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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, with a mean deviation of 0.026 Å, and makes a dihedral angle of 75.16 (7)° with the plane of the benzene ring.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040821/ww6464sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040821/ww6464Isup2.hkl
Contains datablock I

CCDC reference: 296707

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C)= 0.005 Å
  • R factor = 0.035
  • wR factor = 0.098
  • Data-to-parameter ratio = 15.9

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Comment top

Carbazole derivatives substituted by N-alkylation show useful pharmaceutical properties (Buu-Hoï & Royer, 1950; Harfenist & Joyner, 1983; Caulfield et al., 2002; Harper et al., 2002). In this paper, the structure of 3,6-dibromo-9-(4-chloro-benzyl)-9H-carbazole, (I), is reported; this was synthesized by N-alkylation of 1-chloro-4-(chloromethyl)benzene with 3,6-dibromo-9H-carbazole.

The carbazole ring in (I) is essentially planar, with a mean deviation of 0.026 Å. The dihedral angle formed between the carbazole ring and the plane of the benzene ring is 75.16 (7)°. The C—Cl distance is 1.738 (4) Å and the C—Br distances are 1.906 (4) and 1.909 (3) Å.

Experimental top

The title compound was prepared according to the procedure of Duan et al. (2005). A solution of potassium hydroxide (7.0 g) in dimethylformamide (50 ml) was stirred at room temperature for 20 min. 3,6-Dibromo-9H-carbazole (6.50 g, 20 mmol) (Smith et al., 1992) was added and the mixture stirred for a further 40 min. A solution of with 1-chloro-4-(chloromethyl)benzene (4.83 g, 30 mmol) in dimethylformamide (50 ml) was added dropwise with stirring. The resulting mixture was then stirred at room temperature for 12 h and poured into water (500 ml), yielding a white precipitate. The solid product was filtered off, washed with cold water and recrystallized from EtOH, giving crystals of (I) (yield: 7.88 g, 87.5%; m.p. 443–444 K). Compound (I) (40 mg) was dissolved in a mixture of chloroform (5 ml) and ethanol (5 ml) and the solution was kept at room temperature for 16 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 = 0.93 (aromatic) and 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellopsoids are drawn at the 30% probability level.
3,6-Dibromo-9-(4-chlorobenzyl)-9H-carbazole top
Crystal data top
C19H12Br2ClNDx = 1.812 Mg m3
Mr = 449.57Melting point: 443(1) K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4904 reflections
a = 8.968 (2) Åθ = 2.6–24.9°
b = 16.690 (3) ŵ = 5.08 mm1
c = 22.019 (4) ÅT = 294 K
V = 3295.7 (11) Å3Rod, colourless
Z = 80.28 × 0.26 × 0.22 mm
F(000) = 1760
Data collection top
Bruker SMART CCD area-detector
diffractometer
3315 independent reflections
Radiation source: fine-focus sealed tube2366 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ϕ and ω scansθmax = 26.2°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1011
Tmin = 0.269, Tmax = 0.327k = 820
17184 measured reflectionsl = 2727
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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0503P)2 + 0.6556P]
where P = (Fo2 + 2Fc2)/3
3315 reflections(Δ/σ)max = 0.002
208 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.56 e Å3
Crystal data top
C19H12Br2ClNV = 3295.7 (11) Å3
Mr = 449.57Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 8.968 (2) ŵ = 5.08 mm1
b = 16.690 (3) ÅT = 294 K
