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The title compound, C18H12Br2N2, was synthesized by N-alkyl­ation of 3-(chloro­meth­yl)pyridine with 3,6-dibromo-9H-carbazole. The carbazole ring system is essentially planar, with a mean deviation of 0.0138 Å, and forms a dihedral angle of 96.7 (8)° with the plane of the pyridine ring. In the crystal structure, π–π inter­actions and weak C—H...Br inter­actions are observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040535/bd6019sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040535/bd6019Isup2.hkl
Contains datablock I

CCDC reference: 296518

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C)= 0.005 Å
  • R factor = 0.034
  • wR factor = 0.078
  • Data-to-parameter ratio = 16.0

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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). The title compound 3,6-dibromo-9-(3-pyridylmethyl)-9H-carbazole, (I) (Fig. 1), was synthesized by N-alkylation of 3-(Chloromethyl)pyridine with 3,6-dibromo-9H-carbazole.

The carbazole ring is essentially planar, with mean deviations of 0.0138 Å. These values are consistent with those previously reported (Huang et al., 2005; Duan, Han et al., 2005 or Duan, Huang et al., 2005). The dihedral angle formed between the carbazole ring and the plane of the pyridine ring is 96.7 (su?)°. C—Br distances are in the range 1.905 (3) to 1.907 (3) Å and are consistent with literature values (Allen et al., 1987). In the crystal structure, ππ interactions are observed; the shortest, 3.519 Å, is between the N1, C?–C12 and C7–C12 rings of molecules related by (1 − x, −y, 2 − z). In addition, there are C—H···Br interactions, as shown in Fig. 2 and detailed in Table 1.

Experimental top

The title compound was prepared according to the procedure of Duan, Han et al. (2005) or Duan, Huang 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-carbazole (6.5 g, 20 mmol), prepared according to Smith et al. (1992), was added and the mixture stirred for a further 40 min. A solution of 3-(chloromethyl)pyridine (3.825 g, 30 mmol) in dimethylformamide (50 ml) was added dropwise with stirring. The resulting mixture was then stirred at room temperature for 10 h and poured into water (500 ml), yielding a white precipitate. The solid product (I) was collected by filtration, washed with cold water and recrystallized from EtOH (yield: 7.11 g (85.5%); m.p. 488 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 18 d. Slow evaporation of the solution yielded colourless crystals suitable for X-ray analysis.

