3,6-Dibromo-9-(4-chloro­benz­yl)-9H-carbazole

Cui, J.; Duan, M.; Cai, L.

doi:10.1107/S1600536808042815

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o215

doi:10.1107/S1600536808042815

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3,6-Dibromo-9-(4-chlorobenzyl)-9H-carbazole

Jian-lan Cui,^a ^* Mei Duan ^b and Liu-qing Cai ^a

^aSchool of Chemical Engineering and Environment, North University of China, Taiyuan 030051, People's Republic of China, and ^bShanxi Provincial People's Hospital, Taiyuan 030012, People's Republic of China
^*Correspondence e-mail: cuijianlan2005@yahoo.com.cn

(Received 3 October 2008; accepted 16 December 2008; online 8 January 2009)

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 (mean deviation of 0.028 Å) and makes a dihedral angle of 74.6 (3)° with the plane of the benzene ring.

Related literature

For the pharmaceutical properties of carbazoles, 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 the synthesis of the title compound, see: Duan et al. (2005a ,b ); Smith et al. (1992 ). For related literature, see: Borzatta & Carrozza (1991 ). For a related compound, see: Cui et al. (2009 ).

Experimental

Crystal data

C₁₉H₁₂Br₂ClN
M_r = 449.57
Orthorhombic, P b c a
a = 8.7673 (18) Å
b = 16.732 (3) Å
c = 21.574 (4) Å
V = 3164.8 (10) Å³
Z = 8
Mo Kα radiation
μ = 5.29 mm⁻¹
T = 113 (2) K
0.06 × 0.02 × 0.02 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.742, T_max = 0.902
18205 measured reflections
2794 independent reflections
2369 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.108
S = 1.10
2794 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042815/rn2052sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042815/rn2052Isup2.hkl

checkCIF report

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, we report the structure of 3,6-dibromo-9-(4-chlorobenzyl)-9H-carbazole (I), which 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 mean deviations of 0.0277Å. The carbazole plane is inclined to the benzene ring planes at dihedral angle of 74.6 (3)°. The C—Br distances fall in the range 1.883 (4) to 1.905 (5) Å, consistent with the literature (Allen et al., 1987).

Related literature top

For the pharmaceutical properties of carbazoles, 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 the synthesis of the title compound, see: Duan et al. (2005a,b); Smith et al. (1992). For related literature, see: Borzatta & Carrozza (1991). For a related compound, see: Cui & Cai (2009).

Experimental top

The title compound was prepared according to the procedure of Duan et al. (2005a,b) from 3,6-dibromo-carbazole (Smith et al. 1992) and 1-chloro-4-(chloromethyl)benzene. Compound (I) (40 mg) was dissolved in mixture of chloroform (10 ml) and ethanol (5 ml) and the solution was kept at room temperature for 18 d. Natural evaporation of the solution gave colourless crystals suitable for X-Ray analysis. (m.p. 451–452 K).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A perspective view of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal packing of (I), viewed down the a axis with H atoms omitted for clarity.

3,6-Dibromo-9-(4-chlorobenzyl)-9H-carbazole top

Crystal data top

C₁₉H₁₂Br₂ClN	D_x = 1.887 Mg m⁻³
M_r = 449.57	Melting point = 451–452 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5270 reflections
a = 8.7673 (18) Å	θ = 2.4–27.9°
b = 16.732 (3) Å	µ = 5.29 mm⁻¹
c = 21.574 (4) Å	T = 113 K
V = 3164.8 (10) Å³	Prism, colorless
Z = 8	0.06 × 0.02 × 0.02 mm
F(000) = 1760

Data collection top

Rigaku Saturn diffractometer	2794 independent reflections
Radiation source: rotating anode	2369 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.090
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −10→10
T_min = 0.742, T_max = 0.902	k = −19→13
18205 measured reflections	l = −25→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0488P)² + 2.2242P] where P = (F_o² + 2F_c²)/3
2794 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

C₁₉H₁₂Br₂ClN	V = 3164.8 (10) Å³
M_r = 449.57	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.7673 (18) Å	µ = 5.29 mm⁻¹
b = 16.732 (3) Å	T = 113 K
c = 21.574 (4) Å	0.06 × 0.02 × 0.02 mm

