2-Methyl-3-(3-methyl­phen­yl)acrylic acid

Niaz Muhammad; Saqib Ali; M Nawaz Tahir; Zia-ur-Rehman

doi:10.1107/S1600536808019545

. 2008 Jul 5;64(Pt 8):o1373. doi: 10.1107/S1600536808019545

2-Methyl-3-(3-methylphenyl)acrylic acid

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

PMCID: PMC2962008 PMID: 21203095

Abstract

The crystal structure of the title compound, C₁₁H₁₂O₂, consists of dimers which are formed due to intermolecular O—H⋯O hydrogen bonding. The dimers are linked to each other by C—H⋯O hydrogen bonds, where C—H belongs to the benzene ring and the O atom is of a carbonyl group of an adjoining molecule. There exist two intermolecular C—H⋯O hydrogen bonds which form five-membered rings. There exist two π–π interactions between the benzene rings. The perpendicular distance in these interactions are 3.006 and 3.396 Å. There also exist C—H⋯π and C—O⋯π interactions.

Related literature

For related literature, see: Bernstein et al. (1995 ▶); Liu et al. (1999 ▶); Muhammad et al. (2007 ▶); Natella et al. (1999 ▶); Niaz et al. (2008 ▶); Parez-Alvarez et al. (2001 ▶); Wiesner et al. (2001 ▶).

Experimental

Crystal data

C₁₁H₁₂O₂
M _r = 176.21
Monoclinic,
a = 7.4430 (9) Å
b = 13.4094 (16) Å
c = 10.2746 (12) Å
β = 110.745 (4)°
V = 959.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 (2) K
0.26 × 0.18 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.980, T _max = 0.986
11342 measured reflections
2820 independent reflections
1075 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.185
S = 1.02
2820 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 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 publication routines (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019545/at2580sup1.cif

e-64-o1373-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019545/at2580Isup2.hkl

e-64-o1373-Isup2.hkl^{(135.6KB, hkl)}

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

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

Cg is the centroid of the C4–C9 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.83	2.611 (3)	160
C3—H3⋯O1	0.93	2.27	2.703 (3)	108
C8—H8⋯O1ⁱⁱ	0.93	2.59	3.394 (3)	145
C10—H10A⋯O2	0.96	2.31	2.783 (3)	109
C10—H10C⋯Cgⁱⁱⁱ	0.96	2.75	3.610 (3)	149
C1—O2⋯Cg^iv	1.25 (1)	3.57 (1)	3.895 (3)	95 (1)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Cinnamic acids and their derivatives have been studied for their pharmacological properties, including hepatoprotactive (Parez-Alvarez et al., 2001), antimalarial (Wiesner et al., 2001), antioxident (Natella et al., 1999) and antihyperglycemic activities (Liu et al., 1999). In continuation of our efforts to synthesize various derivatives of cinamic acids (Niaz et al., 2008) and their complexes, we herein report the structure of the title compound (I).

The crystal structure of 3-(4-bromophenyl)-2-methylacrylic acid (Muhammad et al., 2007) has been reported. The title compound (I) have a similar environment about the carboxylate group but the attachement of methyl instead of Br-atom is at meta-position instead of para-position.

In the crystal structure of the title compound, the C—C bonds are in the range 1.462 (3)–1.500 (3) Å, and C═C have a value of 1.339 (3) Å. The resonant C—O bonds have values of 1.250 (3) and 1.271 (3) Å. In the asymmetric unit, there are two interamolecular H-bonds of C—H···O type (Table 2, Fig 1). Due to these H-bonds, two five membered rings (O1/C1/C2/C3/H3···O1) and (O2/C1/C2/C10/H10A···O2) are formed. The intermolecular (O1—H1···O2ⁱ [symmetry code: i = -x, -y, -z + 1]) hydrogen bond forces the molecules into centrosymmetric dimers, forming a R₂²(8) motif (Bernstein et al. 1995). These dimers are linked to each other by the second intermolecular H-bonding, C8—H8···O2ⁱⁱ [symmetry code: ii = -x + 1, y + 1/2, -z + 1/2] as shown in Fig 2. There exist π–π interactions between the centroids (Cg) of benzene (C4—C9) rings of adjacent molecules. The Cg···Cgⁱⁱⁱ [symmetry code: iii = x, -y + 1/2, z - 1/2] and Cg···Cg^iv [symmetry code: iv = x, -y + 1/2, z + 1/2] have a perpendicular distance of 3.006 and 3.396 Å, respectively. There exist also C10—H10C···Cg^iv interaction, with a distance of 3.610 (3) Å between C10 and Cg^iv. Similarly another π-interaction is present between C1–O2 and Cg^v [symmetry code: v = x - 1, y, z] with a distance of 3.895 (3) Å between C1 and Cg^v. The detail of these interactions is also included in Table 1.

Experimental

Compound (I) was prepared according to our previously reported method (Muhammad et al., 2007). A mixture of 3-methylbenzaldehyde (10 mmol, 1.18 ml), methylmalonic acid (2.36 g, 20 mmol) and piperidine (20 mmol, 1.98 ml) in 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 [yield; 90%, m.p. 321 K].