(E)-1-(4-Chloro­phen­yl)ethanone semi­carbazone

Hoong-Kun Fun; Ching Kheng Quah; Mahesh Padaki; Shridhar Malladi; Arun M Isloor

doi:10.1107/S160053680902279X

. 2009 Jun 20;65(Pt 7):o1634–o1635. doi: 10.1107/S160053680902279X

(E)-1-(4-Chlorophenyl)ethanone semicarbazone

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Mahesh Padaki ^b, Shridhar Malladi ^b, Arun M Isloor ^b

PMCID: PMC2969321 PMID: 21582900

Abstract

In the title compound, C₉H₁₀ClN₃O, the semicarbazone group is approximately planar, with an r.m.s. deviation from the mean plane of 0.054 (1) Å. The dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 30.46 (5)°. In the solid state, molecules are linked via intermolecular N—H⋯O and N—H⋯N hydrogen bonds, generating R ₂ ²(9) ring motifs which, together with R ₂ ²(8) ring motifs formed by pairs of intermolecular N—H⋯O hydrogen bonds, lead to the formation of a seldom-observed molecular trimer. Furthermore, N—H⋯O hydrogen bonds form R ₂ ¹(7) ring motifs with C—H⋯O hydrogen bonds, further consolidating the crystal structure. Molecules are linked by these intermolecular interactions, forming two-dimensional networks parallel to (100).

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 a related structure, see: Fun et al. (2009 ▶). For the preparation, see: Furniss et al. (1978 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₉H₁₀ClN₃O
M _r = 211.65
Monoclinic,
a = 21.8191 (4) Å
b = 7.0484 (1) Å
c = 13.7249 (2) Å
β = 109.633 (1)°
V = 1988.04 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.41 × 0.20 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.867, T _max = 0.991
28636 measured reflections
3539 independent reflections
2912 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.101
S = 1.04
3539 reflections
167 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.27 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/S160053680902279X/sj2631sup1.cif

e-65-o1634-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902279X/sj2631Isup2.hkl

e-65-o1634-Isup2.hkl^{(173.6KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.884 (19)	2.007 (19)	2.8866 (12)	173.3 (19)
N3—H1N3⋯N1ⁱⁱ	0.835 (18)	2.264 (18)	3.0904 (14)	170.5 (16)
N3—H2N3⋯O1ⁱⁱⁱ	0.826 (17)	2.316 (17)	3.0499 (13)	148.4 (15)
C9—H9C⋯O1ⁱ	0.94 (2)	2.55 (2)	3.2162 (16)	128.1 (16)

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia (USM) for the Research University Golden Goose Grant (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

In organic chemistry, a semicarbazone is a derivative of an aldehyde or ketone formed by a condensation between a ketone or aldehyde and semicarbazide. Semicarbazones find numerous applications in the field of synthetic chemistry, such as medicinal chemistry (Warren et al., 1977), organometalics (Chandra & Gupta, 2005), polymers (Jain et al., 2002) and herbicides (Pilgram, 1978). 4-Sulphamoylphenyl semicarbazones were synthesized and were found to possess anticonvulsant activity (Yogeeswari et al., 2004). Herein we report the crystal structure of the title semicarbazone which may have commercial and synthetic importance.

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges, and are comparable to those observed in a closely related structure (Fun et al., 2009). The semicarbazone group (C9/C6/C7/N1/N2/C8/O1/N3) is approximately planar, with an r.m.s. deviation of 0.054 (1) Å for atom N2 while the dihedral angle between the least-squares planes through the semicarbazone group and the benzene ring is 30.46 (5)°.

In the solid state, the molecules are linked via intermolecular N3—H2N3···O1 and N3—H1N3···N1 hydrogen bonds to generate R₂²(9) ring motifs which, together with the R₂²(8) ring motifs formed by pairs of intermolecular N2—H1N2···O1 hydrogen bonds, lead to the formation of a seldom-observed molecular trimer (Fig. 2). Furthermore, N2—H1N2···O1 hydrogen bonds form R₂¹(7) ring motifs (Fig. 2) with C9—H9C···O1 hydrogen bonds to further consolidated the crystal structure. The molecules are linked by these intermolecular interactions to form two-dimensional networks parallel to the (1 0 0) plane.

Experimental

0.780 g (7.0 mmol) of semicarbazide hydrochloride and 0.698 g (8.5 mmol) of crystallized sodium acetate was dissolved in 10 ml of water (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this (1 g, 6.5 mmol) of 4-choloacetophenone was added and shaken well. A little alcohol was added to dissolve the turbidity. It was shaken for 10 more minutes and allowed to stand. The semicarbazone crystallizes on standing for 6 h. The separated crystals were filtered, washed with cold water and recrystallized from alcohol. Yield was found to be 1.1 g, 80.35%. M.p. 478–479 K.