Data collection top

Rigaku Saturn diffractometer	2794 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2369 reflections with I > 2σ(I)
T_min = 0.742, T_max = 0.902	R_int = 0.090
18205 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.10	Δρ_max = 0.54 e Å⁻³
2794 reflections	Δρ_min = −0.53 e Å⁻³
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 > 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

	x	y	z	U_iso*/U_eq
Br1	0.22114 (6)	0.09041 (3)	0.56121 (2)	0.02566 (18)
Br2	0.65417 (6)	−0.19402 (3)	0.84401 (2)	0.02964 (19)
Cl1	0.54034 (14)	0.40983 (8)	0.94634 (5)	0.0248 (3)
N1	0.2015 (4)	0.0764 (3)	0.83555 (17)	0.0200 (9)
C1	0.1896 (5)	0.0868 (3)	0.7726 (2)	0.0181 (10)
C2	0.1017 (5)	0.1422 (3)	0.7406 (2)	0.0205 (11)
H2	0.0388	0.1783	0.7611	0.025*
C3	0.1123 (5)	0.1410 (3)	0.6772 (2)	0.0208 (11)
H3	0.0562	0.1771	0.6536	0.025*
C4	0.2067 (5)	0.0860 (3)	0.6482 (2)	0.0193 (11)
C5	0.2911 (5)	0.0299 (3)	0.6790 (2)	0.0193 (11)
H5	0.3511	−0.0071	0.6580	0.023*
C6	0.2827 (5)	0.0308 (3)	0.7433 (2)	0.0163 (10)
C7	0.3559 (5)	−0.0160 (3)	0.7902 (2)	0.0170 (10)
C8	0.4580 (5)	−0.0795 (3)	0.7888 (2)	0.0198 (11)
H8	0.4890	−0.1020	0.7515	0.024*
C9	0.5117 (6)	−0.1080 (3)	0.8443 (2)	0.0236 (12)
C10	0.4625 (5)	−0.0769 (3)	0.9006 (2)	0.0240 (12)
H10	0.4999	−0.0977	0.9375	0.029*
C11	0.3590 (5)	−0.0155 (3)	0.9018 (2)	0.0224 (11)
H11	0.3259	0.0052	0.9395	0.027*
C12	0.3041 (5)	0.0154 (3)	0.8466 (2)	0.0182 (11)
C13	0.1391 (6)	0.1292 (3)	0.8828 (2)	0.0230 (12)
H13A	0.1194	0.0985	0.9201	0.028*
H13B	0.0425	0.1505	0.8683	0.028*
C14	0.2447 (5)	0.1977 (3)	0.8982 (2)	0.0190 (11)
C15	0.2722 (5)	0.2589 (3)	0.8562 (2)	0.0208 (11)
H15	0.2264	0.2568	0.8174	0.025*
C16	0.3654 (5)	0.3226 (3)	0.8703 (2)	0.0198 (11)
H16	0.3825	0.3628	0.8414	0.024*
C17	0.4333 (5)	0.3259 (3)	0.9281 (2)	0.0220 (11)
C18	0.4101 (6)	0.2650 (3)	0.9700 (2)	0.0237 (11)
H18	0.4579	0.2666	1.0084	0.028*
C19	0.3168 (5)	0.2020 (3)	0.9553 (2)	0.0214 (11)
H19	0.3018	0.1614	0.9841	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0279 (3)	0.0322 (4)	0.0169 (3)	−0.0001 (2)	0.00008 (19)	0.0030 (2)
Br2	0.0277 (3)	0.0238 (4)	0.0375 (3)	0.0038 (2)	−0.0060 (2)	0.0027 (2)
Cl1	0.0296 (7)	0.0222 (8)	0.0225 (6)	−0.0055 (5)	−0.0011 (5)	−0.0009 (5)
N1	0.025 (2)	0.018 (3)	0.0176 (19)	−0.0014 (18)	0.0005 (16)	−0.0021 (18)
C1	0.023 (2)	0.013 (3)	0.018 (2)	−0.003 (2)	−0.0011 (19)	−0.005 (2)
C2	0.019 (2)	0.016 (3)	0.027 (3)	−0.003 (2)	−0.003 (2)	−0.005 (2)
C3	0.021 (3)	0.020 (3)	0.021 (2)	−0.004 (2)	−0.004 (2)	0.001 (2)
C4	0.017 (2)	0.023 (3)	0.017 (2)	−0.004 (2)	−0.0016 (19)	0.000 (2)
C5	0.021 (2)	0.016 (3)	0.021 (2)	−0.001 (2)	0.0007 (19)	0.000 (2)
C6	0.016 (2)	0.016 (3)	0.017 (2)	−0.003 (2)	0.0019 (18)	−0.002 (2)
C7	0.017 (2)	0.015 (3)	0.019 (2)	−0.006 (2)	0.0002 (18)	−0.001 (2)
C8	0.018 (2)	0.022 (3)	0.020 (2)	−0.003 (2)	0.0014 (19)	0.001 (2)
C9	0.021 (3)	0.020 (3)	0.030 (3)	−0.003 (2)	−0.004 (2)	0.004 (2)
C10	0.027 (3)	0.023 (3)	0.022 (2)	−0.007 (2)	−0.006 (2)	0.004 (2)
C11	0.028 (3)	0.021 (3)	0.019 (2)	−0.005 (2)	−0.001 (2)	−0.003 (2)
C12	0.017 (2)	0.018 (3)	0.019 (2)	−0.008 (2)	−0.0026 (18)	0.003 (2)
C13	0.025 (3)	0.026 (3)	0.018 (2)	0.000 (2)	0.008 (2)	−0.007 (2)
C14	0.019 (2)	0.020 (3)	0.018 (2)	0.001 (2)	0.0044 (19)	−0.008 (2)
C15	0.017 (2)	0.028 (3)	0.017 (2)	0.003 (2)	0.0022 (19)	−0.002 (2)
C16	0.019 (2)	0.020 (3)	0.020 (2)	0.006 (2)	0.0042 (19)	0.002 (2)
C17	0.023 (3)	0.024 (3)	0.020 (2)	−0.001 (2)	0.000 (2)	−0.001 (2)
C18	0.032 (3)	0.024 (3)	0.015 (2)	0.003 (2)	−0.002 (2)	0.001 (2)
C19	0.027 (3)	0.016 (3)	0.021 (2)	−0.002 (2)	0.008 (2)	0.004 (2)

