2-Azido-1-(4-methyl­phen­yl)ethanone

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

doi:10.1107/S1600536812018491

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1608

doi:10.1107/S1600536812018491

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

Muhammad Arshad,^a,^b Sammer Yousuf,^a ^* 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 13 April 2012; accepted 25 April 2012; online 5 May 2012)

In the molecule of the title compound, C₉H₉N₃O, the angle formed by the least-squares line through the azide group with the normal to the plane of the benzene plane ring is 46.62 (16)°. The crystal structure features C—H⋯O hydrogen bonds, which link the molecules into zigzag chains running parallel to [010].

Related literature

For a related structure, see: Yousuf et al. (2012 ). For the biological activity of triazoles, see: Genin et al. (2000 ); Parmee et al. (2000 ); Koble et al. (1995 ); Moltzen et al. (1994 ).

Experimental

Crystal data

C₉H₉N₃O
M_r = 175.19
Monoclinic, P 2₁ /c
a = 7.696 (3) Å
b = 9.025 (3) Å
c = 14.248 (4) Å
β = 118.726 (15)°
V = 867.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 K
0.30 × 0.21 × 0.17 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.973, T_max = 0.985
4915 measured reflections
1595 independent reflections
1464 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.090
S = 1.07
1595 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1ⁱ	0.97	2.40	3.2404 (19)	145
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536812018491/rz2744sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018491/rz2744Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812018491/rz2744Isup3.cml

checkCIF report

Comment top

Triazoles are considered an important class of compounds due to their therapeutic potential (Genin et al., 2000; Parmee et al., 2000; Koble et al., 1995; Moltzen et al., 1994). The title compound was obtained as an intermediate during our attempt to synthesize biologically active triazoles.

The structure of the title compound (Fig. 1) is similar to that of our recently published compound 2-azido-1-(4-fluorophenyl)ethanone (Yousuf et al., 2012) with the difference that the fluorophenyl ring is replaced by a toluene ring. The bond lengths and angles are similar to those found in the previously reported compound. The azide group is not linear (N3–N2–N1 = 170.84 (11)°) and the least-square line through it forms with the normal to the plane of benzene ring an angle of 46.62 (16)°. The crystal structure is stabilized by C—H···O intermolecular hydrogen bonds (Table 1) forming zig-zag chains parallel to the b axis (Fig. 2).

Related literature top

For a related structure, see: Yousuf et al. (2012). For the biological activity of triazoles, see: Genin et al. (2000); Parmee et al. (2000); Koble et al. (1995); Moltzen et al. (1994).

Experimental top

1-p-Tolylethanone (8.32 mmol, 1.0 equiv.) was dissolved in acetonitrile (20 ml) in a round bottom flask. To the stirred mixture, p-toluene sulphonic acid (12.5 mmol, 1.5 equiv.) and N-bromosuccinimide (11.6 mmol, 1.4 equiv.) were added, and the mixtyre refluxed for 1 to 1.5 h until TLC analysis showed no starting material present. The reaction mixture was cooled to room temperature, sodium azide (24.9 mmol, 3.0 equiv.) was added and the mixture further stirred for 2 to 3 hrs followed by the addition of ice cooled water to quench the reaction. The reaction mixture was extracted with ethylacetate (25 ml × 2) and the combined organic layer were 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 crystalline title compound in 70% yield. The crystals were found to be suitable for single-crystal X-ray studies. All chemicals were purchased from Sigma-Aldrich.

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 cmpound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Crystal packing of the title compound viewed along the a axis. Hydrogen atoms not involved in hydrogen bonds (dashed lines) are omitted for clearity.

