5-Amino-3-anilino-1H-pyrazole-4-carbonitrile

Shaaban K Mohamed; Mehmet Akkurt; Frank R Fronczek; Mahmoud A A El-Remaily; Antar A Abdelhamid

doi:10.1107/S1600536812036045

. 2012 Aug 25;68(Pt 9):o2784. doi: 10.1107/S1600536812036045

5-Amino-3-anilino-1H-pyrazole-4-carbonitrile

Shaaban K Mohamed ^a, Mehmet Akkurt ^b,^*, Frank R Fronczek ^c, Mahmoud A A El-Remaily ^d, Antar A Abdelhamid ^a

PMCID: PMC3435815 PMID: 22969661

Abstract

In the title compound, C₁₀H₉N₅, the phenyl ring is twisted with respect to the pyrazole ring, forming a dihedral angle of 24.00 (6)°. In the crystal, molecules are linked by N—H⋯N hydrogen bonds into chains running parallel to [010] containing alternating R ₂ ²(6) and R ₂ ²(12) rings. Further interactions are found in the crystal, viz. N—H⋯π(phenyl) interactions and weak face-to-face π–π stacking interactions [centroid–centroid distance = 3.8890 (6) Å] between the centroids of the pyrazole and phenyl rings are observed.

Related literature

For biological activities of pyrazoles, see: Kaushik et al. (2010 ▶); Sheikh et al. (2009 ▶); Krishnamurthy et al. (2004 ▶); Grimmett (1970 ▶). For the use of related compounds as bridging ligands, see: Lynch & McClenaghan (2005 ▶). For the synthesis of the title compound, see: Soliman et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₀H₉N₅
M _r = 199.22
Orthorhombic,
a = 6.3441 (1) Å
b = 11.1354 (2) Å
c = 13.7754 (3) Å
V = 973.15 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 90 K
0.25 × 0.17 × 0.08 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.978, T _max = 0.993
32878 measured reflections
2975 independent reflections
2767 reflections with I > 2σ(I)
R _int = 0.035
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.086
S = 1.09
2975 reflections
152 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036045/tk5143sup1.cif

e-68-o2784-sup1.cif^{(19.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036045/tk5143Isup2.hkl

e-68-o2784-Isup2.hkl^{(146KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036045/tk5143Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg2 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N5ⁱ	0.84 (2)	2.15 (2)	2.9934 (13)	179 (2)
N3—H3N⋯N2ⁱⁱ	0.87 (2)	2.09 (2)	2.8947 (13)	154 (2)
N4—H12⋯Cg2ⁱⁱⁱ	0.85 (2)	2.51 (2)	3.2011 (12)	140 (2)

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

Acknowledgments

We thank Sohag University for financial support of this project. Manchester Metropolitan University, Erciyes University and Louisiana State University are gratefully acknowledged for supporting this study.

supplementary crystallographic information

Comment

The interest in pyrazole compounds stems from their pharmaceutical and agricultural applications such as drugs, dyes and anaesthetics (Grimmett, 1970; Sheikh et al., 2009; Kaushik et al., 2010; Krishnamurthy et al., 2004). In addition, such pyrazoles and related compounds are common molecules used in coordination or organometallic chemistry as bridging ligands, utilizing the ring positions of the two N atoms (Lynch & McClenaghan, 2005). We report herein the crystal structure of the title compound which was synthesized by our team as a precursor having two functional substituents (amino and nitrile groups) for the purposes of synthesis of multi-fused pyrazolo-heterocyclic compounds such as nitrogen bridgehead derivatives having potential biological activities (Soliman et al., 2010).

In the molecule of the title compound, (Fig. 1), the phenyl and 1H-pyrazole ring makes a dihedral angle of 24.00 (6)° with each other.

The crystal structure is stabilized by N—H···N hydrogen bonds (Table 1, Fig. 2) which link the molecules into chains running parallel to [010] with alternating R₂²(6) and R₂²(12) motifs (Bernstein et al., 1995). In addition, the crystal structure exhibits N—H···π(phenyl) interactions, Table 1, and weak face-to-face π—π stacking interactions [Cg1···Cg2 (1 + x, y, z) = 3.8890 (6) Å; where Cg1 and Cg2 are the centroid of the (N2/N3/C7–C9) 1H-pyrazole and (C1–C6) phenyl rings].

Experimental

The title compound was prepared according to the literature procedure (Soliman et al., 2010). Crystals were obtained from an ethanol solution of (I) by slow evaporation (M.pt: 481 K).