9-Benzyl-3-bromo-9H-carbazole

Huang, P.-M.; Wang, X.-C.

doi:10.1107/S1600536809024969

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1763

doi:10.1107/S1600536809024969

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9-Benzyl-3-bromo-9H-carbazole

Peng-Mian Huang ^a and Xiao-Chun Wang ^b ^*

^aCollege of Chemistry & Bioengineering, Changsha University of Science & Technology, Changsha 410076, People's Republic of China, and ^bDepartment of Clinical Laboratory, XiangYa Medical College of Central South University, Changsha 410013, People's Republic of China
^*Correspondence e-mail: huangpengmian@126.com

(Received 26 June 2009; accepted 29 June 2009; online 4 July 2009)

The title compound, C₁₉H₁₄BrN, was synthesized by the N-alkylation of (chloromethyl)benzene with 3-bromo-9H-carbazole. The carbazole ring system is essentially planar (r.m.s. deviation = 0.013 Å) and forms a dihedral angle of 87.1 (2)° with the phenyl ring.

Related literature

For the synthesis, see: Duan et al. (2005 ). For the pharmaceutical properties of N-alkyl carbazoles, see: Buu-Hoï & Royer (1950 ).

Experimental

Crystal data

C₁₉H₁₄BrN
M_r = 336.22
Orthorhombic, P n a 2₁
a = 17.629 (3) Å
b = 14.666 (2) Å
c = 5.6420 (8) Å
V = 1458.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.81 mm⁻¹
T = 113 K
0.14 × 0.12 × 0.10 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.682, T_max = 0.755
14426 measured reflections
3441 independent reflections
2801 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.069
S = 0.98
3441 reflections
191 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 1521 Friedel pairs
Flack parameter: −0.005 (10)

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/S1600536809024969/hb5016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024969/hb5016Isup2.hkl

checkCIF report

Comment top

N-Alkyl carbazoles possess valuable pharmaceutical properties (Buu-Hoï & Royer, 1950). In this paper, the synthesis and the crystal structure of the title compound, (I), is reported.

The carbazole ring is essentially planar, with a r.m.s. deviation from the mean plane of 0.013 Å for the non-hydrogen atoms. The dihedral angle formed between the carbazole unit and the benzene ring is 92.9 (2) Å.

Related literature top

For the synthesis, see: Duan et al. (2005). For the pharmaceutical properties of N-alkyl carbazoles, see: Buu-Hoï & Royer (1950).

Experimental top

The title compound was prepared according to the procedure of Duan et al. (2005). The title compound (40 mg) was dissolved in a mixture of chloroform (5 ml) and ethanol (7 ml) and the solution was kept at room temperature for 11 days. Evaporation of the solution gave colourless blocks of (I).

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. Molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. H atoms are presented as spheres of arbitrary radius.

9-Benzyl-3-bromo-9H-carbazole top

Crystal data top

C₁₉H₁₄BrN	D_x = 1.531 Mg m⁻³
M_r = 336.22	Melting point = 392–394 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2c -2n	Cell parameters from 3798 reflections
a = 17.629 (3) Å	θ = 1.8–27.9°
b = 14.666 (2) Å	µ = 2.81 mm⁻¹
c = 5.6420 (8) Å	T = 113 K
V = 1458.7 (4) Å³	Block, colorless
Z = 4	0.14 × 0.12 × 0.10 mm
F(000) = 680

Data collection top

Rigaku Saturn diffractometer	3441 independent reflections
Radiation source: rotating anode	2801 reflections with I > 2σ(I)
Confocal multilayer X-ray optic monochromator	R_int = 0.045
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 1.8°
ω and ϕ scans	h = −23→23
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −19→19
T_min = 0.682, T_max = 0.755	l = −7→7
14426 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0241P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.069	(Δ/σ)_max = 0.001
S = 0.98	Δρ_max = 0.95 e Å⁻³
3441 reflections	Δρ_min = −0.52 e Å⁻³
191 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0148 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1521 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.005 (10)

Crystal data top

C₁₉H₁₄BrN	V = 1458.7 (4) Å³
M_r = 336.22	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 17.629 (3) Å	µ = 2.81 mm⁻¹
b = 14.666 (2) Å	T = 113 K
c = 5.6420 (8) Å	0.14 × 0.12 × 0.10 mm

