Methyl 2-[(E)-(4-nitro­phen­yl)hydrazono]-3-oxobutyrate

Yong-Hong Liu; Gui-You Sun; Jian-Feng Liu; Jun Ye; Xiao-Lan Liu

doi:10.1107/S160053680802312X

. 2008 Jul 26;64(Pt 8):o1608. doi: 10.1107/S160053680802312X

Methyl 2-[(E)-(4-nitrophenyl)hydrazono]-3-oxobutyrate

Yong-Hong Liu ^a,^*, Gui-You Sun ^a, Jian-Feng Liu ^b, Jun Ye ^a, Xiao-Lan Liu ^a

PMCID: PMC2962099 PMID: 21203301

Abstract

The molecule of the title compound, C₁₁H₁₁N₃O₅, exists as the E isomer as it is stabilized by an intramolecular hydrogen bond. Except for the methyl H atoms, all atoms lie in special positions on a mirror plane and form a large conjugated system; the methyl H atoms are disordered about the mirror plane. In the crystalline state, bifurcated intra- and intermolecular N—H⋯O hydrogen bonds and four intermolecular C—H⋯O hydrogen bonds link the molecules into large perfectly planar sheets. Along the c axis, the N—N bond center approaches the phenyl-ring centroids of its neighbouring molecules above and below to give π–π overlap (at a distance of ca 3.57 Å), thus fusing the molecules into a three-dimensional framework.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Lewis et al. (1999 ▶); Liu et al. (2007 ▶, 2008 ▶); Mague et al. (1997 ▶); Mahy et al. (1993 ▶); Serbutoviez et al. (1995 ▶); Thami et al. (1992 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

C₁₁H₁₁N₃O₅
M _r = 265.2
Orthorhombic,
a = 12.880 (3) Å
b = 14.299 (3) Å
c = 6.6328 (14) Å
V = 1221.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 (2) K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.966, T _max = 0.977
10245 measured reflections
1546 independent reflections
968 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.121
S = 1.03
1546 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802312X/cs2083sup1.cif

e-64-o1608-sup1.cif^{(16KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802312X/cs2083Isup2.hkl

e-64-o1608-Isup2.hkl^{(76.3KB, 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
N1—H1⋯O4	0.86	1.98	2.618 (3)	130
C2—H2⋯O3ⁱ	0.93	2.55	3.279 (3)	135
C11—H11B⋯O1ⁱⁱ	0.96	2.57	3.128 (3)	117
N1—H1⋯O2ⁱⁱⁱ	0.86	2.64	3.439 (3)	154
C5—H5⋯O2ⁱⁱⁱ	0.93	2.62	3.467 (4)	153
C4ⁱⁱⁱ—H4ⁱⁱⁱ⋯O4	0.93	2.61	3.518 (3)	167

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

Acknowledgments

The authors thank the Natural Science Foundation of Yangzhou University (grant No. 2006XJJ03) for financial support of this work.

supplementary crystallographic information

Comment

Phenylhydrazone and its derivatives show remarkable stability and high tendency to form non-centrosymmetric crystal packing (Lewis et al., 1999; Mague et al., 1997) and exceptional electronic, bioactive and chemical properties useful for analytic purposes (Mahy et al., 1993), for biological chemistry (Thami et al., 1992) and also for optical materials (Serbutoviez et al., 1995). As a part of our ongoing research (Liu et al., 2007; Liu et al., 2008), the crystal structure of the title compound was solved.

The molecule of the title compound exists in the (E)-isomer configuration, not as the generally more stable (Z)-isomer (Schemes 1 and 2). The (E)-isomer exists here because of the N—H···O intra-molecular hydrogen bond stabilizes it by forming a pseudo-ring S(6) (Bernstein et al., 1995) motif (Fig. 1, Table 1 and 2). The N1—C6 bond distance at 1.397 (3) Å is longer than the expected C═N double bond (1.32 Å) but is shorter than a C—N single bond (1.47 Å) because of the classic sp²-hybrid nitrogen atom, as also found in our earlier work (Liu et al., 2007, 2008). All these effects may help all non-hydrogen atoms to form a perfect plane which coincides with the mirror plane of the space group, less for the hydrogen atoms of the two methyl groups whose six H atoms are disordered over two orientations.

In the crystal packing the molecules are linked into larger perfectly planar sheets via by four C—H···O inter-molecular hydrogen bonds and one N—H···O intra-molecular hydrogen bond running parallel to the [001] plane (Fig. 2, Table 2). H1 atom of the N1 atom is a part of a bifurcated system and makes both intra- and intermolecular H-bridges, with angles around the H1 adding up to 360°. Finally, along the c axis the N1—N2 bond centers of molecules combine its up and down neighbours' phenyl rings into three dimensional framework (Fig. 2). Consecutive bond centers···phenyl ring centers are at a distance of ca. 3.57 Å and an incline at an angle of ca. 137° (Fig. 3).

Experimental

The title compound was synthesized according to literature procedure (Wang et al. 2005; Liu et al. 2008). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in dichloromethane at room temperature over a period of 6 d.