2-Azido-1-(4-nitro­phen­yl)ethanone

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

doi:10.1107/S1600536812021241

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1952

doi:10.1107/S1600536812021241

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2-Azido-1-(4-nitrophenyl)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, Karachi, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

(Received 28 April 2012; accepted 10 May 2012; online 31 May 2012)

In the title compound, C₈H₆N₄O₃, the ketone [C—C(=O)—C] and nitro groups are tilted with respect to the benzene ring by 18.92 (6) and 24.11 (15)°, respectively. In the crystal, molecules are linked into interwoven chains running parallel to the [100] direction by C—H⋯N hydrogen bonds and weak π–π stacking interactions, with centroid–centroid separations of 3.897 (3) Å.

Related literature

For the crystal structure of the related compound 2-azido-1-(4-fluorophenyl)ethanone, see: Yousuf et al. (2012 ). For the biological activities of triazoles, see: Genin et al. (2000 ); Parmee et al. (2000 ); Koble et al. (1995 ); Moltzen et al. (1994 ).

Experimental

Crystal data

C₈H₆N₄O₃
M_r = 206.17
Orthorhombic, P c a 2₁
a = 7.6307 (5) Å
b = 9.5168 (6) Å
c = 12.4097 (8) Å
V = 901.19 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 273 K
0.50 × 0.23 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.942, T_max = 0.987
4914 measured reflections
1649 independent reflections
1461 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.074
S = 1.06
1649 reflections
136 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.11 e Å⁻³
Absolute structure: Flack (1983 ), 767 Friedel pairs
Flack parameter: 0.2 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯N2ⁱ	0.97	2.48	3.422 (3)	165
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+1, z]$ .

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/S1600536812021241/rz2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021241/rz2752Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021241/rz2752Isup3.cml

checkCIF report

Comment top

The title compound was obtained as intermediate during an attempt to synthesize new triazoles, an important class of organic compounds with a wide range of biological activities (Genin et al., 2000; Parmee et al., 2000; Koble et al., 1995; Moltzen et al., 1994).

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 nitrobenzene ring. The benzene ring forms dihedral angles of 18.92 (6) and 24.11 (15)° with the planes through the ketone (O3/C3/C7/C8) and nitro (N1/O1/O2) groups, respectively. The azide group is not linear (N3–N2–N1 = 171.7 (2)°). The bond lengths and angle are similar to those found in the previously reported compound (Yousuf et al., 2012). The crystal structure is stabilized by intermolecular C—H···N (Table 1) hydrogen bonds and π–π stacking interactions (centroid-to-centroid separations of 3.897 (3) Å) forming interwoven chains parallel to the a axis (Fig. 2).

Related literature top

For the crystal structure of the related compound 2-azido-1-(4-fluorophenyl)ethanone, see: Yousuf et al. (2012). For the biological activities of triazoles, see: Genin et al. (2000); Parmee et al. (2000); Koble et al. (1995); Moltzen et al. (1994).

Experimental top

1-(4-Nitrophenyl)ethanone (6.05 mmoL, 1.0 eq.) was dissolved in acetonitrile (18 ml) in a round bottom flask. To the stirred mixture, p-toluene sulphonic acid (9.08 mmoL, 1.5 eq.) and N-bromosuccinimide (8.48 mmol, 1.4 eq.) were added, and then heated to reflux for 1 to 1.5 h until TLC analysis showed no starting material present in the mixture. The reaction mixture was cooled to room temperature, sodium azide (18.16 mmoL, 3.0 eq.) was added and further stirred for 2 to 3 hrs followed by the addition of the ice cooled water 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 70% yield. Recrystallization from ethanol afforded crystals 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 compound with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal packing of the title compound. Hydrogen atoms not involved in hydrogen bonding (dashed lines) are omitted for clarity.

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

Crystal data top

C₈H₆N₄O₃	F(000) = 424
M_r = 206.17	D_x = 1.520 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c 2ac	Cell parameters from 1557 reflections
a = 7.6307 (5) Å	θ = 3.3–24.2°
b = 9.5168 (6) Å	µ = 0.12 mm⁻¹
c = 12.4097 (8) Å	T = 273 K
V = 901.19 (10) Å³	Block, colourles
Z = 4	0.50 × 0.23 × 0.11 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1649 independent reflections
Radiation source: fine-focus sealed tube	1461 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scan	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.942, T_max = 0.987	k = −11→11
4914 measured reflections	l = −15→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)] = 0.032	H-atom parameters constrained
wR(F²) = 0.074	w = 1/[σ²(F_o²) + (0.0342P)² + 0.0663P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1649 reflections	Δρ_max = 0.11 e Å⁻³
136 parameters	Δρ_min = −0.11 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 767 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (14)