Data collection top

Rigaku Saturn diffractometer	3441 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2801 reflections with I > 2σ(I)
T_min = 0.682, T_max = 0.755	R_int = 0.045
14426 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.95 e Å⁻³
S = 0.98	Δρ_min = −0.52 e Å⁻³
3441 reflections	Absolute structure: Flack (1983), 1521 Friedel pairs
191 parameters	Absolute structure parameter: −0.005 (10)
1 restraint

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.257493 (13)	0.192950 (18)	0.66598 (14)	0.02943 (11)
N1	0.53686 (13)	0.19508 (14)	0.0539 (4)	0.0196 (5)
C1	0.46874 (12)	0.20289 (15)	0.1699 (6)	0.0180 (5)
C2	0.40547 (16)	0.25415 (17)	0.1164 (5)	0.0229 (7)
H2	0.4049	0.2918	−0.0206	0.027*
C3	0.34289 (16)	0.25037 (19)	0.2638 (5)	0.0231 (7)
H3	0.2988	0.2849	0.2278	0.028*
C4	0.34503 (16)	0.19535 (18)	0.4663 (5)	0.0206 (7)
C5	0.40726 (15)	0.14351 (19)	0.5264 (5)	0.0191 (6)
H5	0.4072	0.1064	0.6643	0.023*
C6	0.47028 (15)	0.14744 (17)	0.3781 (5)	0.0176 (6)
C7	0.58394 (13)	0.13641 (16)	0.1792 (6)	0.0191 (6)
C8	0.65823 (14)	0.10891 (17)	0.1344 (6)	0.0228 (7)
H8	0.6848	0.1303	−0.0013	0.027*
C9	0.69198 (16)	0.0502 (2)	0.2913 (5)	0.0269 (7)
H9	0.7424	0.0303	0.2617	0.032*
C10	0.65424 (18)	0.0186 (2)	0.4947 (5)	0.0260 (7)
H10	0.6794	−0.0215	0.6010	0.031*
C11	0.58048 (16)	0.04587 (18)	0.5403 (5)	0.0222 (7)
H11	0.5547	0.0246	0.6774	0.027*
C12	0.54435 (15)	0.10506 (18)	0.3825 (5)	0.0179 (6)
C13	0.56053 (16)	0.25418 (18)	−0.1405 (5)	0.0224 (7)
H13A	0.5185	0.2588	−0.2563	0.027*
H13B	0.6042	0.2258	−0.2223	0.027*
C14	0.58274 (15)	0.34943 (19)	−0.0620 (5)	0.0197 (6)
C15	0.62312 (14)	0.36493 (17)	0.1461 (6)	0.0241 (6)
H15	0.6360	0.3154	0.2470	0.029*
C16	0.64439 (15)	0.4530 (2)	0.2054 (6)	0.0307 (8)
H16	0.6726	0.4631	0.3464	0.037*
C17	0.6255 (2)	0.5257 (2)	0.0643 (6)	0.0344 (9)
H17	0.6402	0.5858	0.1077	0.041*
C18	0.58455 (17)	0.5108 (2)	−0.1427 (7)	0.0336 (8)
H18	0.5713	0.5605	−0.2424	0.040*
C19	0.56306 (16)	0.42221 (19)	−0.2030 (6)	0.0261 (7)
H19	0.5345	0.4120	−0.3432	0.031*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01928 (15)	0.03967 (17)	0.02934 (18)	0.00396 (12)	0.0029 (2)	−0.0045 (2)
N1	0.0176 (13)	0.0205 (12)	0.0208 (13)	−0.0014 (10)	0.0012 (11)	0.0036 (11)
C1	0.0175 (12)	0.0180 (12)	0.0184 (14)	−0.0031 (10)	−0.002 (2)	−0.0038 (16)
C2	0.0249 (15)	0.0199 (14)	0.024 (2)	−0.0015 (12)	−0.0055 (13)	0.0013 (13)
C3	0.0202 (16)	0.0211 (15)	0.0279 (17)	0.0034 (13)	−0.0056 (13)	−0.0036 (13)
C4	0.0152 (15)	0.0237 (16)	0.0228 (16)	0.0004 (12)	0.0026 (13)	−0.0038 (13)
C5	0.0179 (15)	0.0189 (14)	0.0204 (16)	−0.0040 (12)	−0.0021 (12)	−0.0011 (12)
C6	0.0166 (15)	0.0150 (14)	0.0213 (15)	−0.0022 (11)	−0.0031 (13)	−0.0029 (12)
C7	0.0185 (12)	0.0173 (12)	0.0214 (14)	−0.0035 (10)	−0.0027 (18)	−0.0048 (16)
C8	0.0159 (13)	0.0259 (14)	0.0268 (19)	−0.0044 (11)	0.0002 (14)	−0.0051 (15)
C9	0.0186 (16)	0.0258 (17)	0.0364 (19)	−0.0017 (13)	−0.0015 (15)	−0.0078 (15)
C10	0.0228 (17)	0.0225 (15)	0.0326 (18)	0.0020 (13)	−0.0053 (14)	0.0002 (14)
C11	0.0201 (16)	0.0231 (15)	0.0233 (16)	−0.0031 (12)	−0.0031 (13)	−0.0015 (13)
C12	0.0178 (15)	0.0140 (13)	0.0217 (16)	−0.0042 (11)	0.0010 (13)	−0.0034 (12)
C13	0.0195 (16)	0.0267 (16)	0.0209 (15)	−0.0024 (12)	0.0024 (13)	0.0004 (14)
C14	0.0170 (15)	0.0208 (14)	0.0215 (17)	0.0003 (12)	0.0076 (13)	0.0035 (14)
C15	0.0272 (14)	0.0229 (14)	0.0222 (16)	−0.0034 (11)	0.0000 (18)	0.0000 (17)
C16	0.0311 (16)	0.0336 (17)	0.028 (2)	−0.0080 (13)	0.0013 (15)	−0.0054 (16)
C17	0.039 (2)	0.0210 (16)	0.043 (2)	−0.0068 (15)	0.0162 (16)	−0.0033 (16)
C18	0.0319 (19)	0.0247 (16)	0.044 (2)	0.0040 (14)	0.0113 (18)	0.0080 (16)
C19	0.0213 (16)	0.0324 (17)	0.0244 (17)	0.0004 (13)	0.0045 (14)	0.0051 (14)

