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

Affan, M.A.; Salam, M.A.; Siew, E.V.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811013717

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1163

doi:10.1107/S1600536811013717

Open

access

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

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

^aFaculty of Resource Science and Technology, Universiti Malaysia Sarawak, 94300 Kota Samarahan, Sarawak, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 11 April 2011; accepted 12 April 2011; online 16 April 2011)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.043
wR(F²) = 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

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
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z+1.

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); 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).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view in projection down the a axis of the supramolecular double layer in (I). The O—H···O and N—H···O hydrogen bonds are shown as orange and blue dashed lines, respectively.
	Fig. 3. A view in projection down the b axis of the crystal packing in (I) showing the connection between layers via C—H···π interactions. The O—H···O and N—H···S hydrogen bonds are shown as orange and blue dashed lines, respectively, and the C—H···π contacts are shown as purple dashed lines.

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

Crystal data top

C₉H₁₀N₂O₂	F(000) = 376
M_r = 178.19	D_x = 1.399 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2940 reflections
a = 7.3239 (3) Å	θ = 2.7–29.2°
b = 12.0837 (7) Å	µ = 0.10 mm⁻¹
c = 9.6836 (4) Å	T = 100 K
β = 99.119 (4)°	Block, yellow
V = 846.17 (7) Å³	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	1920 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1544 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.042
Detector resolution: 10.4041 pixels mm^-1	θ_max = 27.5°, θ_min = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→15
T_min = 0.734, T_max = 1.000	l = −12→12
7879 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0516P)² + 0.2722P] where P = (F_o² + 2F_c²)/3
1920 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₉H₁₀N₂O₂	V = 846.17 (7) Å³
M_r = 178.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3239 (3) Å	µ = 0.10 mm⁻¹
b = 12.0837 (7) Å	T = 100 K
c = 9.6836 (4) Å	0.20 × 0.15 × 0.10 mm
β = 99.119 (4)°

Data collection top

Agilent Supernova Dual diffractometer with an Atlas detector	1920 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1544 reflections with I > 2σ(I)
T_min = 0.734, T_max = 1.000	R_int = 0.042
7879 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.21 e Å⁻³
1920 reflections	Δρ_min = −0.22 e Å⁻³
127 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.64494 (15)	0.79085 (9)	0.40334 (10)	0.0218 (3)
O2	0.56711 (14)	0.78175 (8)	0.17390 (10)	0.0207 (3)
N2	0.69829 (16)	0.46664 (10)	0.44283 (12)	0.0175 (3)
N1	0.68674 (15)	0.57591 (10)	0.41916 (11)	0.0158 (3)
C1	0.60689 (18)	0.73282 (12)	0.28486 (13)	0.0168 (3)
C2	0.61419 (18)	0.61094 (12)	0.29678 (13)	0.0164 (3)
C3	0.5429 (2)	0.54090 (12)	0.17314 (14)	0.0196 (3)
H3A	0.6342	0.4838	0.1615	0.029*
H3B	0.5208	0.5872	0.0891	0.029*
H3C	0.4269	0.5057	0.1876	0.029*
C4	0.78824 (18)	0.42878 (12)	0.57266 (14)	0.0163 (3)
C5	0.7901 (2)	0.31539 (12)	0.59907 (15)	0.0205 (3)
H5	0.7321	0.2656	0.5297	0.025*
C6	0.87695 (19)	0.27559 (13)	0.72715 (16)	0.0242 (4)
H6	0.8773	0.1984	0.7455	0.029*
C7	0.9634 (2)	0.34750 (14)	0.82876 (15)	0.0248 (4)
H7	1.0229	0.3200	0.9163	0.030*
C8	0.96165 (19)	0.45980 (13)	0.80084 (15)	0.0228 (3)
H8	1.0207	0.5094	0.8700	0.027*
C9	0.87518 (19)	0.50122 (13)	0.67369 (15)	0.0193 (3)
H9	0.8753	0.5785	0.6557	0.023*
H1	0.656 (3)	0.7447 (18)	0.472 (2)	0.044 (6)*
H2	0.628 (2)	0.4184 (16)	0.3834 (19)	0.032 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0340 (6)	0.0160 (6)	0.0142 (5)	0.0001 (4)	−0.0003 (4)	−0.0001 (4)
O2	0.0272 (5)	0.0187 (6)	0.0157 (5)	0.0014 (4)	0.0018 (4)	0.0027 (4)
N2	0.0218 (6)	0.0138 (6)	0.0157 (6)	0.0001 (5)	−0.0007 (5)	0.0008 (5)
N1	0.0166 (6)	0.0149 (6)	0.0158 (6)	0.0009 (4)	0.0026 (4)	0.0007 (4)
C1	0.0175 (7)	0.0172 (8)	0.0153 (6)	−0.0006 (5)	0.0014 (5)	−0.0006 (5)
C2	0.0159 (6)	0.0180 (8)	0.0153 (6)	−0.0003 (5)	0.0027 (5)	0.0006 (5)
C3	0.0240 (7)	0.0175 (8)	0.0162 (6)	−0.0013 (6)	0.0002 (6)	−0.0008 (5)
C4	0.0146 (6)	0.0195 (8)	0.0153 (6)	0.0022 (5)	0.0043 (5)	0.0032 (5)
C5	0.0209 (7)	0.0181 (8)	0.0223 (7)	0.0016 (6)	0.0024 (6)	0.0010 (6)
C6	0.0226 (7)	0.0211 (8)	0.0288 (8)	0.0042 (6)	0.0034 (6)	0.0088 (6)
C7	0.0195 (7)	0.0345 (9)	0.0194 (7)	0.0039 (6)	0.0005 (6)	0.0093 (6)
C8	0.0189 (7)	0.0302 (9)	0.0182 (7)	−0.0008 (6)	−0.0003 (6)	0.0014 (6)
C9	0.0188 (7)	0.0195 (8)	0.0196 (7)	−0.0013 (5)	0.0025 (6)	0.0010 (6)

