(E)-1-Phenyl­ethanone semicarbazone

Hoong-Kun Fun; Chin Sing Yeap; Mahesh Padaki; Shridhar Malladi; Arun M Isloor

doi:10.1107/S1600536809025847

. 2009 Jul 11;65(Pt 8):o1807–o1808. doi: 10.1107/S1600536809025847

(E)-1-Phenylethanone semicarbazone

Hoong-Kun Fun ^a,^*,^‡, Chin Sing Yeap ^a,^§, Mahesh Padaki ^b, Shridhar Malladi ^b, Arun M Isloor ^b

PMCID: PMC2977181 PMID: 21583511

Abstract

In the title compound, C₉H₁₁N₃O, the benzene ring is disordered over two positions with refined occupancies of 0.922 (5) and 0.078 (5). The program PLATON [Spek (2009 ▶). Acta Cryst. D65, 148–155] recommends the solution in the space group C2/m with a = 7.3050 (3), b = 6.6745 (2), c = 18.3853 (6) Å and β = 96.986 (2)°. However, the large number of non-extinct reflections needed to be ignored if C2/m is chosen suggested that the space group is incorrect, even though the R values are lower than that for P2₁/c. The semicarbazone group is essentially planar, with a maximum deviation of 0.046 (1) Å for one of the N atoms. The mean plane of the semicarbazone group forms dihedral angles of 33.61 (8) and 39.1 (9)° with the benzene ring of the major and minor components, respectively. In the crystal structure, molecules are linked by intermolecular N—H⋯O hydrogen bonds into extended chains along the c axis. The crystal structure is further stabilized by weak intermolucular C—H⋯π interactions.

Related literature

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

Experimental

Crystal data

C₉H₁₁N₃O
M _r = 177.21
Monoclinic,
a = 18.3853 (6) Å
b = 6.6745 (2) Å
c = 7.3050 (3) Å
β = 96.986 (2)°
V = 889.76 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.32 × 0.13 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.881, T _max = 0.997
9294 measured reflections
2034 independent reflections
1449 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.181
S = 1.08
2034 reflections
148 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 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/S1600536809025847/lh2857sup1.cif

e-65-o1807-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025847/lh2857Isup2.hkl

e-65-o1807-Isup2.hkl^{(100.1KB, 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	0.88 (3)	2.02 (3)	2.901 (3)	177.2 (19)
N3—H2N3⋯O1ⁱⁱ	0.86 (3)	2.04 (3)	2.894 (3)	173 (3)
C2A—H2AA⋯Cgⁱⁱⁱ	0.93	2.93	3.707 (2)	142
C5A—H5AA⋯Cg^iv	0.93	2.90	3.678 (2)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg is the centroid of the C1A,C2A,C3,C4A,C5A,C6 benzene ring.

Acknowledgments

HKF thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. CSY thanks the Malaysian Government and Universiti Sains Malaysia for the award of the post of Research Officer under the Science Fund grant No. 305/PFIZIK/613312. 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. Semicarbazone find immense 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). We hereby report the crystal structure of a semicarbazone of potential commercial importance, (I).

The bond lengths and angles of the title compound (I), (Fig. 1) are comparable to related structures (Fun et al., 2009a, b, c). A maximum deviation of -0.046 (1) Å for atom N2 from atoms O1, N1, N2, N3, C6, C7, C8 and C9 indicates that the semicarbazone group is essentially coplanar. This mean plane makes dihedral angle of 33.61 (8) and 39.1 (9)° with benzene ring of the major and minor component (C1A-C2A-C3-C4A-C5A-C6 and C1B-C2B-C3-C4B-C5B-C6), respectively. The molecules are linked together into infinite one-dimensional chains by the intermolecular N2—H1N2···O1ⁱ and N3—H2N3···O1ⁱⁱ (see Table 1 for symmetry codes) hydrogen bonds along the c axis (Fig. 2) and these hydrogen bonds generate R₂²(8) ring motifs (Bernstein et al., 1995). The crystal structure is stabilized by the weak intermolucular C—H···π interactions (Table 1).

Experimental

Semicarbazide hydrochloride (1.0 g, 8.9 mmol) and freshly recrystallized sodium acetate (0.9 g, 10.9 mmol) were dissolved in water (10 ml) following a literature procedure (Furniss et al., 1978). The reaction mixture was stirred at room temperature for 10 minutes. To this, (1.0 g, 8.32 mmol) acetophenone 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: 1.37 g (93%). M.p. 473-478 K.