2-Azido-1-(4-fluoro­phen­yl)ethanone

Yousuf, S.; Arshad, M.; Butt, H.M.; Saeed, S.; Basha, F.Z.

doi:10.1107/S1600536812013426

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1268

doi:10.1107/S1600536812013426

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2-Azido-1-(4-fluorophenyl)ethanone

Sammer Yousuf,^a ^* Muhammad Arshad,^a,^b Hafiza Madiha Butt,^a Sumayya Saeed ^b and Fatima Z. Basha ^a ‡

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi 75270, Pakistan, and ^bDepartment of Chemistry, University of Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 22 March 2012; accepted 28 March 2012; online 31 March 2012)

The crystal structure of the title compound, C₈H₆FN₃O, is stabilized by C—H⋯O hydrogen bonds, which link the molecules into chains running parallel to the a axis.

Related literature

The title compound is an intermediate obtained during an attempt to synthesize biologically active triazoles. For the biological activity of triazoles, see: Genin et al. (2000 ); Parmee et al. (2000 ); Koble et al. (1995 ); Moltzen et al. (1994 ). For standard bond lengths: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₆FN₃O
M_r = 179.16
Orthorhombic, P b c a
a = 10.7985 (16) Å
b = 8.3971 (12) Å
c = 17.485 (3) Å
V = 1585.5 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 273 K
0.35 × 0.28 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.959, T_max = 0.976
8606 measured reflections
1476 independent reflections
1239 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.090
S = 1.06
1476 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1ⁱ	0.93	2.45	3.3722 (17)	174
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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 PARST (Nardelli, 1995 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812013426/rz2730sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013426/rz2730Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013426/rz2730Isup3.cml

checkCIF report

Comment top

The synthesis of 1,2,3-trizoles via click chemistry approach has gained much attention by synthetic chemists due to their immensely known medicinal importance (Genin et al., 2000, Parmee et al., 2000, Koble et al., 1995, Moltzen et al., 1994). In our quest for the synthesis of therapeutically active triazoles starting from commercially available acetophenone derivatives, a number of azides including the title compound, whose crystal structure is reported herein, have been prepared as an intermediate.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. The crystal structure (Fig. 2) is stabilized by intermolecular hydrogen bonds (Table 1) linking the m olecules to form chains parallel to the a axis.

Related literature top

The title compound is an intermediate obtained during an attempt to synthesize biologically active triazoles. For the biological activity of triazoles, see: Genin et al. (2000); Parmee et al. (2000); Koble et al. (1995); Moltzen et al. (1994). For standard bond lengths: Allen et al. (1987).

Experimental top

1-(4-Fluorophenyl)ethanone (7.239 mmol, 1.0 equiv.) was dissolved in acetonitrile (18 ml) in a round bottom flask. To the stirred mixture, p-toluenesulphonic acid (10.858 mmol, 1.5 equiv.) and N-bromosuccinimide (10.134 mmol, 1.4 equiv.) were added, and the solution was heated to reflux for 1 to 1.5 h until completion of the reaction as monitored by TLC analysis. The reaction mixture was cooled to room temperature and sodium azide (21.717 mmol, 3.0 equiv.) was added. After additional stirring for 2 to 3 h, ice cooled water was added to quench the reaction. The reaction mixture was extracted with diethyl ether (2 × 25 ml) and the combined organic layer was dried over anhydrous Na₂SO₄, filtered and concentrated in vacuum to get the crude product. The crude product was purified by flash silica gel chromatography (EtOAc/hexane, 1:9–3:7 v/v) to afford the title compound in 65% yield. Recrystallization by slow evaporation of an ethanol solution afforded crystals suitable for single-crystal X-ray studies. All chemicals were purchased from Sigma-Aldrich.

Structure description top

The title compound is an intermediate obtained during an attempt to synthesize biologically active triazoles. For the biological activity of triazoles, see: Genin et al. (2000); Parmee et al. (2000); Koble et al. (1995); Moltzen et al. (1994). For standard bond lengths: Allen et al. (1987).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Hydrogen atoms not involved in hydrogen bonds (dashed lines) are omitted.

