Crystal structure of (4Z)-4-[(di­methyl­amino)­methyl­idene]-3,5-dioxo-2-phenyl­pyrazolidine-1-carbaldehyde

Joel T Mague; Shaaban K Mohamed; Mehmet Akkurt; Eman A Ahmed; Ahmed Khodairy

doi:10.1107/S2056989015010038

. 2015 Jun 3;71(Pt 7):o440–o441. doi: 10.1107/S2056989015010038

Crystal structure of (4Z)-4-[(dimethylamino)methylidene]-3,5-dioxo-2-phenylpyrazolidine-1-carbaldehyde

Joel T Mague ^a, Shaaban K Mohamed ^b,^c, Mehmet Akkurt ^d, Eman A Ahmed ^e,^*, Ahmed Khodairy ^e

PMCID: PMC4518909 PMID: 26279896

Abstract

In the title compound, C₁₃H₁₃N₃O₃, the pyrazolidine ring adopts a shallow envelope conformation, with the carbonyl C atom closest to the benzene ring as the flap [deviation of 0.126 (1) Å from the plane through the remaining atoms (r.m.s. deviation = 0.011 Å)]. The dihedral angle between the pyrazolidine ring (all atoms) and the benzene ring is 51.09 (4)°. An extremely short (2.08 Å) intramolecular C—H⋯O contact is seen. In the crystal, molecules are linked by C—H⋯O bonds, generating [010] chains. Extremely weak C—H⋯π interactions are also observed.

Keywords: crystal structure, pyrazolones, short intramolecular C—H⋯O contact, C—H⋯O hydrogen bonds, C—H⋯π interactions

Related literature

For biological studies of azole compounds, see: Patel et al. (2012 ▸); Vijesh et al. (2011 ▸). For various medicinal and industrial applications of pyrrazole-containing compounds, see: Jin et al. (2011 ▸); Zhang et al. (2010 ▸); El-Sabbagh et al. (2009 ▸); Dekhane et al. (2011 ▸); Rostom et al. (2003 ▸); Zhou et al. (2010 ▸); Finkelstein & Strock (1997 ▸). graphic file with name e-71-0o440-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₃N₃O₃
M _r = 259.26
Monoclinic,
a = 26.4235 (9) Å
b = 6.1033 (2) Å
c = 16.8611 (6) Å
β = 113.272 (1)°
V = 2497.96 (15) Å³
Z = 8
Cu Kα radiation
μ = 0.84 mm⁻¹
T = 150 K
0.24 × 0.15 × 0.05 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009 ▸) T _min = 0.82, T _max = 0.96
26486 measured reflections
4565 independent reflections
3979 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.104
S = 1.04
4565 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015010038/hb7425sup1.cif

e-71-0o440-sup1.cif^{(211.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015010038/hb7425Isup2.hkl

e-71-0o440-Isup2.hkl^{(250.5KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015010038/hb7425Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015010038/hb7425fig1.tif

The title molecule with 50% probability ellipsoids.

Click here for additional data file.^{(1.2MB, tif)}

b . DOI: 10.1107/S2056989015010038/hb7425fig2.tif

Packing viewed down the b axis. C—H⋯π interactions are shown by dotted lines.

CCDC reference: 1402532

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 is the centroid of the C1/C2/C3/N1/N2 ring.

DHA	DH	HA	D A	DHA
C6H6AO2	0.98	2.08	3.016(2)	160
C5H5CO3ⁱ	0.98	2.52	3.1803(19)	124
C7H7O2ⁱⁱ	0.95	2.29	3.0663(16)	139
C5H5B Cg1ⁱⁱⁱ	0.98	2.98	3.8823(18)	153

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

Acknowledgments

The support of NSF–MRI grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

supplementary crystallographic information

S1. Comment

Azole compounds are extensively studied and widely used as anti-microbial agents (Patel et al., 2012; Vijesh et al., 2011). Recently, urea derivatives of pyrazole have been reported as potent inhibitors of p38 kinase (Jin et al., 2011). Many of other pyrazole scaffold compounds are reported to have broad spectra of biological activities, such as anti-fungal (Zhang et al., 2010), anti-viral (El-Sabbagh et al., 2009), anti-inflammatory (Dekhane et al., 2011), anti-tumor, anti-HCV (Rostom et al., 2003), herbicidal (Zhou et al., 2010) and insecticidal activities (Finkelstein & Strock, 1997). In view of such findings and as a continuation of our study on the synthesis of potential bio-active heterocyclic molecules, we report here the synthesis and crystal structure of the title compound.

In the title compound, the pyrazolidine ring is slightly twisted with an r.m.s. deviation from the mean plane of the 5 atoms forming the ring of 0.036 Å. The dihedral angle between this plane and that of the phenyl ring is 51.09 (4)° (Fig. 1).

S2. Experimental

To phosphorous oxychloride (0.1 mol, 10 ml), in a conical flask with a magnetic stirrer, dry dimethylformamide (35 ml) was added drop-wise with stirring at 303–308 K for 30 min. Then a solution of 1-phenylpyrazolidine-3,5-dione (0.05 mol, 8.8 g) in dimethylformamide (15 ml), was added drop-wise with continuous stirring while ensuring that the temperature did not exceed 318 K. The reaction mixture was stirred overnight and poured onto crushed ice. The solid product was collected by filtration and recrystallized from ethanol to give colourless crystals in 75% yield (m. p. 453–455 K).