Geometric parameters (Å, º) top

Br1—C4	1.883 (4)	C8—H8	0.9300
Br2—C9	1.905 (5)	C9—C10	1.390 (7)
Cl1—C17	1.734 (5)	C10—C11	1.370 (7)
N1—C1	1.373 (6)	C10—H10	0.9300
N1—C12	1.382 (6)	C11—C12	1.384 (6)
N1—C13	1.455 (6)	C11—H11	0.9300
C1—C2	1.390 (7)	C13—C14	1.510 (7)
C1—C6	1.393 (7)	C13—H13A	0.9700
C2—C3	1.370 (6)	C13—H13B	0.9700
C2—H2	0.9300	C14—C19	1.386 (7)
C3—C4	1.387 (7)	C14—C15	1.389 (7)
C3—H3	0.9300	C15—C16	1.377 (7)
C4—C5	1.368 (7)	C15—H15	0.9300
C5—C6	1.389 (6)	C16—C17	1.383 (6)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.431 (7)	C17—C18	1.376 (7)
C7—C8	1.390 (7)	C18—C19	1.372 (7)
C7—C12	1.402 (6)	C18—H18	0.9300
C8—C9	1.371 (6)	C19—H19	0.9300

C1—N1—C12	108.3 (4)	C9—C10—H10	119.9
C1—N1—C13	126.0 (4)	C10—C11—C12	119.6 (5)
C12—N1—C13	124.9 (4)	C10—C11—H11	120.2
N1—C1—C2	128.2 (4)	C12—C11—H11	120.2
N1—C1—C6	108.6 (4)	N1—C12—C11	130.7 (4)
C2—C1—C6	123.2 (4)	N1—C12—C7	109.7 (4)
C3—C2—C1	116.7 (5)	C11—C12—C7	119.6 (5)
C3—C2—H2	121.7	N1—C13—C14	112.6 (4)
C1—C2—H2	121.7	N1—C13—H13A	109.1
C2—C3—C4	119.9 (5)	C14—C13—H13A	109.1
C2—C3—H3	120.0	N1—C13—H13B	109.1
C4—C3—H3	120.0	C14—C13—H13B	109.1
C5—C4—C3	124.1 (4)	H13A—C13—H13B	107.8
C5—C4—Br1	118.3 (4)	C19—C14—C15	117.5 (5)
C3—C4—Br1	117.6 (4)	C19—C14—C13	121.0 (5)
C4—C5—C6	116.6 (5)	C15—C14—C13	121.5 (4)
C4—C5—H5	121.7	C16—C15—C14	122.0 (4)
C6—C5—H5	121.7	C16—C15—H15	119.0
C5—C6—C1	119.5 (4)	C14—C15—H15	119.0
C5—C6—C7	132.5 (5)	C15—C16—C17	119.1 (5)
C1—C6—C7	108.1 (4)	C15—C16—H16	120.5
C8—C7—C12	120.9 (4)	C17—C16—H16	120.5
C8—C7—C6	133.9 (4)	C18—C17—C16	119.9 (5)
C12—C7—C6	105.3 (4)	C18—C17—Cl1	122.1 (4)
C9—C8—C7	118.0 (5)	C16—C17—Cl1	118.0 (4)
C9—C8—H8	121.0	C19—C18—C17	120.4 (5)
C7—C8—H8	121.0	C19—C18—H18	119.8
C8—C9—C10	121.7 (5)	C17—C18—H18	119.8
C8—C9—Br2	119.0 (4)	C18—C19—C14	121.2 (5)
C10—C9—Br2	119.3 (4)	C18—C19—H19	119.4
C11—C10—C9	120.2 (5)	C14—C19—H19	119.4
C11—C10—H10	119.9

