5-(4-Meth­oxy­phen­yl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothio­amide

Phonpawee Nonthason; Thitipone Suwunwong; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536811050033

. 2011 Nov 30;67(Pt 12):o3501–o3502. doi: 10.1107/S1600536811050033

5-(4-Methoxyphenyl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide

Phonpawee Nonthason ^a, Thitipone Suwunwong ^a, Suchada Chantrapromma ^a,^*,^‡, Hoong-Kun Fun ^b,^§

PMCID: PMC3239124 PMID: 22199972

Abstract

In the title compound, C₁₆H₁₆N₄OS, the dihedral angle between the pyridine and benzene rings is 81.08 (6)°. The pyrazole ring makes dihedral angles of 12.36 (7) and 87.96 (6)°, respectively, with the pyridine and benzene rings. In the crystal, molecules are linked by N—H⋯O and N—H⋯S hydrogen bonds and a weak C—H⋯S interaction into a layer parallel to the ab plane. Weak C—H⋯π and π–π interactions [centroid–centroid distances = 3.7043 (9) and 3.8120 (7) Å] are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Fun et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008 ▶); Bai et al. (2007 ▶); Gong et al. (2011 ▶); Husain et al. (2008 ▶); Ji & Shi (2006 ▶); Manna & Agrawal (2009 ▶); Shoman et al. (2009 ▶).

Experimental

Crystal data

C₁₆H₁₆N₄OS
M _r = 312.40
Triclinic,
a = 6.2434 (2) Å
b = 9.9348 (4) Å
c = 13.6564 (6) Å
α = 107.762 (1)°
β = 99.506 (1)°
γ = 94.331 (1)°
V = 788.43 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 297 K
0.48 × 0.34 × 0.19 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.906, T _max = 0.961
19134 measured reflections
4529 independent reflections
3927 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.122
S = 1.05
4529 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.18 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 datablock(s) global, I. DOI: 10.1107/S1600536811050033/is5010sup1.cif

e-67-o3501-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050033/is5010Isup2.hkl

e-67-o3501-Isup2.hkl^{(221.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811050033/is5010Isup3.cml

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

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

Cg3 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H2N4⋯O1ⁱ	0.845 (19)	2.278 (19)	3.0238 (18)	147.4 (17)
N4—H1N4⋯S1ⁱⁱ	0.839 (19)	2.603 (19)	3.4090 (13)	161.6 (18)
C14—H14A⋯S1ⁱⁱⁱ	0.93	2.82	3.7033 (14)	158
C1—H1A⋯Cg3^iv	0.93	2.60	3.5005 (15)	162

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

Acknowledgments

PN thanks the Development and Promotion of Science and Technology Talents Project for a fellowship. The authors thank the Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Pyrazoline derivatives which contain two N atoms in their 5-membered heterocyclic structures are ultilised in bioactivity studies for their antimicrobial (Manna & Agrawal, 2009), antiamoebic (Husain et al., 2008), anti-inflammatory (Amir et al., 2008; Shoman et al., 2009) and analgesic (Amir et al., 2008) properties as well as in optical studies involving fluorescence dyes (Ji & Shi, 2006; Bai et al., 2007) and fluorescent sensors (Gong et al., 2011). For our research on the biological properties of pyrazoline derivatives, the title compound (I) was synthesized from the cyclization reaction of the heteroaryl chalcone derivative and thiosemicarbazide. Crystals of (I) were grown in order to study the structural and activity relationship with another pyrazoline derivative (Fun et al., 2011).

In the title molecule (Fig. 1), C₁₆H₁₆N₄OS, the dihedral angle between the pyridine and benzene ring is 81.08 (6)°, whereas the pyrazole ring makes dihedral angles of 12.36 (7) and 81.08 (6)° with the pyridine and benzene rings, respectively. The carbothioamide unit lies on the same plane with pyrazole ring with an r.m.s. of 0.0468 (1) Å for the eight non H atoms (C6, C7, C8, C15, N1, N2, N4 and S1). The methoxy group is co-planar with its attached benzene ring with a torsion angle C16–O1–C12–C13 = -0.5 (2)° and an r.m.s. of 0.0102 (1) Å for the eight non H atoms. Bond distances of (I) are in normal range (Allen et al., 1987).

In the crystal packing (Fig. 2), the molecules are linked by N—H···O, and N—H···S hydrogen bonds as well as with weak C—H···S interactions (Table 1) into a layer parallel to the ab plane. π–π interactions with the distances of Cg1···Cg2 (-1 + x, y, z) = 3.8120 (7) Å and Cg2···Cg2 (3 - x, -y, 1 - z) = 3.7043 (9) Å are also present. Cg1 and Cg2 are the centroids of N1/N2/C8/C7/C6 and N3/C1–C5 rings, respectively.

Experimental

The title compound was synthesized by the cyclization reaction of E-3-(4-methoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (0.24 g, 1 mmol) with excess thiosemicarbazide (0.18 g, 2 mmol) in a solution of KOH (0.11 g, 2 mmol) in ethanol (10 ml). The reaction mixture was vigorously stirred and refluxed for 3 h. The pale-yellow solid of the title compound obtained after cooling off the reaction was then filtered off under vacuum. Pale yellow block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystallized from methanol/ethanol (1:2 v/v) by slow evaporation of the solvent at room temperature after several days (m.p. 468–469 K).