N-[(2-Hydr­oxy-1-naphth­yl)(2-hydroxy­phen­yl)meth­yl]acetamide

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

doi:10.1107/S1600536809007983

. 2009 Mar 11;65(Pt 4):o740. doi: 10.1107/S1600536809007983

N-[(2-Hydroxy-1-naphthyl)(2-hydroxyphenyl)methyl]acetamide

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

PMCID: PMC2968777 PMID: 21582473

Abstract

In the asymmetric unit of the title compound, C₁₉H₁₇NO₃, there are two crystallographically independent molecules, which are connected to each other by O—H⋯O hydrogen bonds, forming molecular chains as well as cyclic centrosymmetric R ₂ ²(16) dimers.

Related literature

For background literature, see: Barker et al. (2008 ▶); Gade (2002 ▶); Linton & Hamilton (1997 ▶); Valeur & Leray (2000 ▶); Wabnitz & Spencer (2002 ▶). For related structures, see: Gowda et al. (2000 ▶, 2006 ▶, 2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Fun et al. (2008 ▶).

Experimental

Crystal data

C₁₉H₁₇NO₃
M _r = 307.34
Monoclinic,
a = 21.286 (5) Å
b = 17.9288 (4) Å
c = 19.524 (7) Å
β = 121.428 (1)°
V = 6358 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.980, T _max = 0.986
33278 measured reflections
6464 independent reflections
4384 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.146
S = 1.02
6464 reflections
417 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.50 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 for Windows (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/S1600536809007983/pv2141sup1.cif

e-65-0o740-sup1.cif^{(29.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007983/pv2141Isup2.hkl

e-65-0o740-Isup2.hkl^{(310.1KB, 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
O1—H1⋯O3ⁱ	0.82	1.99	2.792 (2)	166
O2A—H2A1⋯O3ⁱⁱ	0.82	1.89	2.702 (2)	170
O2—H2⋯O3Aⁱⁱⁱ	0.82	1.81	2.588 (2)	159
O1A—H1A1⋯O3A	0.82	2.16	2.928 (2)	156

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

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 Presidency College, Chennai, India, for providing computer and internet facilities.

supplementary crystallographic information

Comment

β-Acetamido ketones serve as potential intermediates in the synthesis of natural products and antibiotics (Wabnitz & Spencer, 2002). Due to the nucleophilic nature of benzylic hydroxyl groups these are usually protected during multi-step organic synthesis (Barker et al., 2008). Amide moiety and their metal ion complexes are widely used for their properties and potential applications (Gade, 2002; Valeur & Leray, 2000; Linton & Hamilton, 1997). 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. The effect of substituents on the solid state structures of N-aromatic amides have been described in the literature (Gowda et al., 2000, 2006, 2007). As part of our investigations on acetamide derivatives, the title compound, (I), has been prepared and its crystal structure is presented here.

Figs. 1 and 2 show the molecular structures and conformations of the two crystallographically independent molecules, A (C1—C19, N1, O1, O2, O3) and B (C1A—C19A, N1A, O1A, O2A, O3A), in the asymmetric unit of (I), with the atomic numbering scheme. The bond lengths and angles in the two independent molecules agree with each other. The normal probability plot analyses (International Tables for X-ray Crystallography, 1974, Vol. IV, pp. 293–309) for both bond lengths and angles show that the differences between the two symmetry independent molecules are of a statistical nature. The bond distances of C18 = O3 and C18A = O3A [1.245 (2) and 1.244 (2) Å] for the molecules A and B, respectively, which are typical for double bonds (Fun et al., 2008).

In the molecules A and B, benzene and naphthalene rings are individually planar as expected. The deviations of the atoms O2 and O2A from the least-squares plane of the naphthalene rings are -0.075 (1) and 0.164 (1) Å. The deviations of the atoms O1 and O1A from the least-squares plane of the benzene rings are 0.056 (1) and 0.021 (1) Å. The dihedral angles between the naphthalene ring system and benzene rings are 75.7 (1) and 82.9 (1)° for molecules A and B respectively, and those between the fused rings are 0.3 (1) and 2.8 (1) °.

The crystal packing is stabilized by strong O—H···O inter and intramolecular hydrogen bonds and each molecule has a week intramolecular C—H···O interaction (Table 1). Considering only A-type molecules, atom O1 acts as a donar in a strong intermolecular O—H···O interaction via H1 with acetamido atom O3 of a symmetry related molecule, generating centrosymmetric hydrogen bonded dimers with a cyclic R₂²(16) ring system (Bernstein et al., 1995) (Fig. 3). The interlinking of A and B molecules via strong O—H···O hydrogen bond generates infinite chains running along c axis. The atoms O3 and O3a act as a acceptors for all inter and intramolecular interactions.

Experimental

A mixture of 2-hydroxybenzaldehyde (10 mmol), β-naphthol (10 mmol) and iodine (0.4 mmol, 4 mol%) were mixed in acetonitrile (5 ml). To the suspension acetyl chloride (2.8 mmol, 0.2 ml) was added and the reaction mixture was stirred at room temperature for 6 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.