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

Crystal data top

C₉H₉N₃O	F(000) = 368
M_r = 175.19	D_x = 1.341 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3299 reflections
a = 7.696 (3) Å	θ = 2.8–25.5°
b = 9.025 (3) Å	µ = 0.09 mm⁻¹
c = 14.248 (4) Å	T = 273 K
β = 118.726 (15)°	Block, colourless
V = 867.8 (5) Å³	0.30 × 0.21 × 0.17 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 independent reflections
Radiation source: fine-focus sealed tube	1464 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scan	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.973, T_max = 0.985	k = −10→10
4915 measured reflections	l = −16→15

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0506P)² + 0.1892P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1595 reflections	Δρ_max = 0.24 e Å⁻³
120 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (4)

Crystal data top

C₉H₉N₃O	V = 867.8 (5) Å³
M_r = 175.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.696 (3) Å	µ = 0.09 mm⁻¹
b = 9.025 (3) Å	T = 273 K
c = 14.248 (4) Å	0.30 × 0.21 × 0.17 mm
β = 118.726 (15)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1464 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.985	R_int = 0.019
4915 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	Δρ_max = 0.24 e Å⁻³
1595 reflections	Δρ_min = −0.28 e Å⁻³
120 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	0.37626 (11)	0.32286 (8)	0.67821 (6)	0.0259 (2)
N1	0.30617 (13)	0.53889 (11)	0.79105 (8)	0.0250 (3)
N2	0.46826 (13)	0.49335 (10)	0.86119 (7)	0.0220 (2)
N3	0.60533 (15)	0.45093 (11)	0.93395 (8)	0.0285 (3)
C1	0.27074 (15)	0.33313 (12)	0.45933 (9)	0.0225 (3)
H1B	0.3054	0.2413	0.4929	0.027*
C2	0.22351 (15)	0.34548 (12)	0.35311 (9)	0.0234 (3)
H2A	0.2257	0.2615	0.3159	0.028*
C3	0.17253 (15)	0.48218 (12)	0.30073 (9)	0.0217 (3)
C4	0.17304 (15)	0.60668 (12)	0.35936 (9)	0.0238 (3)
H4B	0.1425	0.6991	0.3264	0.029*
C5	0.21797 (15)	0.59490 (12)	0.46497 (9)	0.0226 (3)
H5A	0.2157	0.6789	0.5022	0.027*
C6	0.26701 (14)	0.45736 (11)	0.51680 (9)	0.0198 (3)
C7	0.31704 (14)	0.43963 (11)	0.63045 (9)	0.0201 (3)
C8	0.29227 (16)	0.57461 (12)	0.68730 (9)	0.0224 (3)
H8A	0.3935	0.6468	0.6981	0.027*
H8B	0.1643	0.6195	0.6418	0.027*
C9	0.11424 (17)	0.49495 (13)	0.18444 (9)	0.0275 (3)
H9A	0.1646	0.5861	0.1723	0.041*
H9B	−0.0276	0.4939	0.1426	0.041*
H9C	0.1684	0.4130	0.1640	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0310 (4)	0.0219 (4)	0.0239 (4)	0.0038 (3)	0.0125 (4)	0.0038 (3)
N1	0.0204 (5)	0.0313 (5)	0.0230 (5)	0.0014 (4)	0.0103 (4)	−0.0017 (4)
N2	0.0254 (5)	0.0220 (5)	0.0229 (5)	−0.0032 (4)	0.0151 (5)	−0.0038 (4)
N3	0.0296 (5)	0.0333 (6)	0.0225 (5)	0.0008 (4)	0.0125 (5)	0.0017 (4)
C1	0.0214 (5)	0.0199 (5)	0.0245 (6)	0.0039 (4)	0.0097 (4)	0.0022 (4)
C2	0.0226 (5)	0.0233 (6)	0.0239 (6)	0.0029 (4)	0.0109 (4)	−0.0020 (4)
C3	0.0155 (5)	0.0282 (6)	0.0222 (6)	−0.0008 (4)	0.0096 (4)	0.0014 (4)
C4	0.0234 (5)	0.0198 (5)	0.0261 (6)	−0.0005 (4)	0.0104 (5)	0.0045 (4)
C5	0.0227 (5)	0.0187 (5)	0.0246 (6)	−0.0018 (4)	0.0100 (5)	−0.0016 (4)
C6	0.0152 (5)	0.0204 (5)	0.0222 (6)	−0.0010 (4)	0.0076 (4)	−0.0001 (4)
C7	0.0152 (5)	0.0212 (5)	0.0219 (6)	−0.0014 (4)	0.0074 (4)	0.0001 (4)
C8	0.0215 (5)	0.0224 (5)	0.0209 (6)	−0.0002 (4)	0.0083 (4)	−0.0014 (4)
C9	0.0270 (6)	0.0333 (6)	0.0254 (6)	0.0025 (5)	0.0151 (5)	0.0041 (5)

