3-(4-Chloro­phen­yl)-2-methyl­acrylic acid

Niaz Muhammad; Muhammad Nawaz Tahir; Zia-ur-Rehman; Saqib Ali; Farkhanda Shaheen

doi:10.1107/S1600536808022198

. 2008 Jul 19;64(Pt 8):o1542. doi: 10.1107/S1600536808022198

3-(4-Chlorophenyl)-2-methylacrylic acid

Niaz Muhammad ^a, Muhammad Nawaz Tahir ^b,^*, Zia-ur-Rehman ^a, Saqib Ali ^a, Farkhanda Shaheen ^a

PMCID: PMC2962166 PMID: 21203246

Abstract

In the crystal structure of the title compound, C₁₀H₉ClO₂, dimers form as a result of intermolecular O—H⋯O bonding. These dimers are linked to each other via C—H⋯O bonds, where the CH group belongs to the benzene ring and the O atom is from the carbonyl group of an adjacent molecule. There exist two intermolecular C—H⋯O hydrogen bonds, which individually form five-membered rings. There also exists a π–π interaction between the aromatic ring and its symmetry counterpart, with a centroid–centroid distance of 4.0202 (17) Å, and a C—H⋯π interaction between a methyl CH group and the aromatic ring.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Bravo (1998 ▶); Burt (2004 ▶); Hertog et al. (1995 ▶); Muhammad et al. (2007a ▶,b ▶, 2008a ▶,b ▶); Muhammad, Ali et al. (2008 ▶); Niaz et al. (2008 ▶).

Experimental

Crystal data

C₁₀H₉ClO₂
M _r = 196.62
Triclinic,
a = 7.2164 (6) Å
b = 8.2746 (7) Å
c = 9.1762 (8) Å
α = 115.182 (4)°
β = 108.022 (4)°
γ = 90.052 (5)°
V = 465.91 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 296 (2) K
0.28 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.910, T _max = 0.930
7513 measured reflections
2692 independent reflections
1782 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.217
S = 1.10
2692 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808022198/bq2090sup1.cif

e-64-o1542-sup1.cif^{(14.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022198/bq2090Isup2.hkl

e-64-o1542-Isup2.hkl^{(129.5KB, 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
O1—H1⋯O2ⁱ	0.88 (4)	1.76 (4)	2.643 (3)	176.4 (14)
C3—H3A⋯O2	0.96	2.41	2.765 (4)	101
C4—H4⋯O1	0.93	2.32	2.720 (3)	106
C9—H9⋯O2ⁱⁱ	0.93	2.57	3.458 (3)	159
C3—H3a⋯Cgⁱⁱⁱ	0.96	2.84	3.638 (3)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg is the centroid of the C5–C10 ring.

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore, and for financial support to NM for a PhD under the Indigenous Scholarship Scheme.

supplementary crystallographic information

Comment

Cinnamic acids compose a relatively large family of organic acid isomers (Bravo, 1998). In nature, cinnamic acid derivatives are important metabolic building blocks in the production of lignins for higher plants. Cinnamic acid possesses antibacterial, antifungal and parasite fighting abilities (Burt, 2004). A derivative of cinnamic acid is an important pharmaceutical for high blood pressure, stroke prevention and possess antitumour activity (Hertog et al., 1995). In continuation of our efforts to synthesize various derivatives of cinnamic acids (Niaz et al., 2008, Muhammad, Ali et al., 2008) and their tin complexes (Muhammad et al., 2008a, 2008b), we herein report the structure of the title compound (I).

The crystal structure of 3-(4-Bromophenyl)-2-methylacrylic acid (II) (Muhammad et al., 2007a) and 3-(4-Bromophenyl)-2-ethylacrylic acid (Muhammad et al., 2007b) has been previously reported. The title compound (I) have a replacement of Br-atom with Cl-atom. Thus the reported compound (II) is the best example for the comparison of bond geometry etc.

In the crystal structure of the title compound, the C—C bonds are in the range [1.467 (3)–1.503 (4) Å], and C==C have a value of 1.341 (3) Å. The resonant C—O bonds have values of 1.231 (3) and 1.310 (3) Å. In the asymmetric unit, there are two intermolecular H-bonds of C—H···O type (Table 2, Fig 1). Due to these H-bonds two five membered rings (O1/C1/C2/C4/H4···O1) and (O2/C1/C2/C3/H3A···O2) are formed. Centrosymmetric dimers, R₂²(8) (Bernstein et al. 1995) are formed due to the intermolecular O1—H1···O2ⁱ [symmetry code: i = -x - 1, -y + 1, -z] hydrogen bonding. These dimers are linked to each other by intermolecular H-bonding, C9—H9···O2ⁱⁱ [symmetry code: ii = x + 1, y, z + 1] as shown in Fig 2. There exist an interaction, C3—H3A···Cgⁱⁱⁱ [symmetry code: iii = -x, -y, -z] with a distance of 3.638 (3) Å between C3 and Cgⁱⁱⁱ [Cg is the center of the (C5-C10) benzene ring]. There also exist a π···π-interaction between the benzene rings of adjacent molecules. The distance between the centroids of Cg and Cg^iv [symmetry code: iv = -x + 1, -y + 1, -z + 1], is 4.0202 (17) Å.

Experimental

Compound (I) was prepared according to the reported procedure (Muhammad et al., 2007a). A mixture of 4-chlorobenzaldehyde (1.40 g, 10 mmol), methylmalonic acid (2.36 g, 20 mmol) and piperidine (1.98 ml, 20 mmol) in a pyridine (12.5 ml) solution was heated on a steam-bath for 24 h. The reaction mixture was cooled and added to a mixture of 25 ml of concentrated HCl and 50 g of ice. The precipitate formed in the acidified mixture was filtered off and washed with ice-cold water. The product was recrystallized from ethanol. The yield was 89%.