Crystal data top

C₈H₆N₄O₃	V = 901.19 (10) Å³
M_r = 206.17	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 7.6307 (5) Å	µ = 0.12 mm⁻¹
b = 9.5168 (6) Å	T = 273 K
c = 12.4097 (8) Å	0.50 × 0.23 × 0.11 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1649 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1461 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.987	R_int = 0.020
4914 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.074	Δρ_max = 0.11 e Å⁻³
S = 1.06	Δρ_min = −0.11 e Å⁻³
1649 reflections	Absolute structure: Flack (1983), 767 Friedel pairs
136 parameters	Absolute structure parameter: 0.2 (14)
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
O1	0.9428 (3)	1.19359 (17)	0.40028 (13)	0.0815 (5)
O2	0.9798 (2)	1.30833 (17)	0.54808 (15)	0.0744 (5)
O3	0.6676 (2)	0.72287 (15)	0.81581 (12)	0.0673 (4)
N1	0.9448 (2)	1.20158 (19)	0.49879 (14)	0.0553 (5)
N2	0.7720 (3)	0.45389 (18)	0.76819 (14)	0.0603 (5)
N3	0.8183 (2)	0.45144 (17)	0.86298 (15)	0.0553 (4)
N4	0.8503 (3)	0.4344 (2)	0.95022 (17)	0.0740 (6)
C1	0.9238 (2)	0.9459 (2)	0.51250 (14)	0.0478 (5)
H1A	0.9657	0.9388	0.4423	0.057*
C2	0.8824 (3)	0.8273 (2)	0.57102 (15)	0.0472 (5)
H2B	0.8991	0.7389	0.5407	0.057*
C3	0.8160 (2)	0.83847 (19)	0.67466 (14)	0.0418 (4)
C4	0.7943 (2)	0.9715 (2)	0.71966 (14)	0.0474 (5)
H4A	0.7489	0.9796	0.7889	0.057*
C5	0.8386 (2)	1.0906 (2)	0.66373 (16)	0.0482 (4)
H5A	0.8264	1.1791	0.6946	0.058*
C6	0.9017 (2)	1.0752 (2)	0.56038 (14)	0.0438 (4)
C7	0.7632 (3)	0.7125 (2)	0.73869 (14)	0.0459 (4)
C8	0.8367 (3)	0.57217 (19)	0.70483 (15)	0.0520 (5)
H8A	0.8079	0.5563	0.6297	0.062*
H8B	0.9634	0.5754	0.7107	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1121 (14)	0.0726 (11)	0.0598 (10)	−0.0001 (10)	0.0104 (9)	0.0177 (8)
O2	0.0870 (11)	0.0473 (9)	0.0889 (12)	−0.0090 (8)	−0.0091 (10)	0.0089 (9)
O3	0.0804 (11)	0.0609 (9)	0.0606 (8)	−0.0032 (7)	0.0250 (8)	0.0022 (7)
N1	0.0540 (10)	0.0514 (12)	0.0607 (12)	0.0034 (8)	−0.0015 (9)	0.0086 (9)
N2	0.0725 (12)	0.0476 (10)	0.0607 (10)	−0.0110 (9)	−0.0118 (9)	0.0040 (8)
N3	0.0606 (11)	0.0435 (9)	0.0617 (11)	−0.0068 (8)	−0.0014 (9)	0.0033 (8)
N4	0.0883 (14)	0.0733 (14)	0.0603 (11)	−0.0078 (11)	−0.0024 (11)	0.0088 (10)
C1	0.0507 (10)	0.0538 (13)	0.0390 (9)	0.0025 (9)	0.0020 (8)	−0.0012 (9)
C2	0.0520 (10)	0.0424 (11)	0.0472 (10)	0.0023 (9)	0.0000 (9)	−0.0059 (8)
C3	0.0402 (9)	0.0447 (11)	0.0406 (9)	−0.0012 (8)	−0.0020 (8)	−0.0021 (8)
C4	0.0498 (10)	0.0512 (12)	0.0413 (9)	−0.0013 (9)	0.0033 (8)	−0.0052 (9)
C5	0.0510 (10)	0.0419 (11)	0.0516 (10)	0.0002 (8)	−0.0032 (9)	−0.0080 (9)
C6	0.0399 (9)	0.0439 (11)	0.0475 (9)	−0.0005 (8)	−0.0050 (8)	0.0046 (9)
C7	0.0460 (9)	0.0490 (11)	0.0426 (9)	−0.0047 (9)	−0.0030 (9)	−0.0025 (8)
C8	0.0594 (12)	0.0456 (12)	0.0510 (10)	−0.0008 (10)	−0.0012 (10)	0.0031 (9)