2-Azido-1-(4-fluorophenyl)ethanone top

Crystal data top

C₈H₆FN₃O	F(000) = 736
M_r = 179.16	D_x = 1.501 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2831 reflections
a = 10.7985 (16) Å	θ = 2.3–27.8°
b = 8.3971 (12) Å	µ = 0.12 mm⁻¹
c = 17.485 (3) Å	T = 273 K
V = 1585.5 (4) Å³	Block, colourless
Z = 8	0.35 × 0.28 × 0.20 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1476 independent reflections
Radiation source: fine-focus sealed tube	1239 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scan	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→13
T_min = 0.959, T_max = 0.976	k = −10→10
8606 measured reflections	l = −21→21

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0469P)² + 0.2956P] where P = (F_o² + 2F_c²)/3
1476 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₆FN₃O	V = 1585.5 (4) Å³
M_r = 179.16	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.7985 (16) Å	µ = 0.12 mm⁻¹
b = 8.3971 (12) Å	T = 273 K
c = 17.485 (3) Å	0.35 × 0.28 × 0.20 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1476 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1239 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.976	R_int = 0.034
8606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.06	Δρ_max = 0.20 e Å⁻³
1476 reflections	Δρ_min = −0.19 e Å⁻³
118 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
O1	0.61761 (8)	0.03188 (12)	0.73973 (5)	0.0358 (3)
N1	0.77319 (12)	−0.13811 (15)	0.83252 (7)	0.0361 (3)
N2	0.68380 (11)	−0.09577 (14)	0.87237 (7)	0.0336 (3)
N3	0.60363 (13)	−0.07646 (17)	0.91283 (7)	0.0451 (4)
C1	0.89336 (12)	0.19093 (16)	0.64990 (8)	0.0305 (3)
H1B	0.9536	0.1521	0.6830	0.037*
C2	0.92779 (14)	0.28254 (17)	0.58742 (8)	0.0348 (4)
H2A	1.0106	0.3060	0.5782	0.042*
C3	0.83684 (14)	0.33759 (17)	0.53966 (8)	0.0342 (3)
C4	0.71318 (14)	0.30861 (18)	0.55138 (8)	0.0366 (4)
H4A	0.6536	0.3492	0.5182	0.044*
C5	0.67981 (13)	0.21777 (17)	0.61363 (8)	0.0333 (3)
H5A	0.5965	0.1968	0.6227	0.040*
C6	0.76889 (12)	0.15677 (16)	0.66330 (7)	0.0273 (3)
C7	0.72692 (12)	0.05618 (16)	0.72799 (7)	0.0277 (3)
C8	0.82354 (13)	−0.01705 (17)	0.78080 (8)	0.0313 (3)
H8A	0.8882	−0.0650	0.7499	0.038*
H8B	0.8611	0.0669	0.8110	0.038*
F1	0.87045 (9)	0.42468 (11)	0.47751 (5)	0.0478 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0225 (6)	0.0481 (6)	0.0370 (5)	−0.0033 (4)	−0.0003 (4)	−0.0021 (5)
N1	0.0337 (7)	0.0341 (7)	0.0405 (7)	0.0037 (5)	0.0029 (6)	0.0004 (5)
N2	0.0346 (7)	0.0329 (7)	0.0333 (6)	−0.0019 (5)	−0.0049 (6)	0.0031 (5)
N3	0.0413 (8)	0.0548 (9)	0.0392 (7)	0.0024 (7)	0.0065 (6)	0.0069 (6)
C1	0.0248 (7)	0.0338 (8)	0.0328 (7)	0.0029 (6)	−0.0019 (6)	−0.0054 (6)
C2	0.0293 (8)	0.0374 (8)	0.0376 (7)	−0.0015 (6)	0.0049 (6)	−0.0064 (6)
C3	0.0414 (9)	0.0314 (7)	0.0299 (7)	−0.0013 (6)	0.0036 (6)	−0.0031 (6)
C4	0.0355 (9)	0.0378 (8)	0.0366 (8)	0.0021 (6)	−0.0068 (6)	−0.0006 (6)
C5	0.0260 (7)	0.0343 (8)	0.0394 (8)	0.0003 (6)	−0.0025 (6)	−0.0041 (6)
C6	0.0241 (7)	0.0274 (7)	0.0304 (7)	0.0011 (6)	0.0005 (5)	−0.0075 (5)
C7	0.0232 (7)	0.0287 (7)	0.0313 (7)	0.0004 (5)	−0.0009 (5)	−0.0098 (5)
C8	0.0254 (7)	0.0336 (7)	0.0348 (7)	−0.0004 (6)	0.0003 (6)	−0.0012 (6)
F1	0.0544 (6)	0.0501 (6)	0.0389 (5)	−0.0045 (4)	0.0040 (4)	0.0089 (4)