Geometric parameters (Å, º) top

Br1—C4	1.911 (3)	C9—H9	0.9500
N1—C1	1.373 (3)	C10—C11	1.385 (4)
N1—C7	1.389 (3)	C10—H10	0.9500
N1—C13	1.459 (3)	C11—C12	1.397 (4)
C1—C2	1.379 (3)	C11—H11	0.9500
C1—C6	1.429 (4)	C13—C14	1.517 (4)
C2—C3	1.382 (4)	C13—H13A	0.9900
C2—H2	0.9500	C13—H13B	0.9900
C3—C4	1.399 (4)	C14—C19	1.376 (4)
C3—H3	0.9500	C14—C15	1.392 (4)
C4—C5	1.377 (4)	C15—C16	1.385 (4)
C5—C6	1.392 (4)	C15—H15	0.9500
C5—H5	0.9500	C16—C17	1.373 (4)
C6—C12	1.446 (3)	C16—H16	0.9500
C7—C8	1.393 (3)	C17—C18	1.390 (5)
C7—C12	1.419 (4)	C17—H17	0.9500
C8—C9	1.371 (4)	C18—C19	1.395 (4)
C8—H8	0.9500	C18—H18	0.9500
C9—C10	1.405 (4)	C19—H19	0.9500

C1—N1—C7	109.4 (2)	C9—C10—H10	120.0
C1—N1—C13	124.0 (2)	C10—C11—C12	119.3 (3)
C7—N1—C13	125.4 (2)	C10—C11—H11	120.4
N1—C1—C2	130.5 (3)	C12—C11—H11	120.4
N1—C1—C6	109.1 (2)	C11—C12—C7	119.5 (2)
C2—C1—C6	120.4 (3)	C11—C12—C6	133.6 (3)
C1—C2—C3	119.5 (3)	C7—C12—C6	106.9 (2)
C1—C2—H2	120.3	N1—C13—C14	113.7 (2)
C3—C2—H2	120.3	N1—C13—H13A	108.8
C2—C3—C4	119.5 (3)	C14—C13—H13A	108.8
C2—C3—H3	120.2	N1—C13—H13B	108.8
C4—C3—H3	120.2	C14—C13—H13B	108.8
C5—C4—C3	122.8 (3)	H13A—C13—H13B	107.7
C5—C4—Br1	119.2 (2)	C19—C14—C15	119.3 (3)
C3—C4—Br1	118.1 (2)	C19—C14—C13	118.7 (3)
C4—C5—C6	117.7 (3)	C15—C14—C13	121.9 (2)
C4—C5—H5	121.2	C16—C15—C14	119.6 (3)
C6—C5—H5	121.2	C16—C15—H15	120.2
C5—C6—C1	120.2 (2)	C14—C15—H15	120.2
C5—C6—C12	133.8 (3)	C17—C16—C15	121.3 (3)
C1—C6—C12	106.0 (2)	C17—C16—H16	119.4
N1—C7—C8	130.4 (3)	C15—C16—H16	119.4
N1—C7—C12	108.6 (2)	C16—C17—C18	119.4 (3)
C8—C7—C12	121.0 (3)	C16—C17—H17	120.3
C9—C8—C7	118.2 (3)	C18—C17—H17	120.3
C9—C8—H8	120.9	C17—C18—C19	119.5 (3)
C7—C8—H8	120.9	C17—C18—H18	120.2
C8—C9—C10	121.9 (3)	C19—C18—H18	120.2
C8—C9—H9	119.0	C14—C19—C18	120.9 (3)
C10—C9—H9	119.0	C14—C19—H19	119.6
C11—C10—C9	120.1 (3)	C18—C19—H19	119.6
C11—C10—H10	120.0

C7—N1—C1—C2	178.6 (3)	C8—C9—C10—C11	0.7 (4)
C13—N1—C1—C2	10.5 (4)	C9—C10—C11—C12	−0.1 (4)
C7—N1—C1—C6	−0.3 (3)	C10—C11—C12—C7	−0.3 (4)
