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

Wang, C.-F.

doi:10.1107/S160053680901976X

organic compounds

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Volume 65| Part 7| July 2009| Page o1589

doi:10.1107/S160053680901976X

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

Cheng-Feng Wang ^a ^*

^aCollege of Chemistry & Bioengineering, Changsha University of Science & Technology, Changsha 410076, People's Republic of China
^*Correspondence e-mail: wang2009chengfeng@126.com

(Received 13 May 2009; accepted 25 May 2009; online 17 June 2009)

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 ). For the synthetic procedure, see: Duan et al. (2005a ,b ).

Experimental

Crystal data

C₁₉H₁₃BrFN
M_r = 354.21
Orthorhombic, P n a 2₁
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 ) 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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.070
S = 0.99
2577 reflections
199 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.69 e Å⁻³
Absolute structure: Flack (1983 ), 1139 Friedel pairs
Flack parameter: 0.004 (12)

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/S160053680901976X/gk2211sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

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

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

Crystal data top

C₁₉H₁₃BrFN	D_x = 1.606 Mg m⁻³
M_r = 354.21	Melting point = 420–422 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4959 reflections
a = 17.407 (4) Å	θ = 1.8–27.9°
b = 15.068 (3) Å	µ = 2.81 mm⁻¹
c = 5.5865 (11) Å	T = 113 K
V = 1465.3 (5) Å³	Prism, colorless
Z = 4	0.18 × 0.12 × 0.08 mm
F(000) = 712

Data collection top

Rigaku Saturn diffractometer	2577 independent reflections
Radiation source: rotating anode	2294 reflections with I > 2σ(I)
Confocal multilayer X-ray optic monochromator	R_int = 0.050
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 1.8°
ω and ϕ scans	h = −20→20
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −11→17
T_min = 0.632, T_max = 0.806	l = −6→6
9581 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0325P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.002
2577 reflections	Δρ_max = 0.43 e Å⁻³
199 parameters	Δρ_min = −0.69 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1139 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.004 (12)

Crystal data top

C₁₉H₁₃BrFN	V = 1465.3 (5) Å³
M_r = 354.21	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 17.407 (4) Å	µ = 2.81 mm⁻¹
b = 15.068 (3) Å	T = 113 K
c = 5.5865 (11) Å	0.18 × 0.12 × 0.08 mm

Data collection top

Rigaku Saturn diffractometer	2577 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2294 reflections with I > 2σ(I)
T_min = 0.632, T_max = 0.806	R_int = 0.050
9581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.43 e Å⁻³
S = 0.99	Δρ_min = −0.69 e Å⁻³
2577 reflections	Absolute structure: Flack (1983), 1139 Friedel pairs
199 parameters	Absolute structure parameter: 0.004 (12)
1 restraint