c = 22.019 (4) Å0.28 × 0.26 × 0.22 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3315 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2366 reflections with I > 2σ(I)
Tmin = 0.269, Tmax = 0.327Rint = 0.053
17184 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.07Δρmax = 0.54 e Å3
3315 reflectionsΔρmin = 0.56 e Å3
208 parameters
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 > 2σ(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
Br10.22200 (5)0.91093 (3)0.062574 (15)0.05711 (16)
Br20.65046 (5)1.19415 (3)0.34265 (2)0.06650 (17)
Cl10.53505 (11)0.59285 (6)0.44585 (4)0.0547 (3)
N10.2047 (3)0.92621 (19)0.33511 (12)0.0406 (7)
C10.2832 (3)0.9709 (2)0.24310 (14)0.0332 (7)
C20.2923 (4)0.9708 (2)0.17977 (14)0.0372 (8)
H20.35331.00680.15920.045*
C30.2080 (4)0.9156 (2)0.14901 (14)0.0397 (8)
C40.1144 (4)0.8611 (2)0.17806 (15)0.0423 (8)
H40.05840.82510.15530.051*
C50.1050 (4)0.8607 (2)0.24053 (15)0.0418 (8)
H50.04260.82490.26060.050*
C60.1911 (3)0.9153 (2)0.27271 (14)0.0354 (7)
C70.3058 (4)0.9866 (2)0.34581 (14)0.0372 (8)
C80.3602 (4)1.0170 (2)0.40073 (15)0.0465 (9)
H80.32830.99610.43770.056*
C90.4613 (4)1.0780 (2)0.39866 (16)0.0502 (10)
H90.49881.09910.43460.060*
C100.5089 (4)1.1090 (2)0.34322 (17)0.0470 (9)
C110.4576 (4)1.0793 (2)0.28841 (15)0.0415 (8)
H110.49071.10060.25180.050*
C120.3564 (3)1.0177 (2)0.28954 (14)0.0343 (7)
C130.1432 (4)0.8726 (2)0.38182 (15)0.0442 (9)
H13A0.04930.85090.36740.053*
H13B0.12280.90350.41820.053*
C140.2458 (4)0.8047 (2)0.39766 (14)0.0366 (8)
C150.2739 (4)0.7441 (2)0.35599 (14)0.0431 (8)
H150.23080.74670.31760.052*
C160.3642 (4)0.6801 (2)0.37021 (15)0.0420 (8)
H160.38160.63990.34190.050*
C170.4289 (4)0.6764 (2)0.42716 (15)0.0390 (8)
C180.4052 (4)0.7361 (2)0.46899 (15)0.0463 (9)
H180.45000.73370.50700.056*
C190.3144 (4)0.7996 (2)0.45399 (15)0.0466 (9)
H190.29870.84010.48230.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0605 (3)0.0756 (3)0.0352 (2)0.0012 (2)0.00100 (16)0.00966 (18)
Br20.0573 (3)0.0542 (3)0.0879 (3)0.0085 (2)0.0156 (2)0.0084 (2)
Cl10.0624 (6)0.0518 (6)0.0501 (5)0.0143 (5)0.0024 (4)0.0024 (4)
N10.0416 (15)0.0474 (19)0.0328 (13)0.0023 (15)0.0031 (12)0.0067 (13)
C10.0279 (15)0.0356 (19)0.0362 (16)0.0046 (15)0.0008 (13)0.0007 (14)
C20.0379 (17)0.039 (2)0.0345 (16)0.0001 (17)0.0039 (14)0.0011 (15)
C30.0373 (17)0.050 (2)0.0323 (16)0.0086 (18)0.0010 (14)0.0024 (15)
C40.0340 (17)0.046 (2)0.0467 (19)0.0018 (17)0.0069 (15)0.0014 (17)
C50.0310 (17)0.045 (2)0.049 (2)0.0025 (17)0.0017 (15)0.0089 (17)
C60.0306 (16)0.0369 (19)0.0387 (16)0.0065 (15)0.0005 (13)0.0047 (15)
C70.0388 (17)0.038 (2)0.0353 (16)0.0099 (16)0.0011 (13)0.0005 (15)
C80.056 (2)0.050 (2)0.0335 (17)0.012 (2)0.0007 (15)0.0012 (16)
C90.054 (2)0.052 (2)0.045 (2)0.012 (2)0.0106 (17)0.0112 (18)
C100.0422 (19)0.042 (2)0.057 (2)0.0049 (18)0.0050 (16)0.0059 (18)
C110.0393 (18)0.043 (2)0.0420 (18)0.0057 (17)0.0027 (14)0.0012 (16)
C120.0339 (16)0.0330 (19)0.0361 (16)0.0063 (16)0.0018 (13)0.0024 (14)
C130.0411 (19)0.051 (2)0.0406 (18)0.0019 (18)0.0099 (15)0.0099 (17)
C140.0354 (17)0.041 (2)0.0333 (16)0.0054 (16)0.0075 (13)0.0082 (15)
C150.048 (2)0.047 (2)0.0338 (16)0.0039 (19)0.0002 (15)0.0047 (16)
C160.050 (2)0.039 (2)0.0368 (17)0.0041 (18)0.0028 (16)0.0018 (15)
C170.0387 (18)0.039 (2)0.0390 (18)0.0032 (16)0.0049 (14)0.0060 (15)
C180.057 (2)0.048 (2)0.0339 (17)0.0057 (19)0.0040 (15)0.0002 (17)
C190.058 (2)0.046 (2)0.0363 (17)0.0057 (19)0.0044 (16)0.0027 (16)
Geometric parameters (Å, º) top
