1-(4-Fluoro­phen­yl)-2-(1H-imidazol-1-yl)ethanone

Liu, D.; Li, C.; Yu, G.; Xiao, T.

doi:10.1107/S1600536811026432

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2036

doi:10.1107/S1600536811026432

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1-(4-Fluorophenyl)-2-(1H-imidazol-1-yl)ethanone

Dong-liang Liu,^a Chen Li,^a Guang-yan Yu ^a and Tao Xiao ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: taoxiao@njut.edu.cn

(Received 28 June 2011; accepted 3 July 2011; online 13 July 2011)

In the title compound, C₁₁H₉FN₂O, the dihedral angle between the rings is 87.50 (4)°. In the crystal, intermolecular C—H⋯N hydrogen bonds link the molecules in a stacked arrangement along the c axis.

Related literature

For related compounds containing a 2-(1H-imidazol-1-yl)-1-phenylethanone fragment, see: Akira et al. (1985 ); North et al. (1968 ); Yoshimi et al. (2000 ); Yuan et al. (2007 ); Tao et al. (2007 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉FN₂O
M_r = 204.20
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.6730 (17) Å
b = 10.132 (2) Å
c = 11.088 (2) Å
V = 974.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968) T_min = 0.969, T_max = 0.990
3790 measured reflections
1052 independent reflections
778 reflections with I > 2σ(I)
R_int = 0.045
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.093
S = 1.01
1052 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.09 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯N2ⁱ	0.97	2.51	3.454 (4)	164
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo,1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811026432/zq2112sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026432/zq2112Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536811026432/zq2112Isup3.cml

checkCIF report

Comment top

The title compound, C₁₁H₉O₁N₂F₁, is the key intermediate in the synthesis of a new kind of antifungal drug (Akira et al., 1985; Yoshimi et al., 2000). The crystal structure determination has been carried out in order to elucidate the molecular conformation (Fig. 1).

In the crystal structure, the bond lengths and angles of the title compound are within normal ranges (Allen et al., 1987). The phenyl and imidazole rings are planar (rms deviations of 0.0038 and 0.0036, respectively) and almost perpendicular to each other. The dihedral angle between the mean planes is 87.50 (4)°. In the crystal structure, intermolecular C—H···N hydrogen bonds (Table 1) link the molecules in a stacked arrangement along the a axis (Fig. 2).

Related literature top

For related compounds containing a 2-(1H-imidazol-1-yl)-1-phenylethanone fragment, see: Akira et al. (1985); North et al. (1968); Yoshimi et al. (2000); Yuan et al. (2007); Tao et al. (2007).

Experimental top

Sodium hydride (4.8 g, 120 mmol) was suspended in dimethylformamide (DMF, 30 ml). Imidazole (6.8 g, 120 mmol) dissolved in DMF (30 ml) was slowly added dropwise at 273 K, and reacted atroom temperature for 30 min. 2-chloro-1-(4-fluorophenyl)ethanone (15.48 g, 90 mmol) dissolved in DMF (30 ml) was then slowly added dropwise, and reacted at room temperature for 4 h. The mixture was placed in ice-water (300 ml), and 1 mol hydrochloric acid (50 ml) was then added. After filtration, the filtrate was neutralized with sodium bicarbonate to pH = 6, and a yellow deposit was obtained (m.p. 423–424 K). Crystals suitable for X-ray analysis were obtained by dissolving the crude product (1.0 g) in ethanol (30 ml) and then allowing the solution to evaporate slowly at room temperature for about 7 d.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo,1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-(4-Fluorophenyl)-2-(1H-imidazol-1-yl)ethanone top

Crystal data top

C₁₁H₉FN₂O	D_x = 1.392 Mg m⁻³
M_r = 204.20	Melting point: 423 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 8.6730 (17) Å	θ = 9–13°
b = 10.132 (2) Å	µ = 0.11 mm⁻¹
c = 11.088 (2) Å	T = 293 K
V = 974.4 (3) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.10 mm
F(000) = 424

Data collection top

Enraf–Nonius CAD-4 diffractometer	778 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 25.4°, θ_min = 2.7°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
T_min = 0.969, T_max = 0.990	l = −13→13
3790 measured reflections	3 standard reflections every 200 reflections
1052 independent reflections	intensity decay: 1%

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)] = 0.037	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0484P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1052 reflections	Δρ_max = 0.10 e Å⁻³
137 parameters	Δρ_min = −0.09 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (5)