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	0.257719 (15)	0.68839 (2)	1.21455 (15)	0.02390 (12)
F1	0.64152 (11)	1.09557 (12)	0.7028 (5)	0.0424 (5)
N1	0.53809 (16)	0.69284 (17)	0.5849 (5)	0.0157 (7)
C1	0.58579 (15)	0.63539 (19)	0.7103 (7)	0.0154 (6)
C2	0.66123 (18)	0.6094 (2)	0.6612 (6)	0.0195 (8)
H2	0.6871	0.6304	0.5270	0.023*
C3	0.69613 (18)	0.5514 (2)	0.8188 (6)	0.0224 (9)
H3	0.7461	0.5328	0.7882	0.027*
C4	0.6585 (2)	0.5198 (2)	1.0230 (7)	0.0240 (9)
H4	0.6837	0.4815	1.1273	0.029*
C5	0.58356 (18)	0.5459 (2)	1.0697 (6)	0.0187 (8)
H5	0.5582	0.5247	1.2046	0.022*
C6	0.54659 (18)	0.6037 (2)	0.9140 (6)	0.0156 (8)
C7	0.47175 (18)	0.6440 (2)	0.9118 (6)	0.0137 (7)
C8	0.40789 (17)	0.6400 (2)	1.0641 (5)	0.0163 (8)
H8	0.4078	0.6034	1.1982	0.020*
C9	0.34574 (19)	0.6916 (2)	1.0091 (6)	0.0165 (8)
C10	0.34296 (18)	0.7470 (2)	0.8090 (6)	0.0183 (8)
H10	0.2991	0.7804	0.7778	0.022*
C11	0.40517 (18)	0.7520 (2)	0.6580 (6)	0.0199 (8)
H11	0.4044	0.7896	0.5260	0.024*
C12	0.46916 (15)	0.70008 (18)	0.7062 (8)	0.0144 (6)
C13	0.56110 (19)	0.7523 (2)	0.3949 (6)	0.0188 (8)
H13A	0.5193	0.7572	0.2808	0.023*
H13B	0.6047	0.7268	0.3119	0.023*
C14	0.58251 (18)	0.8443 (2)	0.4797 (6)	0.0136 (7)
C15	0.62396 (17)	0.8572 (2)	0.6911 (8)	0.0210 (7)
H15	0.6382	0.8084	0.7833	0.025*
C16	0.64408 (18)	0.9420 (2)	0.7646 (6)	0.0253 (10)
H16	0.6720	0.9504	0.9047	0.030*
C17	0.6225 (2)	1.0122 (2)	0.6294 (6)	0.0258 (9)
C18	0.5814 (2)	1.0036 (2)	0.4166 (7)	0.0280 (9)
H18	0.5677	1.0528	0.3257	0.034*
C19	0.56160 (18)	0.9178 (2)	0.3464 (6)	0.0211 (8)
H19	0.5336	0.9097	0.2062	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01522 (18)	0.0313 (2)	0.02516 (18)	0.00202 (13)	0.0037 (3)	−0.0041 (2)
F1	0.0644 (14)	0.0163 (10)	0.0464 (12)	−0.0111 (9)	0.0121 (17)	−0.0079 (14)
N1	0.0132 (16)	0.0153 (16)	0.0187 (16)	−0.0052 (12)	0.0024 (12)	−0.0004 (13)
C1	0.0149 (15)	0.0133 (15)	0.0180 (15)	−0.0033 (12)	−0.003 (2)	−0.004 (2)
C2	0.0160 (17)	0.0242 (19)	0.018 (2)	−0.0069 (15)	0.0010 (14)	−0.0034 (16)
C3	0.0119 (19)	0.020 (2)	0.035 (2)	0.0037 (15)	−0.0007 (16)	−0.0073 (17)
C4	0.023 (2)	0.017 (2)	0.032 (2)	0.0003 (17)	−0.0037 (17)	−0.0009 (18)
C5	0.018 (2)	0.0174 (19)	0.0203 (18)	0.0009 (16)	−0.0073 (16)	−0.0043 (16)
C6	0.0133 (18)	0.0165 (19)	0.0170 (18)	−0.0070 (15)	0.0033 (15)	−0.0080 (16)
C7	0.0151 (18)	0.0103 (18)	0.0158 (17)	0.0010 (15)	−0.0042 (14)	−0.0019 (16)
C8	0.0145 (19)	0.0160 (18)	0.0185 (18)	−0.0024 (16)	−0.0019 (14)	0.0004 (16)
C9	0.0114 (19)	0.018 (2)	0.0197 (19)	−0.0047 (15)	0.0032 (15)	−0.0067 (16)
C10	0.0132 (19)	0.0189 (19)	0.0228 (18)	0.0016 (15)	−0.0032 (14)	−0.0026 (15)
C11	0.0247 (19)	0.0155 (18)	0.020 (2)	−0.0040 (16)	−0.0033 (14)	0.0011 (15)
C12	0.0134 (14)	0.0137 (16)	0.0161 (15)	−0.0035 (12)	0.003 (2)	−0.0022 (19)
C13	0.0177 (19)	0.021 (2)	0.0177 (17)	−0.0020 (16)	0.0011 (15)	0.0000 (17)
C14	0.0124 (18)	0.0126 (18)	0.0158 (17)	−0.0036 (15)	0.0083 (14)	−0.0013 (16)
C15	0.0239 (17)	0.0190 (17)	0.0201 (18)	−0.0012 (14)	0.000 (2)	0.004 (2)
C16	0.0259 (19)	0.027 (2)	0.023 (3)	−0.0048 (16)	0.0036 (15)	−0.0061 (17)
C17	0.031 (2)	0.015 (2)	0.031 (2)	−0.0017 (17)	0.0144 (16)	−0.0045 (17)
C18	0.032 (2)	0.021 (2)	0.031 (2)	0.0086 (19)	0.0079 (19)	0.0025 (19)
C19	0.0169 (19)	0.028 (2)	0.0184 (19)	−0.0005 (17)	0.0032 (15)	0.0038 (17)

Geometric parameters (Å, º) top

Br1—C9	1.915 (3)	C8—H8	0.9300
F1—C17	1.363 (4)	C9—C10	1.396 (5)
N1—C12	1.382 (4)	C10—C11	1.375 (4)
N1—C1	1.389 (4)	C10—H10	0.9300
N1—C13	1.446 (4)	C11—C12	1.387 (4)
C1—C2	1.398 (4)	C11—H11	0.9300
C1—C6	1.410 (5)	C13—C14	1.512 (4)
C2—C3	1.381 (5)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.399 (5)	C14—C19	1.383 (4)
C3—H3	0.9300	C14—C15	1.397 (5)
C4—C5	1.387 (5)	C15—C16	1.387 (4)
C4—H4	0.9300	C15—H15	0.9300
C5—C6	1.389 (5)	C16—C17	1.353 (5)
C5—H5	0.9300	C16—H16	0.9300
C6—C7	1.437 (4)	C17—C18	1.394 (6)
C7—C8	1.401 (4)	C18—C19	1.394 (5)
C7—C12	1.427 (5)	C18—H18	0.9300
C8—C9	1.368 (5)	C19—H19	0.9300