Geometric parameters (Å, º) top

O1—N1	1.225 (2)	C2—H2B	0.9300
O2—N1	1.216 (2)	C3—C4	1.393 (3)
O3—C7	1.207 (2)	C3—C7	1.493 (3)
N1—C6	1.462 (2)	C4—C5	1.372 (3)
N2—N3	1.229 (2)	C4—H4A	0.9300
N2—C8	1.459 (2)	C5—C6	1.378 (3)
N3—N4	1.122 (2)	C5—H5A	0.9300
C1—C6	1.377 (3)	C7—C8	1.508 (3)
C1—C2	1.379 (3)	C8—H8A	0.9700
C1—H1A	0.9300	C8—H8B	0.9700
C2—C3	1.386 (2)

O2—N1—O1	123.83 (18)	C3—C4—H4A	119.4
O2—N1—C6	118.28 (16)	C4—C5—C6	118.00 (18)
O1—N1—C6	117.89 (18)	C4—C5—H5A	121.0
N3—N2—C8	115.67 (17)	C6—C5—H5A	121.0
N4—N3—N2	171.7 (2)	C1—C6—C5	122.64 (18)
C6—C1—C2	118.44 (17)	C1—C6—N1	118.80 (16)
C6—C1—H1A	120.8	C5—C6—N1	118.55 (18)
C2—C1—H1A	120.8	O3—C7—C3	121.29 (19)
C1—C2—C3	120.62 (18)	O3—C7—C8	121.17 (19)
C1—C2—H2B	119.7	C3—C7—C8	117.52 (15)
C3—C2—H2B	119.7	N2—C8—C7	114.03 (16)
C2—C3—C4	119.02 (17)	N2—C8—H8A	108.7
C2—C3—C7	122.04 (17)	C7—C8—H8A	108.7
C4—C3—C7	118.93 (15)	N2—C8—H8B	108.7
C5—C4—C3	121.25 (16)	C7—C8—H8B	108.7
C5—C4—H4A	119.4	H8A—C8—H8B	107.6

C8—N2—N3—N4	−176.5 (17)	O2—N1—C6—C1	−156.72 (18)
C6—C1—C2—C3	1.5 (3)	O1—N1—C6—C1	23.6 (2)
C1—C2—C3—C4	−1.0 (3)	O2—N1—C6—C5	24.0 (2)
C1—C2—C3—C7	177.54 (16)	O1—N1—C6—C5	−155.73 (18)
C2—C3—C4—C5	−0.6 (3)	C2—C3—C7—O3	−161.46 (19)
C7—C3—C4—C5	−179.14 (16)	C4—C3—C7—O3	17.1 (3)
C3—C4—C5—C6	1.5 (3)	C2—C3—C7—C8	19.8 (2)
C2—C1—C6—C5	−0.6 (3)	C4—C3—C7—C8	−161.67 (16)
C2—C1—C6—N1	−179.83 (16)	N3—N2—C8—C7	−67.2 (3)
C4—C5—C6—C1	−0.9 (3)	O3—C7—C8—N2	4.1 (3)
C4—C5—C6—N1	178.33 (16)	C3—C7—C8—N2	−177.17 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···N2ⁱ	0.97	2.48	3.422 (3)	165

Symmetry code: (i) x+1/2, −y+1, z.

Experimental details

Crystal data
Chemical formula	C₈H₆N₄O₃
M_r	206.17
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	273
a, b, c (Å)	7.6307 (5), 9.5168 (6), 12.4097 (8)
V (Å³)	901.19 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.50 × 0.23 × 0.11

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.942, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	4914, 1649, 1461
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.074, 1.06
No. of reflections	1649
No. of parameters	136
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.11
Absolute structure	Flack (1983), 767 Friedel pairs
Absolute structure parameter	0.2 (14)

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—H8B···N2ⁱ	0.9700	2.4800	3.422 (3)	165.00

Symmetry code: (i) x+1/2, −y+1, z.

Footnotes

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

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