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

Abstract

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,

• a = 17.407 (4) Å

• b = 15.068 (3) Å

• c = 5.5865 (11) Å

• V = 1465.3 (5) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were included in the idealized positions and refined in a riding model approximation with C—H distances of 0.93 (benzene) and 0.97 (methylene) Å, and with U_iso(H) = 1.2xU_eq(C).

Figures

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.

Crystal data

C19H13BrFN	Dx = 1.606 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0325P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.002
2577 reflections	Δρmax = 0.43 e Å−3
199 parameters	Δρmin = −0.69 e Å−3
1 restraint	Absolute structure: Flack (1983), 1139 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.004 (12)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)