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

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

doi:10.1107/S1600536812006642

. 2012 Feb 24;68(Pt 3):o830–o831. doi: 10.1107/S1600536812006642

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

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

PMCID: PMC3297890 PMID: 22412693

Abstract

In the title compound, C₁₇H₁₈N₄OS, a pyrazoline derivative, the pyrazoline ring adopts an envelope conformation with the C atom bonded to the benzene ring as the flap atom. The dihedral angle between the pyridine and benzene rings is 80.50 (6)°. The ethoxyphenyl group is approximately planar, with an r.m.s. deviation of 0.0238 (1) Å for the nine non-H atoms. In the crystal, molecules are linked by N—H⋯O and N—H⋯S hydrogen bonds into a tape along the b axis. Weak C—H⋯N and C—H⋯π interactions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related literature on ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2012 ▶); Nonthason et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008 ▶); Gong et al. (2011 ▶); Husain et al. (2008 ▶); Manna & Agrawal (2009 ▶); Özdemir et al. (2007 ▶); Sarkar et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₇H₁₈N₄OS
M _r = 326.42
Monoclinic,
a = 13.4622 (1) Å
b = 9.4175 (1) Å
c = 13.3002 (2) Å
β = 103.146 (1)°
V = 1642.01 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.34 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.934, T _max = 0.960
23465 measured reflections
4784 independent reflections
3970 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.097
S = 1.03
4784 reflections
217 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536812006642/is5069sup1.cif

e-68-0o830-sup1.cif^{(26.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006642/is5069Isup2.hkl

e-68-0o830-Isup2.hkl^{(234.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812006642/is5069Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C1–C5/N3 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯S1ⁱ	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4⋯O1ⁱⁱ	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A⋯N3ⁱⁱⁱ	0.95	2.51	3.4053 (18)	156
C2—H2A⋯Cg2ⁱⁱⁱ	0.95	2.67	3.4401 (14)	138
C7—H7A⋯Cg1^iv	0.99	2.69	3.4841 (13)	138

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

Acknowledgments

The authors thank the Prince of Songkla Univeristy for financial support through the Crystal Materials Research Unit and the Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. PN thanks the Development and Promotion of Science and Technology Talents Project for a fellowship.

supplementary crystallographic information

Comment

Pyrazoline derivatives are of interest in many fields, such as in medicinal chemistry due to their various bioactivities i.e. antidepressant and anticonvulsant (Özdemir et al., 2007), antimicrobial (Manna & Agrawal, 2009), antiamoebic (Husain et al., 2008), analgesic and anti-inflammatory (Amir et al., 2008) properties, as well as being used as fluorescent sensors (Gong et al., 2011) and fluorescent probes (Sarkar et al., 2010). The title pyrazoline derivative (I) was synthesized because we want to modify the structure of heteroaryl chalcone derivative in order to enhance its fluorescence property, by cyclization with thiosemicarbazide. (I) possess fluorescent property as expected which will be reported elsewhere with its closely related compound (Nonthason et al., 2011).

In the molecule of the title pyrazoline derivative (Fig. 1), C₁₇H₁₈N₄OS, the pyrazoline ring adopts envelope conformation with the puckered C8 atom having the maximum deviation of 0.1408 (13) Å, and the puckering parameter Q = 0.2236 (13) Å and φ = 77.6 (3)° (Cremer & Pople, 1975). The dihedral angle between the pyridine and benzene ring is 80.50 (6)°. The conformation of the carbothioamide unit with respect to the pyrazoline ring can be indicated by the torsion angles N1–N2–C15–N4 = 1.90 (17)° and N1–N2–C15–S1 = -177.84 (8)°. The ethoxy group is co-planar with its attached benzene ring with the torsion angle C16–O1–C12–C11 = -0.39 (17)° and C12–O1–C16–C17 = 177.61 (11)°, and an r.m.s. deviation of 0.0238 (1) Å for the nine non H atoms (C9–C14/O1/C16/C17). Bond distances of (I) are in normal range (Allen et al., 1987) and comparable with the related structures (Fun et al., 2012; Nonthason et al., 2011)

In the crystal packing (Fig. 2), the molecules are linked by N—H···O, and N—H···S hydrogen bonds into a tape along the b axis. Weak C—H···N and C—H···π interactions are also present (Table 1).

Experimental

The title compound was synthesized by cyclization reaction of E-3-(4-ethoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one (0.25 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 5 h. The pale-yellow solid of the title compound obtained after cooling of 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 ethanol by slow evaporation of the solvent at room temperature after several days (m.p. 480–481 K).