Refinement top

All H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.93 (aromatic) and 0.97 (methylene) Å, and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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. Displacement ellipsoid (30%) plot of (I).
[Figure 2] Fig. 2. Packing diagram of (I), viewed along [001]. Dashed lines indicate C—H···Br interactions.
3,6-Dibromo-9-(3-pyridylmethyl)-9H-carbazole top
Crystal data top
C18H12Br2N2F(000) = 816
Mr = 416.12Dx = 1.769 Mg m3
Monoclinic, P21/cMelting point: 488 K
Hall symbol: -p 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.469 (3) ÅCell parameters from 2796 reflections
b = 16.405 (5) Åθ = 2.5–26.4°
c = 9.866 (3) ŵ = 5.19 mm1
β = 112.761 (4)°T = 294 K
V = 1562.6 (8) Å3Rod, colourless
Z = 40.26 × 0.22 × 0.14 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3194 independent reflections
Radiation source: fine-focus sealed tube2238 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ϕ and ω scansθmax = 26.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1213
Tmin = 0.258, Tmax = 0.484k = 1620
8670 measured reflectionsl = 1012
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)] = 0.034H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0276P)2 + 0.8633P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
3194 reflectionsΔρmax = 0.48 e Å3
200 parametersΔρmin = 0.52 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0233 (8)
Crystal data top
C18H12Br2N2V = 1562.6 (8) Å3
Mr = 416.12Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.469 (3) ŵ = 5.19 mm1
b = 16.405 (5) ÅT = 294 K
c = 9.866 (3) Å0.26 × 0.22 × 0.14 mm
β = 112.761 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3194 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2238 reflections with I > 2σ(I)
Tmin = 0.258, Tmax = 0.484Rint = 0.046
8670 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 1.00Δρmax = 0.48 e Å3
3194 reflectionsΔρmin = 0.52 e Å3
200 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 > 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
Br10.00354 (4)0.11991 (3)0.40210 (4)0.06161 (17)
Br20.80862 (4)0.09086 (2)0.85957 (5)0.06183 (17)
N10.4620 (2)0.16487 (15)0.9894 (3)0.0355 (6)
N20.6579 (3)0.39737 (19)1.0202 (4)0.0605 (9)
C10.3459 (3)0.16398 (18)0.8594 (3)0.0314 (7)
C20.2245 (3)0.20913 (19)0.8188 (4)0.0409 (8)
H20.21240.24770.88190.049*
C30.1226 (3)0.1950 (2)0.6824 (4)0.0426 (8)
H30.04010.22410.65250.051*
C40.1423 (3)0.1373 (2)0.5888 (3)0.0383 (8)
C50.2617 (3)0.09198 (19)0.6256 (3)0.0353 (7)
H50.27290.05390.56130.042*
C60.3652 (3)0.10598 (17)0.7640 (3)0.0307 (7)
C70.5001 (3)0.07045 (17)0.8407 (3)0.0305 (7)
C80.5739 (3)0.01016 (18)0.8028 (3)0.0352 (7)
H80.53820.01560.71170.042*
C90.7025 (3)0.00941 (19)0.9068 (4)0.0393 (8)
C100.7577 (3)0.0265 (2)1.0449 (4)0.0438 (8)
H100.84390.01011.11230.053*
C110.6855 (3)0.0861 (2)1.0820 (4)0.0428 (8)
H110.72210.11121.17360.051*
C120.5557 (3)0.10815 (18)0.9788 (3)0.0332 (7)
C130.4866 (3)0.2169 (2)1.1169 (3)0.0415 (8)
H13A0.51900.18371.20510.050*
H13B0.40010.24221.10850.050*
C140.5693 (4)0.3393 (2)1.0215 (4)0.0482 (9)
H140.48480.33700.94160.058*
C150.5922 (3)0.28248 (19)1.1308 (3)0.0356 (7)
C160.7160 (3)0.2878 (2)1.2504 (4)0.0480 (9)
H160.73580.25161.32840.058*
C170.8103 (4)0.3470 (2)1.2535 (4)0.0573 (10)
H170.89430.35161.33350.069*
C180.7776 (4)0.3992 (2)1.1358 (5)0.0590 (10)
H180.84290.43791.13710.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0346 (2)0.0907 (3)0.0459 (2)0.00194 (19)0.00059 (15)0.0041 (2)
Br20.0535 (3)0.0609 (3)0.0743 (3)0.02057 (19)0.0283 (2)0.0020 (2)
N10.0361 (14)0.0378 (15)0.0310 (14)0.0023 (12)0.0112 (11)0.0048 (11)
N20.065 (2)0.060 (2)0.058 (2)0.0096 (17)0.0262 (18)0.0038 (16)
C10.0302 (15)0.0313 (16)0.0338 (16)0.0012 (13)0.0137 (13)0.0008 (13)
C20.0435 (19)0.0385 (19)0.044 (2)0.0040 (15)0.0206 (16)0.0037 (15)
C30.0310 (17)0.047 (2)0.048 (2)0.0062 (15)0.0128 (15)0.0071 (16)
C40.0305 (16)0.046 (2)0.0331 (17)0.0059 (15)0.0063 (13)0.0015 (14)
C50.0330 (16)0.0377 (17)0.0343 (17)0.0020 (14)0.0120 (13)0.0023 (13)
C60.0292 (15)0.0318 (17)0.0322 (16)0.0006 (12)0.0129 (13)0.0024 (13)
C70.0291 (15)0.0298 (17)0.0329 (16)0.0020 (13)0.0122 (13)0.0016 (13)
C80.0373 (17)0.0355 (18)0.0347 (17)0.0002 (14)0.0161 (14)0.0003 (13)
