2-(Naphthalen-1-yl)-4-(naphthalen-1-yl­methyl­idene)-1,3-oxazol-5(4H)-one

Cevher Gündoğdu; Serap Alp; Yavuz Ergün; Barış Tercan; Tuncer Hökelek

doi:10.1107/S1600536811015340

. 2011 Apr 29;67(Pt 5):o1258–o1259. doi: 10.1107/S1600536811015340

2-(Naphthalen-1-yl)-4-(naphthalen-1-ylmethylidene)-1,3-oxazol-5(4H)-one

Cevher Gündoğdu ^a, Serap Alp ^a, Yavuz Ergün ^a, Barış Tercan ^b, Tuncer Hökelek ^c,^*

PMCID: PMC3089157 PMID: 21754548

Abstract

In the title compound, C₂₄H₁₅NO₂, the oxazole ring is oriented at dihedral angles of 10.09 (4) and 6.04 (4)° with respect to the mean planes of the naphthalene ring systems, while the two naphthalene ring systems make a dihedral angle of 4.32 (3)°. Intramolecular C—H⋯N hydrogen bonds link the oxazole N atom to the naphthalene ring systems. In the crystal, intermolecular weak C—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers. π–π contacts between the oxazole and naphthalene rings and between the naphthalene ring systems [centroid–centroid distances = 3.5947 (9) and 3.7981 (9) Å] may further stabilize the crystal structure. Three weak C—H⋯π interactions also occur.

Related literature

For the roles of oxazolones in the syntheses of amino acids, peptides, antimicrobial or antitumor compounds, immunomodulators, heterocyclic precursors for biosensors coupling and/or photosensitive composition devices for proteins, see: Gottwald & Seebach (1999 ▶); Meiwes et al. (1997 ▶); Martinez et al. (1964 ▶); Gelmi et al. (1997 ▶); Croce et al. (1994 ▶); Cannella et al. (1996 ▶); Kojima et al. (1998 ▶). For applications of the 5-oxazolones, including their use in semiconductor devices because of their promising photophysical and photochemical activity, see: Gündoğdu et al. (2010 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₄H₁₅NO₂
M _r = 349.37
Monoclinic,
a = 18.6927 (5) Å
b = 6.0646 (2) Å
c = 15.6262 (5) Å
β = 107.212 (2)°
V = 1692.11 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.42 × 0.35 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.964, T _max = 0.986
29257 measured reflections
4260 independent reflections
2911 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.136
S = 1.07
4260 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536811015340/xu5196sup1.cif

e-67-o1258-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015340/xu5196Isup2.hkl

e-67-o1258-Isup2.hkl^{(204.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811015340/xu5196Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2 and Cg4 are the centroids of the C1—C3/C8—C10, C3—C8 and C15—C19/C24 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯N1	0.95	2.34	3.0110 (19)	127
C10—H10⋯O2ⁱ	0.95	2.46	3.324 (2)	152
C11—H11⋯O2ⁱ	0.95	2.47	3.3601 (18)	155
C23—H23⋯N1	0.95	2.25	2.908 (2)	126
C9—H9⋯Cg4ⁱⁱ	0.95	2.87	3.543 (2)	129
C18—H18⋯Cg1ⁱⁱⁱ	0.95	2.61	3.381 (2)	139
C20—H20⋯Cg2ⁱⁱⁱ	0.95	2.75	3.450 (2)	131

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

Acknowledgments

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of the diffractometer.

supplementary crystallographic information

Comment

Oxazolones that are internal anhydrides of acyl amino acids are important class of five-membered heterocycles. They are highly versatile intermediates used for the syntheses of several organic molecules, including amino acids, peptides (Gottwald & Seebach, 1999; Meiwes et al., 1997), antimicrobial or antitumor compounds (Martinez et al., 1964; Gelmi et al., 1997), immunomodulators, heterocyclic precursors for biosensors coupling (Croce et al., 1994; Cannella et al., 1996) and/or photosensitive composition devices for proteins (Kojima et al., 1998). They can be easily prepared from N-acyl amino acids by dehydration. 5-Oxazolones have also a wide range of applications including their use in semiconductor devices because of their promising photophysical and photochemical activities (Gündoğdu et al., 2010). The present study was undertaken to ascertain the crystal structure of the title compound.

The title compound consists of an oxazol ring and two naphthalene groups (Fig. 1), where the bond lengths are close to standard values (Allen et al., 1987). The intramolecular C-H···N hydrogen bonds link the oxazol nitrogen atoms to the naphthalene groups (Table 1 and Fig. 1).

An examination of the deviations from the least-squares planes through individual rings shows that rings A (C1—C3/C8—C10), B (C3—C8), C (O1/N1/C12—C14), D (C15—C19/C24) and E (C19—C24) are planar. The naphthalene groups, containing the rings A, B and D, E are also nearly planar [with maximum deviations of 0.022 (2) Å for atom C6 and -0.061 (2) Å for atom C17] with dihedral angles of A/B = 1.62 (3) and D/E = 3.58 (4) °. Ring C is oriented with respect to the planar naphthalene groups at dihedral angles of 10.09 (4) and 6.04 (4) °, respectively, while the two naphthalene groups are oriented at a dihedral angle of 4.32 (3)°.

In the crystal, intermolecular weak C—H···O hydrogen bonds link the molecules into centrosymmetric dimers (Table 1 and Fig. 2). The π–π contacts between the oxazol and naphthalene rings and between the naphthalene groups Cg3—Cg4ⁱ and Cg1—Cg5ⁱ [symmetry code: (i) x, y - 1, z, where Cg1, Cg3, Cg4 and Cg5 are centroids of the rings A (C1—C3/C8—C10), C (O1/N1/C12—C14), D (C15—C19/C24) and E (C19—C24), respectively, may further stabilize the structure, with centroid-centroid distances of 3.5947 (9) and 3.7981 (9) Å, respectively. There also exist three weak C-H···π interactions (Table 1).

Experimental

For the preparation of the title compound, (I), α-naphtaldehyde (0.74 g, 5 mmol), naphthalen-1-yl glycine (1.14 g, 5 mmol), acetic anhydride (2.49 ml, 12 mmol) and sodium acetate (0.41 g, 5 mmol) were heated until the mixture just liquefied, and then heating was continued for a further 2 h at 353 K. After completion of the reaction, ethanol (25 ml) was added and the mixture was kept at room temperature for 18 h. The solid product obtained was purified by washing with cold ethanol, hot water and a small amount of hexane, respectively. It was crystallized from hot ethanol (yield; 0.22 g, 30%, m.p. 453 K).