(2E)-2-(2-Phenyl­hydrazin-1-yl­idene)propanoic acid

Md Abu Affan; M A Salam; Eleazar Veronica Siew; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811013717

. 2011 Apr 16;67(Pt 5):o1163. doi: 10.1107/S1600536811013717

(2E)-2-(2-Phenylhydrazin-1-ylidene)propanoic acid

Md Abu Affan ^a,^‡, M A Salam ^a, Eleazar Veronica Siew ^a, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC3089133 PMID: 21754470

Abstract

The 13 non-H atoms comprising the title compound, C₉H₁₀N₂O₂, are close to planar (r.m.s. deviation = 0.140 Å), with maximum deviations of 0.292 (1) and 0.210 (1) Å to either side of the least-squares plane exhibited by the hydroxy and carbonyl O atoms, respectively. The observed conformation is stabilized by an intramolecular O—H⋯N hydrogen bond. The conformation about the N=C double bond [1.2909 (16) Å] is E. The hydroxy OH group also forms an intermolecular hydrogen bond to a carbonyl O atom, and the amine H atom similarly forms an N—H⋯O hydrogen bond to a second carbonyl O atom. The result is the formation of a double layer with a flat topology. Layers stack along the a-axis direction connected by C—H⋯π interactions.

Related literature

For background and recent studies on the biological activity of tin/organotin compounds, see: Gielen & Tiekink (2005 ▶); Affan et al. (2009 ▶).

Experimental

Crystal data

C₉H₁₀N₂O₂
M _r = 178.19
Monoclinic,
a = 7.3239 (3) Å
b = 12.0837 (7) Å
c = 9.6836 (4) Å
β = 99.119 (4)°
V = 846.17 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.734, T _max = 1.000
7879 measured reflections
1920 independent reflections
1544 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.114
S = 1.03
1920 reflections
127 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013717/hg5024sup1.cif

e-67-o1163-sup1.cif^{(15.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013717/hg5024Isup2.hkl

e-67-o1163-Isup2.hkl^{(94.5KB, hkl)}

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

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

Cg1 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.86 (2)	2.12 (2)	2.6169 (16)	115.9 (16)
O1—H1⋯O2ⁱ	0.86 (2)	2.18 (2)	2.9039 (14)	141.5 (19)
N2—H2⋯O2ⁱⁱ	0.916 (18)	2.199 (19)	3.0579 (15)	155.9 (15)
C3—H3c⋯Cg1ⁱⁱⁱ	0.98	2.92	3.5830 (16)	126

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

Acknowledgments

This work was financially supported by the Ministry of Science Technology and Innovation (MOSTI) under a research grant (No. 06–01-09-SF0046). The authors would like to thank Universiti Malaysia Sarawak (UNIMAS) for the facilities to carry out the research work. The authors also thank the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

The title compound, (I), was prepared as a potential ligand for tin (Affan et al., 2009), motivated by the wide range of biological activities displayed by organotin compounds (Gielen & Tiekink, 2005). The r.m.s. for the 13 non-hydrogen atoms comprising (I), Fig. 1, is 0.140 Å. The maximum deviations are found for the carboxylic acid-O atoms with the O1 atom being 0.292 (1) Å out of the least-squares plane and the O2 lying 0.210 (1) Å to the other side. The planarity in the molecule is readily explained in terms of an intramolecular O—H···N hydrogen bond as the hydroxy H is directed toward the centre of the molecule, Table 1. The conformation about the N1═ C2 double bond [1.2909 (16) Å] is E. In the crystal packing, the carbonyl-O2 atom accepts hydrogen bonds from both the hydroxy-O1—H and amine-H atoms, derived from different molecules, Table 1. The result is a supramolecular double layer as illustrated in Fig. 2. Layers stack along the a direction and are connected by C—H···π interactions, Fig. 3 and Table 1.

Experimental

Pyruvic acid (0.440 g, 5 mmol) was dissolved in 10 ml absolute ethanol with constant stirring. An ethanolic solution of phenylhydrazine (0.540 g, 5 mmol) was then added to the solution drop-wise. The resulting reaction mixture was refluxed for 5 h. On cooling the solution to room temperature, a light-orange powder separated, which was filtered and washed with ethanol. The powder was recrystallized from ethanol and dried in vacuo over silica gel. (M.pt. 460–462 K. Yield 0.724 g (73.8%). Anal. Calc. for C₉H₁₀N₂O₂: C, 60.66; H, 5.65; N, 15.72%. Found: C, 60.61; H, 5.59; N, 15.68%. FT—IR (KBr, cm^-1) ν_max: 3333 (m, OH), 3285 (s, NH), 1709 (m, C=O), 1595 (w, C=N), 991 (m, N—N).