N-[(2-Hydr­oxy-5-methoxy­phen­yl)(3-nitro­phen­yl)meth­yl]acetamide

M NizamMohideen; S Thenmozhi; A SubbiahPandi; N Panneer Selvam; P T Perumal

doi:10.1107/S1600536809009726

. 2009 Mar 25;65(Pt 4):o829. doi: 10.1107/S1600536809009726

N-[(2-Hydroxy-5-methoxyphenyl)(3-nitrophenyl)methyl]acetamide

M NizamMohideen ^a, S Thenmozhi ^b, A SubbiahPandi ^b,^*, N Panneer Selvam ^c, P T Perumal ^c

PMCID: PMC2968863 PMID: 21582549

Abstract

In the title compound, C₁₆H₁₆N₂O₅, the methoxy group is disordered with site occupancies of 0.20 (3) and 0.80 (3). The dihedral angle between the two aromatic rings is 73.7 (2)°. The crystal structure is characterized by intermolecular N—H⋯O, O—H⋯O, C—H⋯O and C—H⋯π hydrogen bonds.

Related literature

For N-substituted phenyl acetamides as intermediates in organic synthesis, see: Gowda et al. (2007 ▶); Ghosh et al. (2005 ▶). For a related structure, see: NizamMohideen et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₆N₂O₅
M _r = 316.31
Monoclinic,
a = 15.3351 (3) Å
b = 8.1327 (2) Å
c = 14.5308 (3) Å
β = 117.387 (1)°
V = 1609.10 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.32 × 0.28 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: none
23127 measured reflections
6121 independent reflections
3900 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.196
S = 1.03
6121 reflections
216 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009726/bt2901sup1.cif

e-65-0o829-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009726/bt2901Isup2.hkl

e-65-0o829-Isup2.hkl^{(293.6KB, hkl)}

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
O2—H2⋯O5ⁱ	0.82	1.80	2.617 (2)	179
N1—H1⋯O4ⁱⁱ	0.86	2.30	3.159 (2)	174
C10—H10⋯O1ⁱⁱⁱ	0.93	2.47	3.320 (2)	152
C12—H12⋯O2^iv	0.93	2.58	3.397 (2)	147
C14—H14⋯O4ⁱⁱ	0.93	2.55	3.470 (2)	169
C8—H8⋯O5	0.98	2.30	2.714 (2)	105
C11—H11⋯Cg1^iv	0.93	2.83	3.680 (2)	153
C1B—H1B1⋯Cg2^v	0.96	2.61	3.531 (2)	160

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg1 and Cg2 are the centroids of the C2-C7 and C9-C14 rings, respectively.

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help in collecting the X-ray intensity data. MNM and ASP thank Dr J. Jothi Kumar, Principal of the Presidency College (Autonomous), Chennai, India, for providing the computer and internet facilities.

supplementary crystallographic information

Comment

N-(Substituted phenyl) acetamides are well known for their importance as intermediates in organic synthesis (Gowda et al., 2007). Depending on the types of substitution at the α, β and keto-C atoms, and the conformational flexibility of the substituent groups, a variety of β-acetamido ketones offering the possibility of intermolecular interactions can be obtained (Ghosh et al., 2005). The amide linkage [–NHC(O)-] is known to be strong enough to form and maintain protein architectures and has been utilized to create various molecular devices for a spectrum of purposes in organic chemistry. We have synthesized an amide system with an aromatic ring as a terminal group to determine how the rigid ring affects the conformational behavior. As part of our ongoing investigation of acetamide derivatives, the title compound has been prepared and its crystal structure is presented here.

The bond lenghts and angles are comparable with N-[(3-Nitro-phenyl)-(2-hydroxy-napthalen-1-yl)-methyl]-acetamide (NizamMohideen et al., 2009), a structure closely related to the title compound. The nitro group is slighty twisted out of the plane of the benzene ring, as indicated by O4—N2—C13—C14 and O3—N2—C13—C14 torsion angles of -8.6 (3) and 171.0 (2)°, respectively, and comparable with those in the previously reported structure mentioned above.

The dihedral angle between the C2—C7 and C9—C14 benzene rings is 73.7 (2)°. The dihedral angle between the acetamide residue and the benzene rings (C2—C7 and C9—C14) are 70.0 (1) and 37.4 (2)°, respectively.

The intermolecular aggregation of the molecules is determined by combination of N—H···O, C—H···O, O—H···O and C—H···π hydrogen bonds (Table 1). The crystal structure is characterized by intermolecular bifurcated acceptor hydrogen bonds between the benzene and acetamide groups (Fig. 2). Atom N1 and C14 in the molecule at (x, y, z) act as a hydrogen-bond donor via atom H1 and H14 to atom O4 in the molecule at (-x, 1 - y, -z). This intermolecular hydrogen bond links the molecule into dimers with a cyclic R²₂(16) and R²₂(10) (Bernstein et al., 1995) ring system, respectively. Atom C10 in the molecule at (x, y, z) acts as a hydrogen-bond donor via atom H10 to atom O1 in the molecule at (1 - x, 1 - y, 1 - z). This intermolecular hydrogen bond links the molecule into dimers with a cyclic R²₂(16) ring system. The crystal structure is further stabilized by C—H···π interactions involing rings C11—H11···Cg1 (Cg1 is the centroid of the C2—C7 ring) and C1—H1a···Cg2 (where Cg2 is the centroid of the C9—C14 ring).

Experimental

A mixture of 3-nitrobenzaldehyde (10 mmol), 4-methoxyphenol (10 mmol) and iodine (0.4 mmol, 4 mol%) were mixed in acetonitrile (5 ml). To that suspension acetyl chloride (2.8 mmol, 0.2 ml) was added and the reaction mixture was stirred at room temperature for 5 h. After the completion of the reaction (as monitored by TLC), saturated sodium thiosulfate solution (5 ml) was added. The precipitated solid was filtered and dried. The dried sample was washed with diethyl ether (2 × 10 ml) and again dried. Single crystals of the title compound suitable for X-ray diffraction were obtained by slow evaporation of a solution in Ethanol.