Crystal data top

C₁₁H₉FN₂O	V = 974.4 (3) Å³
M_r = 204.20	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.6730 (17) Å	µ = 0.11 mm⁻¹
b = 10.132 (2) Å	T = 293 K
c = 11.088 (2) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	778 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.045
T_min = 0.969, T_max = 0.990	3 standard reflections every 200 reflections
3790 measured reflections	intensity decay: 1%
1052 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.093	H-atom parameters constrained
S = 1.01	Δρ_max = 0.10 e Å⁻³
1052 reflections	Δρ_min = −0.09 e Å⁻³
137 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
F	0.3432 (3)	0.73232 (18)	0.41347 (18)	0.1052 (8)
O	0.4019 (3)	0.2049 (2)	0.7042 (2)	0.0838 (8)
N1	0.1657 (3)	0.0314 (2)	0.6780 (2)	0.0556 (6)
C1	0.2015 (4)	0.4109 (3)	0.4913 (3)	0.0657 (9)
H1A	0.1223	0.3538	0.4695	0.079*
C2	0.2138 (4)	0.5322 (3)	0.4355 (3)	0.0760 (10)
H2A	0.1439	0.5574	0.3763	0.091*
N2	0.1233 (3)	−0.1189 (3)	0.8187 (3)	0.0798 (9)
C3	0.3297 (5)	0.6133 (3)	0.4687 (3)	0.0708 (9)
C4	0.4345 (4)	0.5823 (3)	0.5561 (3)	0.0671 (9)
H4A	0.5123	0.6409	0.5776	0.081*
C5	0.4208 (3)	0.4608 (3)	0.6112 (2)	0.0568 (8)
H5A	0.4906	0.4372	0.6711	0.068*
C6	0.3053 (3)	0.3735 (2)	0.5794 (2)	0.0496 (7)
C7	0.3005 (3)	0.2428 (3)	0.6385 (2)	0.0535 (7)
C8	0.1625 (3)	0.1556 (3)	0.6133 (3)	0.0623 (8)
H8A	0.0694	0.2031	0.6351	0.075*
H8B	0.1579	0.1376	0.5275	0.075*
C9	0.2500 (4)	−0.0773 (3)	0.6483 (3)	0.0689 (9)
H9A	0.3144	−0.0871	0.5818	0.083*
C10	0.2215 (4)	−0.1673 (3)	0.7341 (3)	0.0726 (9)
H10A	0.2634	−0.2517	0.7355	0.087*
C11	0.0935 (4)	0.0013 (3)	0.7805 (3)	0.0702 (9)
H11A	0.0285	0.0594	0.8209	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F	0.143 (2)	0.0728 (12)	0.1000 (14)	−0.0026 (14)	0.0088 (16)	0.0255 (11)
O	0.0624 (13)	0.0863 (16)	0.1027 (17)	−0.0131 (12)	−0.0320 (15)	0.0296 (14)
N1	0.0520 (14)	0.0485 (13)	0.0663 (15)	0.0000 (12)	−0.0001 (13)	−0.0063 (12)
C1	0.064 (2)	0.071 (2)	0.0621 (18)	−0.0075 (18)	−0.0060 (17)	0.0042 (16)
C2	0.081 (3)	0.077 (2)	0.069 (2)	0.006 (2)	−0.013 (2)	0.0144 (18)
N2	0.087 (2)	0.0536 (16)	0.099 (2)	−0.0046 (15)	0.0121 (19)	0.0027 (15)
C3	0.092 (3)	0.0574 (18)	0.063 (2)	0.004 (2)	0.015 (2)	0.0078 (16)
C4	0.073 (2)	0.0598 (18)	0.0681 (19)	−0.0104 (17)	0.009 (2)	−0.0072 (16)
C5	0.0529 (17)	0.0658 (19)	0.0518 (17)	−0.0018 (15)	0.0016 (15)	−0.0025 (14)
C6	0.0467 (16)	0.0559 (16)	0.0463 (15)	0.0017 (14)	0.0002 (13)	−0.0028 (12)
C7	0.0445 (15)	0.0635 (17)	0.0524 (16)	0.0015 (14)	0.0024 (14)	−0.0041 (14)
C8	0.0580 (18)	0.0609 (18)	0.0681 (19)	−0.0017 (15)	−0.0059 (17)	−0.0028 (15)
C9	0.0601 (18)	0.0654 (18)	0.081 (2)	0.0062 (17)	0.0065 (18)	−0.0114 (18)
C10	0.066 (2)	0.0521 (17)	0.100 (2)	0.0043 (16)	0.001 (2)	−0.0078 (19)
C11	0.0656 (19)	0.064 (2)	0.080 (2)	−0.0029 (18)	0.0139 (19)	−0.0142 (18)