Geometric parameters (Å, º) top

O1—C1	1.3358 (16)	C4—C9	1.390 (2)
O1—H1	0.86 (2)	C4—C5	1.393 (2)
O2—C1	1.2205 (16)	C5—C6	1.3871 (19)
N2—N1	1.3405 (16)	C5—H5	0.9500
N2—C4	1.4005 (17)	C6—C7	1.388 (2)
N2—H2	0.916 (18)	C6—H6	0.9500
N1—C2	1.2909 (16)	C7—C8	1.383 (2)
C1—C2	1.478 (2)	C7—H7	0.9500
C2—C3	1.4913 (18)	C8—C9	1.3858 (19)
C3—H3A	0.9800	C8—H8	0.9500
C3—H3B	0.9800	C9—H9	0.9500
C3—H3C	0.9800

C1—O1—H1	107.9 (14)	C9—C4—N2	121.60 (13)
N1—N2—C4	118.90 (11)	C5—C4—N2	118.39 (12)
N1—N2—H2	120.4 (11)	C6—C5—C4	119.65 (14)
C4—N2—H2	119.5 (11)	C6—C5—H5	120.2
C2—N1—N2	119.05 (12)	C4—C5—H5	120.2
O2—C1—O1	119.34 (13)	C5—C6—C7	120.65 (14)
O2—C1—C2	123.52 (12)	C5—C6—H6	119.7
O1—C1—C2	117.13 (11)	C7—C6—H6	119.7
N1—C2—C1	113.77 (12)	C8—C7—C6	119.11 (13)
N1—C2—C3	126.28 (13)	C8—C7—H7	120.4
C1—C2—C3	119.95 (11)	C6—C7—H7	120.4
C2—C3—H3A	109.5	C7—C8—C9	121.11 (14)
C2—C3—H3B	109.5	C7—C8—H8	119.4
H3A—C3—H3B	109.5	C9—C8—H8	119.4
C2—C3—H3C	109.5	C8—C9—C4	119.46 (14)
H3A—C3—H3C	109.5	C8—C9—H9	120.3
H3B—C3—H3C	109.5	C4—C9—H9	120.3
C9—C4—C5	120.01 (13)

C4—N2—N1—C2	175.73 (12)	C9—C4—C5—C6	0.8 (2)
N2—N1—C2—C1	179.08 (12)	N2—C4—C5—C6	−179.52 (13)
N2—N1—C2—C3	−1.5 (2)	C4—C5—C6—C7	−0.6 (2)
O2—C1—C2—N1	169.64 (13)	C5—C6—C7—C8	0.1 (2)
O1—C1—C2—N1	−10.90 (18)	C6—C7—C8—C9	0.1 (2)
O2—C1—C2—C3	−9.8 (2)	C7—C8—C9—C4	0.2 (2)
O1—C1—C2—C3	169.66 (12)	C5—C4—C9—C8	−0.6 (2)
N1—N2—C4—C9	−4.0 (2)	N2—C4—C9—C8	179.71 (13)
N1—N2—C4—C5	176.34 (12)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₂
M_r	178.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.3239 (3), 12.0837 (7), 9.6836 (4)
β (°)	99.119 (4)
V (Å³)	846.17 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.734, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7879, 1920, 1544
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.114, 1.03
No. of reflections	1920
No. of parameters	127
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Footnotes

‡Additional correspondence author, e-mail: maaffan@yahoo.com.

Acknowledgements

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.

References

Affan, M. A., Wan Foo, S., Jusoh, I., Hanapi, S. & Tiekink, E. R. T. (2009). Inorg. Chim. Acta, 362, 5031–5037. Web of Science CSD CrossRef CAS Google Scholar
Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gielen, M. & Tiekink, E. R. T. (2005). Metallotherapeutic Drugs and Metal-Based Diagnostic Agents: The Use of Metals in Medicine, edited by M. Gielen & E. R. T. Tiekink, pp. 421–439. Chichester: John Wiley & Sons. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1163

doi:10.1107/S1600536811013717

Open

access