C12—N1—C1—C2	−178.9 (5)	Br2—C9—C10—C11	−179.4 (4)
C13—N1—C1—C2	−8.9 (8)	C9—C10—C11—C12	−0.1 (7)
C12—N1—C1—C6	1.3 (5)	C1—N1—C12—C11	177.3 (5)
C13—N1—C1—C6	171.2 (4)	C13—N1—C12—C11	7.2 (8)
N1—C1—C2—C3	178.8 (5)	C1—N1—C12—C7	−1.8 (5)
C6—C1—C2—C3	−1.3 (7)	C13—N1—C12—C7	−171.9 (4)
C1—C2—C3—C4	0.4 (7)	C10—C11—C12—N1	−179.6 (5)
C2—C3—C4—C5	1.2 (8)	C10—C11—C12—C7	−0.5 (7)
C2—C3—C4—Br1	−177.8 (4)	C8—C7—C12—N1	−178.6 (4)
C3—C4—C5—C6	−1.8 (7)	C6—C7—C12—N1	1.7 (5)
Br1—C4—C5—C6	177.2 (3)	C8—C7—C12—C11	2.1 (7)
C4—C5—C6—C1	0.8 (7)	C6—C7—C12—C11	−177.6 (4)
C4—C5—C6—C7	−178.1 (5)	C1—N1—C13—C14	−85.7 (6)
N1—C1—C6—C5	−179.4 (4)	C12—N1—C13—C14	82.7 (6)
C2—C1—C6—C5	0.7 (7)	N1—C13—C14—C19	−111.0 (5)
N1—C1—C6—C7	−0.2 (5)	N1—C13—C14—C15	69.5 (6)
C2—C1—C6—C7	179.9 (4)	C19—C14—C15—C16	−1.0 (7)
C5—C6—C7—C8	−1.5 (9)	C13—C14—C15—C16	178.4 (4)
C1—C6—C7—C8	179.5 (5)	C14—C15—C16—C17	−0.2 (7)
C5—C6—C7—C12	178.2 (5)	C15—C16—C17—C18	1.6 (7)
C1—C6—C7—C12	−0.9 (5)	C15—C16—C17—Cl1	−176.0 (4)
C12—C7—C8—C9	−2.9 (7)	C16—C17—C18—C19	−1.7 (8)
C6—C7—C8—C9	176.7 (5)	Cl1—C17—C18—C19	175.8 (4)
C7—C8—C9—C10	2.3 (7)	C17—C18—C19—C14	0.4 (8)
C7—C8—C9—Br2	−179.1 (4)	C15—C14—C19—C18	1.0 (7)
C8—C9—C10—C11	−0.8 (8)	C13—C14—C19—C18	−178.5 (5)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₂Br₂ClN
M_r	449.57
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	113
a, b, c (Å)	8.7673 (18), 16.732 (3), 21.574 (4)
V (Å³)	3164.8 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	5.29
Crystal size (mm)	0.06 × 0.02 × 0.02

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.742, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	18205, 2794, 2369
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.108, 1.10
No. of reflections	2794
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.53

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

References

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. CrossRef Web of Science Google Scholar
Borzatta, V. & Carrozza, P. (1991). European Patent EP 0 462 069. Google Scholar
Buu-Hoï, N. P. & Royer, R. (1950). J. Org. Chem. 15, 123–130. CrossRef CAS Google Scholar
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