Br1—C31.909 (3)C8—H80.9300
Br2—C101.906 (4)C9—C101.393 (5)
Cl1—C171.738 (4)C9—H90.9300
N1—C71.376 (5)C10—C111.383 (5)
N1—C61.392 (4)C11—C121.372 (5)
N1—C131.470 (4)C11—H110.9300
C1—C21.397 (4)C13—C141.501 (5)
C1—C61.404 (4)C13—H13A0.9700
C1—C121.444 (4)C13—H13B0.9700
C2—C31.371 (5)C14—C191.387 (5)
C2—H20.9300C14—C151.389 (5)
C3—C41.393 (5)C15—C161.376 (5)
C4—C51.378 (5)C15—H150.9300
C4—H40.9300C16—C171.383 (5)
C5—C61.389 (5)C16—H160.9300
C5—H50.9300C17—C181.374 (5)
C7—C81.399 (5)C18—C191.377 (5)
C7—C121.418 (4)C18—H180.9300
C8—C91.364 (5)C19—H190.9300
C7—N1—C6108.8 (3)C9—C10—Br2119.2 (3)
C7—N1—C13125.0 (3)C12—C11—C10118.2 (3)
C6—N1—C13125.3 (3)C12—C11—H11120.9
C2—C1—C6119.8 (3)C10—C11—H11120.9
C2—C1—C12132.9 (3)C11—C12—C7120.1 (3)
C6—C1—C12107.2 (3)C11—C12—C1133.9 (3)
C3—C2—C1117.5 (3)C7—C12—C1106.0 (3)
C3—C2—H2121.2N1—C13—C14113.1 (3)
C1—C2—H2121.2N1—C13—H13A109.0
C2—C3—C4123.0 (3)C14—C13—H13A109.0
C2—C3—Br1118.9 (3)N1—C13—H13B109.0
C4—C3—Br1118.1 (3)C14—C13—H13B109.0
C5—C4—C3119.9 (3)H13A—C13—H13B107.8
C5—C4—H4120.0C19—C14—C15117.7 (3)
C3—C4—H4120.0C19—C14—C13121.7 (3)
C4—C5—C6118.1 (3)C15—C14—C13120.5 (3)
C4—C5—H5120.9C16—C15—C14121.4 (3)
C6—C5—H5120.9C16—C15—H15119.3
C5—C6—N1129.7 (3)C14—C15—H15119.3
C5—C6—C1121.6 (3)C15—C16—C17119.2 (3)
N1—C6—C1108.7 (3)C15—C16—H16120.4
N1—C7—C8130.0 (3)C17—C16—H16120.4
N1—C7—C12109.2 (3)C18—C17—C16120.7 (3)
C8—C7—C12120.8 (3)C18—C17—Cl1120.6 (3)
C9—C8—C7118.2 (3)C16—C17—Cl1118.7 (3)
C9—C8—H8120.9C17—C18—C19119.3 (3)
C7—C8—H8120.9C17—C18—H18120.4
C8—C9—C10120.7 (3)C19—C18—H18120.4
C8—C9—H9119.6C18—C19—C14121.6 (3)
C10—C9—H9119.6C18—C19—H19119.2
C11—C10—C9121.9 (4)C14—C19—H19119.2
C11—C10—Br2118.9 (3)
C6—C1—C2—C30.7 (5)C9—C10—C11—C120.2 (5)
C12—C1—C2—C3178.2 (3)Br2—C10—C11—C12179.6 (2)
C1—C2—C3—C40.5 (5)C10—C11—C12—C70.7 (5)
C1—C2—C3—Br1178.0 (2)C10—C11—C12—C1177.9 (3)
C2—C3—C4—C50.7 (5)N1—C7—C12—C11179.4 (3)
Br1—C3—C4—C5177.8 (3)C8—C7—C12—C111.4 (5)
C3—C4—C5—C60.3 (5)N1—C7—C12—C11.6 (4)
C4—C5—C6—N1178.5 (3)C8—C7—C12—C1177.6 (3)
C4—C5—C6—C11.5 (5)C2—C1—C12—C111.8 (6)
C7—N1—C6—C5178.8 (3)C6—C1—C12—C11179.6 (3)
C13—N1—C6—C59.2 (5)C2—C1—C12—C7176.9 (3)
C7—N1—C6—C11.2 (4)C6—C1—C12—C70.8 (3)
C13—N1—C6—C1170.8 (3)C7—N1—C13—C1481.2 (4)
C2—C1—C6—C51.7 (5)C6—N1—C13—C1486.7 (4)
C12—C1—C6—C5179.8 (3)N1—C13—C14—C19111.7 (4)
C2—C1—C6—N1178.3 (3)N1—C13—C14—C1568.8 (4)
C12—C1—C6—N10.2 (3)C19—C14—C15—C161.3 (5)
C6—N1—C7—C8177.3 (3)C13—C14—C15—C16178.1 (3)
C13—N1—C7—C87.7 (6)C14—C15—C16—C170.3 (5)
C6—N1—C7—C121.8 (4)C15—C16—C17—C180.8 (5)
C13—N1—C7—C12171.4 (3)C15—C16—C17—Cl1176.8 (3)
N1—C7—C8—C9180.0 (3)C16—C17—C18—C190.9 (5)
C12—C7—C8—C91.0 (5)Cl1—C17—C18—C19176.7 (3)
C7—C8—C9—C100.1 (5)C17—C18—C19—C140.2 (6)
C8—C9—C10—C110.6 (6)C15—C14—C19—C181.3 (5)
C8—C9—C10—Br2179.9 (3)C13—C14—C19—C18178.2 (3)

Experimental details

Crystal data
Chemical formulaC19H12Br2ClN
Mr449.57
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)294
a, b, c (Å)8.968 (2), 16.690 (3), 22.019 (4)
V3)3295.7 (11)
Z8
Radiation typeMo Kα
µ (mm1)5.08
Crystal size (mm)0.28 × 0.26 × 0.22
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.269, 0.327
No. of measured, independent and
observed [I > 2σ(I)] reflections
17184, 3315, 2366
Rint0.053
(sin θ/λ)max1)0.622
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.099, 1.07
No. of reflections3315
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.56

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

 

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