145 (19)0.0160 (18)0.0185 (18)−0.0024 (16)−0.0019 (14)0.0004 (16)
C90.0114 (19)0.018 (2)0.0197 (19)−0.0047 (15)0.0032 (15)−0.0067 (16)
C100.0132 (19)0.0189 (19)0.0228 (18)0.0016 (15)−0.0032 (14)−0.0026 (15)
C110.0247 (19)0.0155 (18)0.020 (2)−0.0040 (16)−0.0033 (14)0.0011 (15)
C120.0134 (14)0.0137 (16)0.0161 (15)−0.0035 (12)0.003 (2)−0.0022 (19)
C130.0177 (19)0.021 (2)0.0177 (17)−0.0020 (16)0.0011 (15)0.0000 (17)
C140.0124 (18)0.0126 (18)0.0158 (17)−0.0036 (15)0.0083 (14)−0.0013 (16)
C150.0239 (17)0.0190 (17)0.0201 (18)−0.0012 (14)0.000 (2)0.004 (2)
C160.0259 (19)0.027 (2)0.023 (3)−0.0048 (16)0.0036 (15)−0.0061 (17)
C170.031 (2)0.015 (2)0.031 (2)−0.0017 (17)0.0144 (16)−0.0045 (17)
C180.032 (2)0.021 (2)0.031 (2)0.0086 (19)0.0079 (19)0.0025 (19)
C190.0169 (19)0.028 (2)0.0184 (19)−0.0005 (17)0.0032 (15)0.0038 (17)

Geometric parameters (Å, °)

Br1—C91.915 (3)C8—H80.9300
F1—C171.363 (4)C9—C101.396 (5)
N1—C121.382 (4)C10—C111.375 (4)
N1—C11.389 (4)C10—H100.9300
N1—C131.446 (4)C11—C121.387 (4)
C1—C21.398 (4)C11—H110.9300
C1—C61.410 (5)C13—C141.512 (4)
C2—C31.381 (5)C13—H13A0.9700
C2—H20.9300C13—H13B0.9700
C3—C41.399 (5)C14—C191.383 (4)
C3—H30.9300C14—C151.397 (5)
C4—C51.387 (5)C15—C161.387 (4)
C4—H40.9300C15—H150.9300
C5—C61.389 (5)C16—C171.353 (5)
C5—H50.9300C16—H160.9300
C6—C71.437 (4)C17—C181.394 (6)
C7—C81.401 (4)C18—C191.394 (5)
C7—C121.427 (5)C18—H180.9300
C8—C91.368 (5)C19—H190.9300
C12—N1—C1108.7 (3)C9—C10—H10120.1
C12—N1—C13123.5 (3)C10—C11—C12118.9 (3)
C1—N1—C13126.2 (3)C10—C11—H11120.6
N1—C1—C2129.6 (3)C12—C11—H11120.6
N1—C1—C6109.2 (3)N1—C12—C11130.3 (3)
C2—C1—C6121.2 (3)N1—C12—C7108.7 (2)
C3—C2—C1117.8 (3)C11—C12—C7121.0 (3)
C3—C2—H2121.1N1—C13—C14114.0 (3)
C1—C2—H2121.1N1—C13—H13A108.8
C2—C3—C4121.9 (3)C14—C13—H13A108.8
C2—C3—H3119.0N1—C13—H13B108.8
C4—C3—H3119.0C14—C13—H13B108.8
C5—C4—C3119.8 (3)H13A—C13—H13B107.6
C5—C4—H4120.1C19—C14—C15118.7 (3)
C3—C4—H4120.1C19—C14—C13120.0 (3)
C4—C5—C6119.7 (3)C15—C14—C13121.3 (3)
C4—C5—H5120.2C16—C15—C14120.5 (3)
C6—C5—H5120.2C16—C15—H15119.7
C5—C6—C1119.6 (3)C14—C15—H15119.7
C5—C6—C7133.6 (3)C17—C16—C15119.0 (3)
C1—C6—C7106.8 (3)C17—C16—H16120.5
C8—C7—C12119.3 (3)C15—C16—H16120.5
C8—C7—C6134.1 (3)C16—C17—F1119.0 (4)
C12—C7—C6106.6 (3)C16—C17—C18123.1 (3)
C9—C8—C7117.8 (3)F1—C17—C18117.8 (4)
C9—C8—H8121.1C17—C18—C19116.9 (3)
C7—C8—H8121.1C17—C18—H18121.5
C8—C9—C10123.2 (3)C19—C18—H18121.5
C8—C9—Br1118.9 (3)C14—C19—C18121.7 (3)
C10—C9—Br1117.9 (3)C14—C19—H19119.1
C11—C10—C9119.8 (3)C18—C19—H19119.1
C11—C10—H10120.1
C12—N1—C1—C2−178.2 (3)C9—C10—C11—C121.3 (5)
C13—N1—C1—C2−12.3 (5)C1—N1—C12—C11176.9 (3)
C12—N1—C1—C61.0 (3)C13—N1—C12—C1110.5 (5)
C13—N1—C1—C6166.9 (3)C1—N1—C12—C7−1.6 (3)
N1—C1—C2—C3179.3 (3)C13—N1—C12—C7−167.9 (3)
C6—C1—C2—C30.1 (5)C10—C11—C12—N1−179.9 (3)
C1—C2—C3—C4−0.7 (5)C10—C11—C12—C7−1.7 (5)
C2—C3—C4—C50.9 (5)C8—C7—C12—N1−180.0 (3)
C3—C4—C5—C6−0.5 (5)C6—C7—C12—N11.5 (4)
C4—C5—C6—C1−0.1 (5)C8—C7—C12—C111.4 (5)
C4—C5—C6—C7−178.7 (3)C6—C7—C12—C11−177.1 (3)
N1—C1—C6—C5−179.0 (3)C12—N1—C13—C1472.0 (4)
C2—C1—C6—C50.3 (5)C1—N1—C13—C14−92.0 (4)
N1—C1—C6—C7−0.1 (4)N1—C13—C14—C19−141.1 (3)
C2—C1—C6—C7179.2 (3)N1—C13—C14—C1539.5 (4)
C5—C6—C7—C8−0.4 (7)C19—C14—C15—C16−0.4 (5)
C1—C6—C7—C8−179.1 (4)C13—C14—C15—C16179.1 (3)
C5—C6—C7—C12177.9 (4)C14—C15—C16—C170.5 (5)
C1—C6—C7—C12−0.8 (4)C15—C16—C17—F1179.3 (3)
C12—C7—C8—C9−0.8 (5)C15—C16—C17—C18−0.7 (5)
C6—C7—C8—C9177.3 (3)C16—C17—C18—C190.8 (5)
C7—C8—C9—C100.5 (5)F1—C17—C18—C19−179.2 (3)
C7—C8—C9—Br1−179.6 (2)C15—C14—C19—C180.5 (5)
C8—C9—C10—C11−0.8 (5)C13—C14—C19—C18−178.9 (3)
Br1—C9—C10—C11179.4 (2)C17—C18—C19—C14−0.7 (5)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2211).

References

  • 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.
  • Huang, P.-M., Duan, X.-M. & Yang, D.-W. (2007). Acta Cryst. E63, o1264–o1265.
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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