3-Oxo-N′,2-diphenyl-2,3-di­hydro-1H-pyrazole-4-carbohydrazide

Joel T Mague; Shaaban K Mohamed; Mehmet Akkurt; Eman A Ahmed; Mustafa R Albayati

doi:10.1107/S1600536814012392

. 2014 Jun 25;70(Pt 7):o819–o820. doi: 10.1107/S1600536814012392

3-Oxo-N′,2-diphenyl-2,3-dihydro-1H-pyrazole-4-carbohydrazide

Joel T Mague ^a, Shaaban K Mohamed ^b,^c, Mehmet Akkurt ^d, Eman A Ahmed ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4120620 PMID: 25161596

Abstract

In the title compound, C₁₆H₁₄N₄O₂, the pyrazole ring makes a dihedral angle of 10.49 (8)° with its N-bound phenyl group, while it is nearly perpendicular to the other phenyl ring [dihedral angle = 88.47 (5)°]. The molecular conformation is stabilized by intramolecular C—H⋯O and N—H⋯O hydrogen bonds. In the crystal, the packing involves sheets of molecules parallel to (100) linked by N—H⋯O hydrogen bonds. A C—H⋯O interaction is also observed.

Related literature

For the diverse biological activities of pyrazolone compounds, see: Guckian et al. (2010 ▶); Fan et al. (2006 ▶); Castagnolo et al. (2008 ▶); Idrees et al. (2009 ▶); Abdel-Aziz et al. (2009 ▶); Manojkumar et al. (2009 ▶); Shete et al. (2011 ▶); Sujatha et al. (2009 ▶); El-Hawash et al. (2006 ▶); Kawai et al. (1997 ▶); Wu et al. (2002 ▶6). For industrial applications of pyrazolones, see: Basaif et al. (2007 ▶); Ho (2005 ▶); Kirschke et al. (1984 ▶); Chande et al. (1993 ▶); El-Saraf & El-Sayed (2003 ▶). For graph-set motif notation, see: Bernstein et al. (1995 ▶). graphic file with name e-70-0o819-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₄N₄O₂
M _r = 294.31
Monoclinic,
a = 8.4488 (12) Å
b = 11.5605 (17) Å
c = 14.642 (2) Å
β = 91.565 (2)°
V = 1429.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 150 K
0.26 × 0.20 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T _min = 0.85, T _max = 0.99
25571 measured reflections
3674 independent reflections
2895 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.112
S = 1.03
3674 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814012392/bt6982sup1.cif

e-70-0o819-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012392/bt6982Isup2.hkl

e-70-0o819-Isup2.hkl^{(201.7KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814012392/bt6982Isup3.cml

CCDC reference: 1005600

Additional supporting information: 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⋯O2ⁱ	0.91	2.06	2.9244 (14)	158
N2—H2A⋯O2	0.91	2.14	2.8597 (14)	136
N3—H3A⋯O1ⁱⁱ	0.91	1.75	2.6527 (15)	169
C12—H12⋯O2	0.95	2.28	2.9133 (18)	124
C16—H16⋯O1ⁱⁱ	0.95	2.51	3.2745 (18)	137

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

Acknowledgments

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

supplementary crystallographic information

S1. Comment

Compounds containing a pyrazole core and related analogs have received signicant attention due to their chemical, medicinal, and pharmaceutical applications. Several reports showed the pyrazolone moiety to be one of most active pharmacophores and possesses anti-cancer (Guckian et al., 2010), anti-viral (Fan et al., 2006), anti-tubercular (Castagnolo et al., 2008), anti-hyperlipedaemic (Idrees et al., 2009), anti-depressant, anti-convulsant (Abdel-Aziz et al., 2009), anti-oxidant, anti-bacterial (Manojkumar et al., 2009; Shete et al., 2011), anti-HIV (Sujatha et al., 2009), anti-inflammatory, analgesic and anti-pyretic (El-Hawash et al., 2006) activities. The pyrazolone-like edaravone has been developed as a drug for brain ischemia (Kawai et al., 1997) and has also been reported to be effective for myocardial ischemia (Wu et al., 2002). Additionally, pyrazolones have been reported to be the key starting materials for the synthesis of commercial aryl/heteroaropyrazolone dyes (Basaif et al., 2007; Ho, 2005). Halogenated pyrazolones are also useful synthetic intermediates for synthesis of diazo-dyes (Kirschke et al., 1984), fused (Chande et al., 1993) and spiro-heterocyclic compounds (El-Saraf & El-Sayed 2003). In this context we report the synthesis and crystal structure of the title compound.

The phenyl ring C1–C6 is nearly perpendicular to the 5-membered ring (dihedral angle = 88.47 (5)°) while the latter makes a dihedral angle of 10.49 (8)° with the phenyl ring C11–C16. The rotational orientation of the latter phenyl ring as well as that of the N2—H2a unit are determined by the intramolecular C16—H16···O2 and N2—H2a···O2 hydrogen bonds (Table 1, Fig. 1) forming S(6) ring motifs (Bernstein et al., 1995). The packing involves sheets of molecules parallel to the (100) plane formed by N3—H3a···O1 and pairwise N1—H1a···O2 intermolecular hydrogen bonds (Table 1, Figs. 2 and 3).

S2. Experimental

A mixture of 10 mmol (2.31 g) of 4-[(dimethylamino)methylene]-1-phenylpyrazolidine-3,5-dione and 10 mmol (1.08 g) of phenyl hydrazine in 15 ml dioxane was refluxed for 6 h. After cooling, the resulting solid was collected by filtration and recrystallized from ethanol. Colourless crystals, 84%, m.p. = 483 K.