N-[4-(4-Nitro­phen­oxy)phen­yl]acetamide

Asifa Nigar; Zareen Akhter; M Nawaz Tahir

doi:10.1107/S1600536812031856

. 2012 Jul 18;68(Pt 8):o2485. doi: 10.1107/S1600536812031856

N-[4-(4-Nitrophenoxy)phenyl]acetamide

Asifa Nigar ^a, Zareen Akhter ^a, M Nawaz Tahir ^b,^*

PMCID: PMC3414940 PMID: 22904927

Abstract

The asymmetric unit of the title compound, C₁₄H₁₂N₂O₄, contains two molecules that differ principally in the orientation of the acetamide substituent to the adjacent benzene ring with dihedral angles of 44.77 (7) and 19.06 (7)°. The dihedral angles between the benzene rings are 64.46 (4) and 80.84 (4)°. In the crystal, classical N—H⋯O hydrogen bonds form C(4) chains along [100]. These chains are interlinked by C—H⋯O contacts forming R ₂ ²(10) rings. In the crystal, π–π interactions are observed with a distance of 3.5976 (18) Å between the centroids of the nitro-substituted benzene rings of one type of molecule.

Related literature

For a related structure, see: Nigar et al. (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₂N₂O₄
M _r = 272.26
Triclinic,
a = 9.6761 (6) Å
b = 10.4865 (7) Å
c = 14.3805 (14) Å
α = 98.779 (4)°
β = 98.641 (4)°
γ = 109.681 (3)°
V = 1325.57 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.35 × 0.28 × 0.24 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.948, T _max = 0.968
21059 measured reflections
5876 independent reflections
4294 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.118
S = 1.03
5876 reflections
363 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812031856/sj5257sup1.cif

e-68-o2485-sup1.cif^{(33KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031856/sj5257Isup2.hkl

e-68-o2485-Isup2.hkl^{(281.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812031856/sj5257Isup3.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
N1—H1⋯O5ⁱ	0.86	2.04	2.8897 (19)	170
N3—H3⋯O1ⁱⁱ	0.86	2.10	2.941 (2)	165
C11—H11⋯O4ⁱⁱⁱ	0.93	2.58	3.395 (2)	146

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

supplementary crystallographic information

Comment

The crystal structures of N-(4-(4-nitrophenoxy)phenyl)propionamide (Nigar et al. 2008) has been published and is related to that of (I), (Fig. 1).

In (I), two molecules (M1 and M2) are present in the asymmetric unit, which differ slightly from each other geometrically. In molecule M1, the acetamide group A (C1/C2/N1/O1), benzene ring B (C3—C8) and group C (O2/C9—C14/N2/O3/O4) of the 4-nitrophenol are almost planar with r.m.s. deviations of 0.0035 Å, 0.0109 Å and 0.0540 Å, respectively. The dihedral angles between A/B, A/C and B/C are 44.77 (7)°, 77.53 (7)° and 64.46 (4)°, respectively. In the second molecule M2, the comparable groups D (C15/C16/N3/O5), E (C17—C22) and F (O6/C23—C28/N4/O7/O8) are again almost planar with r.m.s. deviations of 0.0062 Å, 0.0031 Å and 0.0137 Å, respectively. The dihedral angles between D/E, D/F and E/F are 19.06 (7)°, 80.26 (5)° and 80.84 (4)°, respectively. Both molecules are interlinked forming C (4) chains (Bernstein et al., 1995) due to classical N—H···O H–bonds (Table 1, Fig. 2). These infinite one-dimensional chains form along [100] and are further interlinked through C–H···O contacts forming R₂²(10) rings (Table 1, Fig. 2). A π–π interaction is also present, Cg1···Cg1ⁱ [i = 1 - x, 1 - y, - z] at a distance of 3.8814 (10) Å, where Cg1 is the centroid of the (C23—C28) benzene ring .

Experimental

In the first step 4-(4-nitrophenoxy)aniline was prepared from a mixture of 4-aminophenol (5.046 g, 50 mmol), 4-nitrofluorobenzene (5.3 ml, 50 mmol) and anhydrous K₂CO₃ (6.91 g, 50 mmol) in 70 ml dimethylformamide (DMF) by heating and stirring at 373 K for 18 h in an inert atmosphere. After cooling to room temperature, the reaction mixture was poured into 800 ml of water to yield a yellow solid. The product was filtered, dried, and then recrystallized from n-hexane (86% yield).

In the second step, acetylchloride was reacted with 4-(4-nitrophenoxy)aniline, in appropriate molar ratios in tetrahydrofuran with 1 ml of triethylamine for 1.0 g of 4-(4-nitrophenoxy)aniline. The reaction mixture was refluxed for 2 h under inert conditions and allowed to stand overnight at room temperature. The settled salt was filtered off and filterate was evaporated to get the crude product, which was recrystallized from toluene (92% yield, m.p. 428 K).