Geometric parameters (Å, º) top

F—C3	1.358 (3)	C4—C5	1.379 (4)
O—C7	1.205 (3)	C4—H4A	0.9300
N1—C11	1.333 (3)	C5—C6	1.382 (4)
N1—C9	1.363 (3)	C5—H5A	0.9300
N1—C8	1.449 (3)	C6—C7	1.478 (4)
C1—C2	1.380 (4)	C7—C8	1.514 (4)
C1—C6	1.381 (4)	C8—H8A	0.9700
C1—H1A	0.9300	C8—H8B	0.9700
C2—C3	1.350 (5)	C9—C10	1.341 (4)
C2—H2A	0.9300	C9—H9A	0.9300
N2—C11	1.315 (4)	C10—H10A	0.9300
N2—C10	1.359 (4)	C11—H11A	0.9300
C3—C4	1.365 (5)

C11—N1—C9	105.9 (3)	C1—C6—C7	122.7 (3)
C11—N1—C8	127.7 (3)	C5—C6—C7	118.7 (3)
C9—N1—C8	126.3 (3)	O—C7—C6	122.2 (3)
C2—C1—C6	120.7 (3)	O—C7—C8	120.2 (3)
C2—C1—H1A	119.6	C6—C7—C8	117.6 (3)
C6—C1—H1A	119.6	N1—C8—C7	113.6 (2)
C3—C2—C1	118.5 (3)	N1—C8—H8A	108.8
C3—C2—H2A	120.7	C7—C8—H8A	108.8
C1—C2—H2A	120.7	N1—C8—H8B	108.8
C11—N2—C10	103.6 (3)	C7—C8—H8B	108.8
C2—C3—F	118.8 (3)	H8A—C8—H8B	107.7
C2—C3—C4	123.3 (3)	C10—C9—N1	106.2 (3)
F—C3—C4	117.9 (3)	C10—C9—H9A	126.9
C3—C4—C5	117.6 (3)	N1—C9—H9A	126.9
C3—C4—H4A	121.2	C9—C10—N2	111.1 (3)
C5—C4—H4A	121.2	C9—C10—H10A	124.4
C4—C5—C6	121.4 (3)	N2—C10—H10A	124.4
C4—C5—H5A	119.3	N2—C11—N1	113.2 (3)
C6—C5—H5A	119.3	N2—C11—H11A	123.4
C1—C6—C5	118.5 (3)	N1—C11—H11A	123.4

C6—C1—C2—C3	0.0 (5)	C5—C6—C7—C8	172.8 (2)
C1—C2—C3—F	179.5 (3)	C11—N1—C8—C7	98.2 (3)
C1—C2—C3—C4	−0.9 (6)	C9—N1—C8—C7	−78.6 (4)
C2—C3—C4—C5	0.8 (5)	O—C7—C8—N1	2.1 (4)
F—C3—C4—C5	−179.5 (3)	C6—C7—C8—N1	−178.2 (2)
C3—C4—C5—C6	0.0 (4)	C11—N1—C9—C10	0.9 (3)
C2—C1—C6—C5	0.8 (4)	C8—N1—C9—C10	178.3 (3)
C2—C1—C6—C7	−177.6 (3)	N1—C9—C10—N2	−0.9 (4)
C4—C5—C6—C1	−0.8 (4)	C11—N2—C10—C9	0.5 (4)
C4—C5—C6—C7	177.6 (3)	C10—N2—C11—N1	0.1 (4)
C1—C6—C7—O	170.8 (3)	C9—N1—C11—N2	−0.6 (4)
C5—C6—C7—O	−7.6 (4)	C8—N1—C11—N2	−177.9 (3)
C1—C6—C7—C8	−8.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N2ⁱ	0.97	2.51	3.454 (4)	164

Symmetry code: (i) −x, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₉FN₂O
M_r	204.20
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.6730 (17), 10.132 (2), 11.088 (2)
V (Å³)	974.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.969, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	3790, 1052, 778
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.093, 1.01
No. of reflections	1052
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.09

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···N2ⁱ	0.97	2.51	3.454 (4)	164

Symmetry code: (i) −x, y+1/2, −z+3/2.

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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