(Z)-1-(2,5-Dichloro-3-thien­yl)ethanone semicarbazone

Hoong-Kun Fun; Ching Kheng Quah; A M Vijesh; Chitrakar Hegde; Arun M Isloor

doi:10.1107/S1600536809026567

. 2009 Jul 15;65(Pt 8):o1852–o1853. doi: 10.1107/S1600536809026567

(Z)-1-(2,5-Dichloro-3-thienyl)ethanone semicarbazone

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, A M Vijesh ^b,^¶, Chitrakar Hegde ^c, Arun M Isloor ^d

PMCID: PMC2977384 PMID: 21583552

Abstract

The title molecule, C₇H₇Cl₂N₃OS, is approximately planar [maximum deviation = 0.062 (1) Å]. Short intermolecular distances between the centroids of the five-membered rings [3.5340 (8) Å] indicate the existence of π–π interactions. An interesting feature of the crystal structure is the presence of short intramolecular Cl⋯N interactions [3.0015 (11) Å]. Molecules are linked via pairs of intermolecular N—H⋯O hydrogen bonds, generating R ₂ ²(8) ring motifs. Furthermore, N—H⋯O hydrogen bonds form R ₂ ¹(7) ring motifs with C—H⋯O contacts, further consolidating the crystal structure. In the crystal, molecules are linked by these intermolecular interactions, forming chains along [001].

Related literature

For the synthetic utility and applications of semicarbazone derivatives, see: Warren et al. (1977 ▶); Chandra & Gupta (2005 ▶); Jain et al. (2002 ▶); Pilgram (1978 ▶); Yogeeswari et al. (2004 ▶). For related structures, see: Fun et al. (2009a ▶,b ▶). For the preparation, see: Furniss et al. (1978 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₇H₇Cl₂N₃OS
M _r = 252.12
Monoclinic,
a = 13.0796 (2) Å
b = 10.4316 (2) Å
c = 14.4352 (2) Å
β = 94.599 (1)°
V = 1963.21 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 100 K
0.49 × 0.22 × 0.08 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.683, T _max = 0.934
16375 measured reflections
3742 independent reflections
3060 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.100
S = 1.13
3742 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.35 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 datablocks global, I. DOI: 10.1107/S1600536809026567/tk2498sup1.cif

e-65-o1852-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026567/tk2498Isup2.hkl

e-65-o1852-Isup2.hkl^{(183.6KB, hkl)}

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

Table 1. Selected interatomic distance (Å).

Cg1⋯Cg1ⁱ

3.7188 (6)

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the S1/C3–C6 five-membered ring.

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1ⁱⁱ	0.86 (2)	2.02 (2)	2.8766 (15)	177.3 (19)
N2—H1N2⋯O1ⁱⁱⁱ	0.863 (19)	2.035 (19)	2.8949 (14)	174.2 (17)
C7—H7A⋯O1ⁱⁱⁱ	0.96	2.38	3.3370 (17)	176

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (No. 1001/PFIZIK/811012). CKQ thanks USM for a Research Fellowship. AMI is grateful to the Head of the Department of Chemistry and the Director, NITK, Surathkal, India, for providing research facilities.

supplementary crystallographic information

Comment

Semicarbazones find immense applications in the field of synthetic chemistry, such as medicinal chemistry (Warren et al., 1977), organometallics (Chandra & Gupta, 2005), polymers (Jain et al., 2002) and herbicides (Pilgram, 1978). Futher, 4-sulphamoylphenyl semicarbazones were found to possess anti-convulsant activity (Yogeeswari et al., 2004). Herein, we report the crystal structure of the title semicarbazone (I).

The bond lengths and angles in (I), Fig. 1, are comparable to those observed in two closely related structures (Fun et al., 2009a, b). The molecule is approximately planar, with an r.m.s. deviation of 0.062 (1) Å for atom O1. The short intramolecular distances between the centroids of five-membered rings [3.5340 (8) Å] prove existence of π–π interactions (Table 1). The interesting feature of the crystal structure is the short intermolecular Cl···N interactions [3.0015 (11) Å]".

The molecules are linked via pairs of intermolecular N1—H1N1···O1 and N2—H1N2···O1 (Table 2) hydrogen bonds to generate R₂²(8) ring motifs (Bernstein et al., 1995) (Fig. 2). Furthermore, N2—H1N2···O1 hydrogen bonds form R₂¹(7) ring motifs with C7—H7A···O1 contacts to further consolidate the crystal structure. The molecules are linked by these intermolecular interactions to form 1-D chains along the [0 0 1] direction.

Experimental

Semicarbazide hydrochloride (1.84 g, 16.5 mmol) and freshly recrystallized sodium acetate (1.64 g, 20.0 mmol) was dissolved in water (15 ml) according to a literature procedure (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, 2,5-dichloro-3-acetylthiophene (3.0 g, 15.4 mmol) in ethanol (15 ml) was added and stirred well for 6 h. The separated semicarbazone was filtered, washed with chilled water and recrystallized from an ethanol/dimethylformamide mixture. Yield: 3.19 g, 82.22%. M.p. 491–493 K.