C13—N1—C1—C6	−168.5 (2)	C10—C11—C12—C6	−178.6 (3)
N1—C1—C2—C3	−179.9 (3)	N1—C7—C12—C11	−179.0 (2)
C6—C1—C2—C3	−1.1 (4)	C8—C7—C12—C11	0.1 (4)
C1—C2—C3—C4	0.7 (4)	N1—C7—C12—C6	−0.2 (3)
C2—C3—C4—C5	−0.4 (4)	C8—C7—C12—C6	178.9 (2)
C2—C3—C4—Br1	179.5 (2)	C5—C6—C12—C11	−1.5 (5)
C3—C4—C5—C6	0.5 (4)	C1—C6—C12—C11	178.5 (3)
Br1—C4—C5—C6	−179.48 (19)	C5—C6—C12—C7	180.0 (3)
C4—C5—C6—C1	−0.8 (4)	C1—C6—C12—C7	0.0 (3)
C4—C5—C6—C12	179.2 (3)	C1—N1—C13—C14	73.6 (3)
N1—C1—C6—C5	−179.8 (2)	C7—N1—C13—C14	−92.7 (3)
C2—C1—C6—C5	1.2 (4)	N1—C13—C14—C19	−141.7 (3)
N1—C1—C6—C12	0.2 (3)	N1—C13—C14—C15	39.1 (4)
C2—C1—C6—C12	−178.9 (2)	C19—C14—C15—C16	−1.5 (4)
C1—N1—C7—C8	−178.7 (3)	C13—C14—C15—C16	177.7 (3)
C13—N1—C7—C8	−10.7 (4)	C14—C15—C16—C17	0.9 (4)
C1—N1—C7—C12	0.3 (3)	C15—C16—C17—C18	−0.4 (5)
C13—N1—C7—C12	168.3 (2)	C16—C17—C18—C19	0.3 (5)
N1—C7—C8—C9	179.3 (3)	C15—C14—C19—C18	1.5 (4)
C12—C7—C8—C9	0.4 (4)	C13—C14—C19—C18	−177.7 (3)
C7—C8—C9—C10	−0.8 (4)	C17—C18—C19—C14	−0.9 (4)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₄BrN
M_r	336.22
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	113
a, b, c (Å)	17.629 (3), 14.666 (2), 5.6420 (8)
V (Å³)	1458.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.14 × 0.12 × 0.10

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.682, 0.755
No. of measured, independent and observed [I > 2σ(I)] reflections	14426, 3441, 2801
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.069, 0.98
No. of reflections	3441
No. of parameters	191
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.95, −0.52
Absolute structure	Flack (1983), 1521 Friedel pairs
Absolute structure parameter	−0.005 (10)

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

Acknowledgements

This work was supported by the Changsha Science and Technology Bureau (k0803061-11) and Scientific Research Foundation of Hunan Provience (S2007F123) .

References

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