3-(2,3-Dimethyl-5-oxo-1-phenyl-2,5-di­hydro-1H-pyrazol-4-yl)sydnone

Jia Hao Goh; Hoong-Kun Fun; Nithinchandra; B Kalluraya

doi:10.1107/S1600536810015667

. 2010 May 8;66(Pt 6):o1251–o1252. doi: 10.1107/S1600536810015667

3-(2,3-Dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazol-4-yl)sydnone

Jia Hao Goh ^a,^‡, Hoong-Kun Fun ^a,^*,^§, Nithinchandra ^b, B Kalluraya ^b

PMCID: PMC2979459 PMID: 21579356

Abstract

In the title sydnone compound [systematic name: 3-(2,3-dimethyl-5-oxo-1-phenyl-2,5-dihydro-1H-pyrazol-4-yl)-1,2,3-oxadiazol-3-ium-5-olate], C₁₃H₁₂N₄O₃, the oxadiazole and pyrazole rings are essentially planar [maximum deviations = 0.006 (1) and 0.019 (1) Å, respectively] and are inclined at interplanar angles of 37.84 (4) and 46.60 (4)°, respectively, with respect to the benzene ring. In the crystal, adjacent molecules are interconnected into a three-dimensional supramolecular network via intermolecular C—H⋯O hydrogen bonds. Weak intermolecular π–π aromatic stacking interactions [centroid–centroid distance = 3.5251 (5) Å] further stabilize the crystal packing.

Related literature

For general background to and applications of sydnone derivatives, see: Baker et al. (1949 ▶); Hedge et al. (2008 ▶); Rai et al. (2008 ▶). For the preparation of 3-aryl sydnones, see Kalluraya et al. (2004 ▶); Rai et al. (2008 ▶). For related structures, see: Baker & Ollis (1957 ▶); Goh et al. (2009a ▶,b ▶, 2010a ▶,b ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₃H₁₂N₄O₃
M _r = 272.27
Monoclinic,
a = 10.6525 (3) Å
b = 7.3014 (3) Å
c = 15.6828 (4) Å
β = 93.982 (1)°
V = 1216.83 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.56 × 0.17 × 0.08 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.941, T _max = 0.992
44010 measured reflections
6426 independent reflections
4895 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.125
S = 1.04
6426 reflections
229 parameters
All H-atom parameters refined
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536810015667/sj2767sup1.cif

e-66-o1251-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015667/sj2767Isup2.hkl

e-66-o1251-Isup2.hkl^{(314.5KB, 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
C1—H1A⋯O3ⁱ	0.981 (14)	2.492 (13)	3.2155 (10)	130.4 (10)
C11—H11A⋯O2ⁱ	0.944 (13)	2.543 (13)	3.4163 (10)	153.9 (11)
C12—H12B⋯O2ⁱⁱ	0.984 (13)	2.369 (13)	3.3022 (10)	158.1 (11)
C13—H13A⋯O3ⁱⁱⁱ	0.958 (14)	2.516 (15)	3.3606 (10)	147.0 (12)

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Sydnones constitute a well-defined class of mesoionic compounds that contain a 1,2,3-oxadiazole ring system. The introduction of the concept of mesoionic structure for certain heterocyclic compounds in the year 1949 has proved to be fruitful development in heterocyclic chemistry (Baker et al., 1949). The study of sydnones still remains a field of interest because of their electronic structure and also because of the various types of biological activities displayed by some of them. Interest in sydnone derivatives has also been encouraged by the discovery that they exhibit various pharmacological activities (Hedge et al., 2008; Rai et al., 2008).

3-aryl sydnones are prepared by the cyclisation of N-nitroso-N-aryl glycines with acetic anhydride. These N-nitroso-N-aryl glycines were obtained by the nitrosation of N-substituted glycines. The N-substituted glycine was obtained by the hydrolysis of corresponding ester with sodiumhydroxide. The ester is in turn obtained by the reaction of appropriately substituted aniline with ethyl aceto acetate in absolute ethanol medium employing anhydrous sodium acetate as the catalyst (Kalluraya et al., 2004; Rai et al., 2008)

In the title sydnone compound (Fig. 1), the 1,2,3-oxadiazole (N3/N4/O1/C10/C11) and pyrazole (N1/N2/C7-C9) rings are essentially planar, with maximum deviations of 0.006 (1) and -0.019 (1) Å, respectively, at atoms N4 and N1. These two rings are inclined at interplanar angles of 37.84 (4) and 46.60 (4)°, respectively, with the C1-C6 benzene ring. As reported previously (Goh et al., 2010a,b), the exocyclic C10–O3 bond length of 1.2205 (9) Å is inconsistent with the formulation of Baker & Ollis (1957), which involves the delocalization of a positive charge in the 1,2,3-oxadiazole ring, and a negative charge in the exocyclic oxygen. The bond lengths (Allen et al., 1987) and angles are within normal range and comparable to those observed in closely related pyrazole (Goh et al., 2009a,b) and sydnone (Goh et al., 2010a,b) structures.

In the crystal packing, C1—H1A···O3, C13—H13A···O3, C11—H11A···O2 and C12—H12B···O2 hydrogen bonds (Table 1) form two different pairs of intermolecular bifurcated acceptor hydrogen bonds, which link the molecules into a three-dimensional supramolecular network. The crystal packing is further stabilized by weak intermolecular π–π aromatic stacking interactions [Cg1···Cg2ⁱⁱ = 3.5251 (5) Å, (ii) = -x+1, y-1/2, -z+1/2 where Cg1 and Cg2 are centroids of pyrazole and benzene rings, respectively].

Experimental

[(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)(nitroso) amino]acetic acid (0.1 mol) was heated with acetic anhydride (0.5 mol) on a water bath for 2–4 h, the reaction mixture was kept aside at room temperature for overnight. It was then poured into ice cold water, filtered and washed with water, sodium bicarbonate solution (5 %) and again with water. The solid product was dried and crystallized from benzene. Single crystals suitable for X-ray analysis were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.