C12—N1—C1	108.7 (3)	C9—C10—H10	120.1
C12—N1—C13	123.5 (3)	C10—C11—C12	118.9 (3)
C1—N1—C13	126.2 (3)	C10—C11—H11	120.6
N1—C1—C2	129.6 (3)	C12—C11—H11	120.6
N1—C1—C6	109.2 (3)	N1—C12—C11	130.3 (3)
C2—C1—C6	121.2 (3)	N1—C12—C7	108.7 (2)
C3—C2—C1	117.8 (3)	C11—C12—C7	121.0 (3)
C3—C2—H2	121.1	N1—C13—C14	114.0 (3)
C1—C2—H2	121.1	N1—C13—H13A	108.8
C2—C3—C4	121.9 (3)	C14—C13—H13A	108.8
C2—C3—H3	119.0	N1—C13—H13B	108.8
C4—C3—H3	119.0	C14—C13—H13B	108.8
C5—C4—C3	119.8 (3)	H13A—C13—H13B	107.6
C5—C4—H4	120.1	C19—C14—C15	118.7 (3)
C3—C4—H4	120.1	C19—C14—C13	120.0 (3)
C4—C5—C6	119.7 (3)	C15—C14—C13	121.3 (3)
C4—C5—H5	120.2	C16—C15—C14	120.5 (3)
C6—C5—H5	120.2	C16—C15—H15	119.7
C5—C6—C1	119.6 (3)	C14—C15—H15	119.7
C5—C6—C7	133.6 (3)	C17—C16—C15	119.0 (3)
C1—C6—C7	106.8 (3)	C17—C16—H16	120.5
C8—C7—C12	119.3 (3)	C15—C16—H16	120.5
C8—C7—C6	134.1 (3)	C16—C17—F1	119.0 (4)
C12—C7—C6	106.6 (3)	C16—C17—C18	123.1 (3)
C9—C8—C7	117.8 (3)	F1—C17—C18	117.8 (4)
C9—C8—H8	121.1	C17—C18—C19	116.9 (3)
C7—C8—H8	121.1	C17—C18—H18	121.5
C8—C9—C10	123.2 (3)	C19—C18—H18	121.5
C8—C9—Br1	118.9 (3)	C14—C19—C18	121.7 (3)
C10—C9—Br1	117.9 (3)	C14—C19—H19	119.1
C11—C10—C9	119.8 (3)	C18—C19—H19	119.1
C11—C10—H10	120.1

C12—N1—C1—C2	−178.2 (3)	C9—C10—C11—C12	1.3 (5)
C13—N1—C1—C2	−12.3 (5)	C1—N1—C12—C11	176.9 (3)
C12—N1—C1—C6	1.0 (3)	C13—N1—C12—C11	10.5 (5)
C13—N1—C1—C6	166.9 (3)	C1—N1—C12—C7	−1.6 (3)
N1—C1—C2—C3	179.3 (3)	C13—N1—C12—C7	−167.9 (3)
C6—C1—C2—C3	0.1 (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—C5	0.9 (5)	C8—C7—C12—N1	−180.0 (3)
C3—C4—C5—C6	−0.5 (5)	C6—C7—C12—N1	1.5 (4)
C4—C5—C6—C1	−0.1 (5)	C8—C7—C12—C11	1.4 (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—C14	72.0 (4)
C2—C1—C6—C5	0.3 (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—C7	179.2 (3)	N1—C13—C14—C15	39.5 (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—C16	179.1 (3)
C5—C6—C7—C12	177.9 (4)	C14—C15—C16—C17	0.5 (5)
C1—C6—C7—C12	−0.8 (4)	C15—C16—C17—F1	179.3 (3)
C12—C7—C8—C9	−0.8 (5)	C15—C16—C17—C18	−0.7 (5)
C6—C7—C8—C9	177.3 (3)	C16—C17—C18—C19	0.8 (5)
C7—C8—C9—C10	0.5 (5)	F1—C17—C18—C19	−179.2 (3)
C7—C8—C9—Br1	−179.6 (2)	C15—C14—C19—C18	0.5 (5)
C8—C9—C10—C11	−0.8 (5)	C13—C14—C19—C18	−178.9 (3)
Br1—C9—C10—C11	179.4 (2)	C17—C18—C19—C14	−0.7 (5)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃BrFN
M_r	354.21
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	113
a, b, c (Å)	17.407 (4), 15.068 (3), 5.5865 (11)
V (Å³)	1465.3 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.18 × 0.12 × 0.08

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.632, 0.806
No. of measured, independent and observed [I > 2σ(I)] reflections	9581, 2577, 2294
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.070, 0.99
No. of reflections	2577
No. of parameters	199
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.69
Absolute structure	Flack (1983), 1139 Friedel pairs
Absolute structure parameter	0.004 (12)

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

References

Duan, X. M., Han, J., Chen, L. G., Xu, Y. J. & Li, Y. (2005a). Fine Chem. 22, 39–40. CAS Google Scholar
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