2-Azido-1-(4-nitro­phen­yl)ethanone

Sammer Yousuf; Muhammad Arshad; Hafiza Madiha Butt; Sumayya Saeed; Fatima Z Basha

doi:10.1107/S1600536812021241

. 2012 May 31;68(Pt 6):o1952. doi: 10.1107/S1600536812021241

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

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

PMCID: PMC3379503 PMID: 22719701

Abstract

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 ▶). graphic file with name e-68-o1952-scheme1.jpg

Experimental

Crystal data

C₈H₆N₄O₃
M _r = 206.17
Orthorhombic,
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[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 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)

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 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021241/rz2752sup1.cif

e-68-o1952-sup1.cif^{(15.6KB, cif)}

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

e-68-o1952-Isup2.hkl^{(81.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812021241/rz2752Isup3.cml

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

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

Open in a new tab

Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

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).

Experimental

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.