2-(2-Hy­droxy-3-meth­oxy­phen­yl)-6H-perimidin-6-one

Hoong-Kun Fun; Kullapa Chanawanno; Suchada Chantrapromma

doi:10.1107/S1600536811006465

. 2011 Feb 26;67(Pt 3):o715–o716. doi: 10.1107/S1600536811006465

2-(2-Hydroxy-3-methoxyphenyl)-6H-perimidin-6-one

Hoong-Kun Fun ^a,^*,^‡, Kullapa Chanawanno ^b, Suchada Chantrapromma ^b,^§

PMCID: PMC3051947 PMID: 21522458

Abstract

The molecule of the title perimidine derivative, C₁₈H₁₂N₂O₃, is essentially planar, the dihedral angle between the benzene and perimidine rings being 3.25 (5)°. The hydroxy and methoxy groups lie in the plane of the benzene ring to which they are bound [O—C—C—C = 179.96 (11)° and C—O—C—C = −177.96 (12)°]. An intramolecular O—H⋯N interaction generates an S(6) ring motif. In the crystal, molecules are linked by pairs of C—H⋯O interactions into dimers, which generate S(16) ring motifs. These dimers are arranged into sheets parallel to the ac plane and further stacked down the b axis by π–π interactions, with centroid–centroid distances in the range 3.5066 (8)–3.7241 (7) Å.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For background to perimidines and their applications, see: Claramunt et al. (1995 ▶); del Valle et al. (1997 ▶); Herbert et al. (1987 ▶); Llamas-Saiz et al. (1995 ▶); Pozharskii & Dalnikovskaya (1981 ▶); Varsha et al. (2010 ▶). For related structures, see: Llamas-Saiz et al. (1995 ▶); Varsha et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₈H₁₂N₂O₃
M _r = 304.30
Monoclinic,
a = 25.4718 (17) Å
b = 7.0666 (3) Å
c = 15.0815 (6) Å
β = 94.373 (3)°
V = 2706.8 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.67 × 0.11 × 0.05 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.933, T _max = 0.994
42939 measured reflections
6529 independent reflections
3471 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.210
S = 1.02
6529 reflections
255 parameters
All H-atom parameters refined
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006465/sj5107sup1.cif

e-67-0o715-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006465/sj5107Isup2.hkl

e-67-0o715-Isup2.hkl^{(319.6KB, 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—H1O2⋯N2	0.91 (2)	1.73 (2)	2.5583 (15)	151 (2)
C15—H15⋯O2ⁱ	0.970 (18)	2.437 (18)	3.3686 (17)	160.8 (12)

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Symmetry code: (i) Inline graphic .

Acknowledgments

KC thanks the Crystal Materials Research Unit (CMRU), Prince of Songkla University, for a research assistance fellowship. Generous support by the Prince of Songkla University is gratefully acknowledged. The authors also thank Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Perimidines (peri-naphtho-fused perimidine ring systems) have received wide interests due to their applications in photophysics (del Valle et al., 1997), usage as coloring materials for polyester fibers (Claramunt et al., 1995) and fluorescent materials (Varsha et al., 2010). They are also noted for their biological activity displaying antiulcer, antifungal, antimicrobial and antitumor properties (Claramunt et al., 1995; Herbert et al., 1987; Pozharskii & Dalnikovskaya, 1981). In an attempt to synthesize a Co(II) Schiff base complex by the reaction of o-vanillin, 1,8-diaminonaphthalene and CoCl₂.6H₂O, the unexpected product was the perimidine derivative, (I), reported here, Fig 1.

In the molecule of the title perimidine derivative (I), C₁₈H₁₂N₂O₃, the perimidine ring system (N1–N2/C7–C17) is planar with an r.m.s deviation 0.0126 (11)Å. The whole molecule is essentially planar with the dihedral angle between the perimidine and phenyl rings being 3.25 (5)°. Both the hydroxy and methoxy groups are co-planar with the attached benzene ring with torsion angles O2–C2–C3–C4 = 179.96 (11)° and C18–O3–C3–C2 = -177.96 (12)°. An intramolecular O—H···N interaction generates an S(6) ring motif (Bernstein et al., 1995) and helps to stabilize the planarity of the molecule (Fig. 1). Bond distances are normal (Allen et al., 1987) and are comparable to those found in related structures (Llamas-Saiz et al., 1995; Varsha et al., 2010).

In the crystal structure (Fig. 2), the molecules are linked by two C—H···O interactions (Table 1) into dimers which generate S(16) ring motifs. These dimers are arranged into sheets parallel to the ac plane and further stacked down the b axis by π–π interactions with centroid to centroid distances Cg₁···Cg₂ⁱⁱ= 3.7241 (7) Å; Cg₂···Cg₃ⁱⁱ= 3.5066 (8) Å; Cg₂···Cg₄ⁱⁱ= 3.7055 (8) Å and Cg₂···Cg₄ⁱⁱⁱ= 3.5988 (8) Å (symmetry codes (ii) = 2 - x, 1 - y, 1 - z and (iii) = 2 - x, 2 - y, 2 - z). Cg1, Cg2, Cg3, and Cg4 are the centroids of the N1–N2/C7–C8/C6–C17, C1–C6, C8–C12/C17, and C12–C17 rings, respectively.

Experimental

The title compound was synthesized by adding a solution of 1,8-diaminonaphthalene (0.50 g, 3.16 mmol) in ethanol (20 ml) dropwise to a solution of o-vanillin (0.96 g, 6.32 mmol) in ethanol (10 ml). The reaction mixture was stirred for 0.5 h at room temperature and a pale-orange precipitate was obtained. After filtration, the pale-orange solid was washed with diethyl ether. A solution of the pale-orange solid (0.20 g, 0.47 mmol) in ethanol (20 ml) was slowly added to a solution of CoCl₂.6H₂O (0.11 g, 0.47 mmol) in 10 ml of ethanol followed by triethylamine (0.06 ml, 0.47 mmol). The mixture was refluxed for 3 h. The title compound was obtained as a purple solid and washed with diethyl ether. The purple needle-shaped single crystals of the unexpected perimidine derivative of the title compound suitable for x-ray structure determination were recrystallized from ethanol by slow evaporation of the solvent at room temperature over several days, Mp. 507–508 K.