Zwitterionic 6-methyl-2-oxo-3-[1-(ureido­iminio)eth­yl]-2H-pyran-4-olate monohydrate

Amel Djedouani; Sihem Boufas; Magali Allain; Gilles Bouet; Mustayeen Khan

doi:10.1107/S1600536808026032

. 2008 Aug 20;64(Pt 9):o1785. doi: 10.1107/S1600536808026032

Zwitterionic 6-methyl-2-oxo-3-[1-(ureidoiminio)ethyl]-2H-pyran-4-olate monohydrate

Amel Djedouani ^a, Sihem Boufas ^b,^*, Magali Allain ^c, Gilles Bouet ^d, Mustayeen Khan ^d

PMCID: PMC2960563 PMID: 21201765

Abstract

The title compound, C₉H₁₁N₃O₄·H₂O, was prepared by the reaction of dehydroacetic acid and semicarbazide hydrochloride. It crystallizes in a zwitterionic form with cationic iminium and anionic enolate groups. In the crystal structure, the almost planar molecules are held together by N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds, some of them involving the water molecules.

Related literature

For related literature, see: Tai et al. (2007 ▶); Zu-Pei Liang et al. (2007 ▶); Wojciechowski et al. (2003 ▶); Petek et al. (2006 ▶); Huang et al. (2006 ▶); Bernstein et al. (1995 ▶); Girija & Begum (2004a ▶); Girija et al. (2004b ▶); Gowda et al. (2007 ▶)..

Experimental

Crystal data

C₉H₁₁N₃O₄·H₂O
M _r = 243.22
Monoclinic,
a = 7.1731 (4) Å
b = 12.6590 (10) Å
c = 12.3698 (3) Å
β = 104.603 (6)°
V = 1086.95 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 173 (2) K
0.35 × 0.05 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
11787 measured reflections
2485 independent reflections
1699 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.121
S = 1.03
2485 reflections
178 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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 Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026032/wk2091sup1.cif

e-64-o1785-sup1.cif^{(14.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808026032/wk2091Isup2.hkl

e-64-o1785-Isup2.hkl^{(119.6KB, 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
N1—H1A⋯O3ⁱ	0.84 (2)	2.18 (2)	3.015 (2)	176.3 (17)
N1—H1B⋯O1Wⁱⁱ	0.87 (2)	2.30 (2)	3.075 (2)	147.9 (19)
N2—H2⋯O1Wⁱⁱ	0.91 (2)	1.98 (2)	2.839 (2)	158 (2)
N3—H3⋯O3	0.98 (2)	1.60 (3)	2.476 (2)	147 (2)
O1W—H11W⋯O4	0.82 (3)	1.99 (3)	2.796 (2)	171 (3)
O1W—H21W⋯O1ⁱⁱⁱ	0.82 (3)	2.00 (3)	2.823 (2)	178.0 (18)
C3—H3B⋯O1	0.96	2.29	2.812 (3)	114
C7—H7⋯O4^iv	0.93	2.49	3.294 (2)	145

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

Acknowledgments

This work was supported by Université Farhet Abbes de Sétif, Sétif, Algeria.

supplementary crystallographic information

Comment

NLO materials play an important role in the field of fibre optic communications and optical signal processing. In the last two decades, extensive research has shown that organic crystals can exhibit nonlinear optical efficiencies which are two orders of magnitude higher than those of inorganic materials. Semicarbazones of substituted benzaldehydes and acetophenones were reported to be some of the potential organic NLO materials.

In this paper, the structure of the title compound (I), C₉H₁₃N₃O₅ is reported. The asymmetric unit of (I) contains one Dehydroacetic acid semicarbazide molecule and one water molecule (Fig. 1).

It is seen that the structure reported here adopts a zwitterion form, because, among other reasons, its N⁺—H bond distances [0.98 (3) Å] is comparable with those from similar zwitterions in the literature [1.11 (3) Å; 1.10 (3) Å] (Petek et al., 2006; Wojciechowski et al., 2003).

The bond distances shown in Table 1 indicate that the C2—N3 iminium bond length of 1.303 (2) Å agree with similar bond in related compounds (Girija & Begum, 2004a; Girija et al., 2004b). This distance is slightly longer than a typical C=N bond (1.269 Å); but much shorter than the single carbon-nitrogen (1.409 Å) (Gowda et al. 2007), because of the resonance.

The C8—O3 bond length [1.282 (2) Å] is intermediate between single and double carbon to oxygen bond lengths (1.362 Å, 1.222 Å) the carbon-carbon bond connecting the enol and imine groups exhibit intermediate distances between a single and a double bond, being closer to latter one. C4—C8 = 1.423 (2) Å, C2—C4 = 1.452 (2) Å, indicate the zwitterionic character of the title compound (Wojciechowski et al. 2003). The molecular configuration is determined by the presence of the intramolecular hydrogen bond O^-···H—N⁺ (Table 2).

The main molecule in (I) is essentially planar, with a maximum deviation from the mean plane for the non-hydrogen atoms of 0.022 (2) Å. The iminium atom H3, participates in a strong intramolecular hydrogen bond with the enolate atom, O1 (Table 1), which generates an S(6) ring motif (Bernstein et al. 1995). Similar intramolecular hydrogen bonds were reported in the above-mentioned zwitterionic phenolates (Huang et al. 2006). This six-membered pseudocycle is almost planar, the maximum deviation from the mean plane being 0.012 Å for atom C2. The bond lengths and angles are in usual ranges (E)-1-(4-Hydroxybenzylidene) semicarbazide hemihydrate (Tai et al., 2007) and (E)-1-(4-Methoxybenzylidene) -semicarbazide (Liang et al., 2007).

The crystal structure of (I) is stabilized by N—H···O; O—H···O, and C—H···O hydrogen bonds (Fig. 2 and Table 2).

Experimental

A mixture of dehydroacetic acid (0.01 mol) and semicarbazide hydrochloride (0.01 mol), in ethanol (20 ml) was refluxed for 1 h. After cooling, filtration and drying, the compound dehydroacetic acid semicarbazide was obtained. A small quantity of this compound (10 mg) was dissolved in aqueous ethanol (95 / 12 ml), and the solution was then allowed to evaporate at room temperature. Prismatic yellow single crystals of the title compound were formed after 8 days.