C90.0359 (17)0.0379 (18)0.049 (2)0.0048 (14)0.0224 (16)0.0026 (15)
C100.0321 (17)0.047 (2)0.046 (2)0.0054 (15)0.0074 (15)0.0050 (16)
C110.0379 (18)0.051 (2)0.0327 (17)0.0030 (16)0.0067 (14)0.0022 (15)
C120.0346 (16)0.0315 (17)0.0333 (17)0.0008 (13)0.0128 (13)0.0002 (13)
C130.0502 (19)0.046 (2)0.0307 (17)0.0016 (16)0.0187 (15)0.0077 (14)
C140.051 (2)0.056 (2)0.0341 (19)0.0037 (18)0.0128 (16)0.0026 (17)
C150.0388 (17)0.0418 (18)0.0290 (16)0.0038 (15)0.0161 (14)0.0096 (14)
C160.046 (2)0.050 (2)0.040 (2)0.0093 (17)0.0080 (16)0.0032 (16)
C170.0337 (19)0.062 (3)0.064 (3)0.0006 (18)0.0062 (17)0.017 (2)
C180.056 (2)0.055 (2)0.075 (3)0.0084 (19)0.035 (2)0.011 (2)
Geometric parameters (Å, º) top
Br1—C41.905 (3)C8—C91.378 (4)
Br2—C91.907 (3)C8—H80.9300
N1—C11.384 (4)C9—C101.388 (5)
N1—C121.385 (4)C10—C111.369 (4)
N1—C131.459 (4)C10—H100.9300
N2—C181.329 (5)C11—C121.395 (4)
N2—C141.333 (4)C11—H110.9300
C1—C21.389 (4)C13—C151.510 (4)
C1—C61.407 (4)C13—H13A0.9700
C2—C31.375 (4)C13—H13B0.9700
C2—H20.9300C14—C151.375 (5)
C3—C41.392 (5)C14—H140.9300
C3—H30.9300C15—C161.377 (4)
C4—C51.376 (4)C16—C171.377 (5)
C5—C61.395 (4)C16—H160.9300
C5—H50.9300C17—C181.375 (6)
C6—C71.443 (4)C17—H170.9300
C7—C81.393 (4)C18—H180.9300
C7—C121.401 (4)
C1—N1—C12108.5 (2)C11—C10—C9120.2 (3)
C1—N1—C13127.2 (3)C11—C10—H10119.9
C12—N1—C13124.3 (2)C9—C10—H10119.9
C18—N2—C14115.8 (3)C10—C11—C12118.2 (3)
N1—C1—C2129.7 (3)C10—C11—H11120.9
N1—C1—C6109.0 (2)C12—C11—H11120.9
C2—C1—C6121.3 (3)N1—C12—C11129.6 (3)
C3—C2—C1117.9 (3)N1—C12—C7109.3 (3)
C3—C2—H2121.0C11—C12—C7121.1 (3)
C1—C2—H2121.0N1—C13—C15111.9 (3)
C2—C3—C4120.4 (3)N1—C13—H13A109.2
C2—C3—H3119.8C15—C13—H13A109.2
C4—C3—H3119.8N1—C13—H13B109.2
C5—C4—C3123.0 (3)C15—C13—H13B109.2
C5—C4—Br1118.7 (2)H13A—C13—H13B107.9
C3—C4—Br1118.3 (2)N2—C14—C15125.6 (3)
C4—C5—C6116.8 (3)N2—C14—H14117.2
C4—C5—H5121.6C15—C14—H14117.2
C6—C5—H5121.6C14—C15—C16116.7 (3)
C5—C6—C1120.5 (3)C14—C15—C13120.9 (3)
C5—C6—C7132.8 (3)C16—C15—C13122.4 (3)
C1—C6—C7106.7 (2)C17—C16—C15119.5 (3)
C8—C7—C12120.7 (3)C17—C16—H16120.2
C8—C7—C6132.7 (3)C15—C16—H16120.2
C12—C7—C6106.6 (3)C18—C17—C16118.6 (3)
C9—C8—C7116.6 (3)C18—C17—H17120.7
C9—C8—H8121.7C16—C17—H17120.7
C7—C8—H8121.7N2—C18—C17123.7 (4)
C8—C9—C10123.2 (3)N2—C18—H18118.1
C8—C9—Br2118.3 (2)C17—C18—H18118.1
C10—C9—Br2118.5 (2)
C12—N1—C1—C2179.2 (3)C8—C9—C10—C111.8 (5)
C13—N1—C1—C22.0 (5)Br2—C9—C10—C11179.0 (2)
C12—N1—C1—C60.1 (3)C9—C10—C11—C121.0 (5)
C13—N1—C1—C6178.8 (3)C1—N1—C12—C11178.7 (3)
N1—C1—C2—C3178.6 (3)C13—N1—C12—C112.4 (5)
C6—C1—C2—C30.6 (5)C1—N1—C12—C70.3 (3)
C1—C2—C3—C40.3 (5)C13—N1—C12—C7178.6 (3)
C2—C3—C4—C50.1 (5)C10—C11—C12—N1178.9 (3)
C2—C3—C4—Br1179.4 (2)C10—C11—C12—C70.0 (5)
C3—C4—C5—C60.2 (5)C8—C7—C12—N1179.5 (3)
Br1—C4—C5—C6179.3 (2)C6—C7—C12—N10.3 (3)
C4—C5—C6—C10.0 (4)C8—C7—C12—C110.4 (5)
C4—C5—C6—C7178.8 (3)C6—C7—C12—C11178.8 (3)
N1—C1—C6—C5178.9 (3)C1—N1—C13—C15107.0 (3)
C2—C1—C6—C50.4 (4)C12—N1—C13—C1571.7 (4)
N1—C1—C6—C70.1 (3)C18—N2—C14—C150.1 (5)
C2—C1—C6—C7179.5 (3)N2—C14—C15—C161.7 (5)
C5—C6—C7—C80.4 (6)N2—C14—C15—C13177.1 (3)
C1—C6—C7—C8179.3 (3)N1—C13—C15—C1460.6 (4)
C5—C6—C7—C12178.6 (3)N1—C13—C15—C16118.1 (3)
C1—C6—C7—C120.3 (3)C14—C15—C16—C171.4 (5)
C12—C7—C8—C90.3 (4)C13—C15—C16—C17177.3 (3)
C6—C7—C8—C9179.2 (3)C15—C16—C17—C180.3 (5)
C7—C8—C9—C101.4 (5)C14—N2—C18—C171.8 (6)
C7—C8—C9—Br2179.4 (2)C16—C17—C18—N22.1 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···Br1i0.932.893.595 (3)134
Symmetry code: (i) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC18H12Br2N2
Mr416.12
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)10.469 (3), 16.405 (5), 9.866 (3)
β (°) 112.761 (4)
V3)1562.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)5.19
Crystal size (mm)0.26 × 0.22 × 0.14
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.258, 0.484
No. of measured, independent and
observed [I > 2σ(I)] reflections
8670, 3194, 2238
Rint0.046
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.078, 1.00
No. of reflections3194
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.52

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11···Br1i0.932.893.595 (3)134
Symmetry code: (i) x+1, y, z+1.
 

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