Geometric parameters (Å, º) top

O1—C7	1.2180 (13)	C4—C5	1.3765 (17)
N1—N2	1.2350 (14)	C4—H4B	0.9300
N1—C8	1.4659 (15)	C5—C6	1.4003 (16)
N2—N3	1.1327 (14)	C5—H5A	0.9300
C1—C2	1.3806 (16)	C6—C7	1.4821 (16)
C1—C6	1.3968 (16)	C7—C8	1.5247 (15)
C1—H1B	0.9300	C8—H8A	0.9700
C2—C3	1.3970 (16)	C8—H8B	0.9700
C2—H2A	0.9300	C9—H9A	0.9600
C3—C4	1.3991 (16)	C9—H9B	0.9600
C3—C9	1.4984 (17)	C9—H9C	0.9600

N2—N1—C8	116.42 (9)	C1—C6—C7	119.08 (10)
N3—N2—N1	170.84 (11)	C5—C6—C7	122.31 (10)
C2—C1—C6	120.60 (10)	O1—C7—C6	122.33 (10)
C2—C1—H1B	119.7	O1—C7—C8	120.22 (10)
C6—C1—H1B	119.7	C6—C7—C8	117.45 (9)
C1—C2—C3	121.02 (10)	N1—C8—C7	113.13 (9)
C1—C2—H2A	119.5	N1—C8—H8A	109.0
C3—C2—H2A	119.5	C7—C8—H8A	109.0
C2—C3—C4	118.09 (10)	N1—C8—H8B	109.0
C2—C3—C9	121.11 (10)	C7—C8—H8B	109.0
C4—C3—C9	120.79 (10)	H8A—C8—H8B	107.8
C5—C4—C3	121.19 (10)	C3—C9—H9A	109.5
C5—C4—H4B	119.4	C3—C9—H9B	109.5
C3—C4—H4B	119.4	H9A—C9—H9B	109.5
C4—C5—C6	120.49 (10)	C3—C9—H9C	109.5
C4—C5—H5A	119.8	H9A—C9—H9C	109.5
C6—C5—H5A	119.8	H9B—C9—H9C	109.5
C1—C6—C5	118.60 (11)

C6—C1—C2—C3	0.53 (16)	C4—C5—C6—C7	179.79 (9)
C1—C2—C3—C4	0.77 (16)	C1—C6—C7—O1	5.82 (15)
C1—C2—C3—C9	−177.81 (9)	C5—C6—C7—O1	−173.48 (10)
C2—C3—C4—C5	−1.46 (16)	C1—C6—C7—C8	−174.32 (9)
C9—C3—C4—C5	177.13 (10)	C5—C6—C7—C8	6.38 (14)
C3—C4—C5—C6	0.84 (16)	N2—N1—C8—C7	65.13 (12)
C2—C1—C6—C5	−1.16 (15)	O1—C7—C8—N1	−11.81 (14)
C2—C1—C6—C7	179.51 (9)	C6—C7—C8—N1	168.33 (8)
C4—C5—C6—C1	0.48 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1ⁱ	0.97	2.40	3.2404 (19)	145

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₉H₉N₃O
M_r	175.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	7.696 (3), 9.025 (3), 14.248 (4)
β (°)	118.726 (15)
V (Å³)	867.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.21 × 0.17

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.973, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	4915, 1595, 1464
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.090, 1.07
No. of reflections	1595
No. of parameters	120
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.28

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
C8—H8A···O1ⁱ	0.97	2.40	3.2404 (19)	145

Symmetry code: (i) −x+1, y+1/2, −z+3/2.

Footnotes

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

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