Geometric parameters (Å, º) top

O1—C7	1.2154 (16)	C3—C4	1.373 (2)
N1—N2	1.2425 (17)	C4—C5	1.377 (2)
N1—C8	1.4652 (19)	C4—H4A	0.9300
N2—N3	1.1296 (17)	C5—C6	1.3936 (19)
C1—C2	1.387 (2)	C5—H5A	0.9300
C1—C6	1.3942 (19)	C6—C7	1.4826 (19)
C1—H1B	0.9300	C7—C8	1.5229 (19)
C2—C3	1.370 (2)	C8—H8A	0.9700
C2—H2A	0.9300	C8—H8B	0.9700
C3—F1	1.3591 (16)

N2—N1—C8	115.85 (12)	C4—C5—H5A	119.5
N3—N2—N1	170.98 (14)	C6—C5—H5A	119.5
C2—C1—C6	120.33 (13)	C5—C6—C1	119.02 (13)
C2—C1—H1B	119.8	C5—C6—C7	118.29 (12)
C6—C1—H1B	119.8	C1—C6—C7	122.69 (12)
C3—C2—C1	118.38 (13)	O1—C7—C6	121.43 (12)
C3—C2—H2A	120.8	O1—C7—C8	119.67 (12)
C1—C2—H2A	120.8	C6—C7—C8	118.90 (11)
F1—C3—C2	118.53 (13)	N1—C8—C7	113.59 (12)
F1—C3—C4	118.33 (13)	N1—C8—H8A	108.8
C2—C3—C4	123.14 (14)	C7—C8—H8A	108.8
C3—C4—C5	118.09 (14)	N1—C8—H8B	108.8
C3—C4—H4A	121.0	C7—C8—H8B	108.8
C5—C4—H4A	121.0	H8A—C8—H8B	107.7
C4—C5—C6	121.04 (13)

C6—C1—C2—C3	−0.2 (2)	C2—C1—C6—C7	178.42 (12)
C1—C2—C3—F1	−178.68 (12)	C5—C6—C7—O1	−2.87 (19)
C1—C2—C3—C4	1.1 (2)	C1—C6—C7—O1	177.86 (12)
F1—C3—C4—C5	178.78 (12)	C5—C6—C7—C8	177.46 (12)
C2—C3—C4—C5	−1.0 (2)	C1—C6—C7—C8	−1.81 (18)
C3—C4—C5—C6	−0.1 (2)	N2—N1—C8—C7	−54.22 (16)
C4—C5—C6—C1	1.0 (2)	O1—C7—C8—N1	11.84 (17)
C4—C5—C6—C7	−178.34 (12)	C6—C7—C8—N1	−168.49 (11)
C2—C1—C6—C5	−0.84 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.93	2.45	3.3722 (17)	174

Symmetry code: (i) x+1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₈H₆FN₃O
M_r	179.16
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	273
a, b, c (Å)	10.7985 (16), 8.3971 (12), 17.485 (3)
V (Å³)	1585.5 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.35 × 0.28 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.959, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	8606, 1476, 1239
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.06
No. of reflections	1476
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.93	2.45	3.3722 (17)	174

Symmetry code: (i) x+1/2, y, −z+3/2.

Footnotes

‡Additional corresponding author, e-mail: bashafz@gmail.com.

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