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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2391.
Published online 2008 November 20. doi:  10.1107/S1600536808037720
PMCID: PMC2960146

Methyl 3-(4-methoxy­benzo­yl)propionate

Abstract

The asymmetric unit of the title compound, C12H14O3, contains two independent mol­ecules, in which the benzene rings are oriented at a dihedral angle of 72.08 (3)°. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds link the mol­ecules into centrosymmetric dimers. There are also C—H(...)π contacts between aromatic CH groups and the benzene rings.

Related literature

For general background, see: Hashem et al. (2007 [triangle]); Husain et al.(2005 [triangle]). For a related structure, see: Ali et al. (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-64-o2391-scheme1.jpg

Experimental

Crystal data

  • C12H14O3
  • M r = 206.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2391-efi1.jpg
  • a = 34.762 (4) Å
  • b = 5.2861 (7) Å
  • c = 27.752 (3) Å
  • β = 117.182 (2)°
  • V = 4536.5 (9) Å3
  • Z = 16
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 294 (2) K
  • 0.28 × 0.26 × 0.23 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.798, T max = 0.980
  • 13099 measured reflections
  • 5456 independent reflections
  • 3364 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.174
  • S = 1.01
  • 5456 reflections
  • 272 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1999 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808037720/hk2571sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037720/hk2571Isup2.hkl

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

Acknowledgments

The authors gratefully acknowledge funds from the Higher Education Commission, Islamabad, Pakistan.

supplementary crystallographic information

Comment

Benzoyl propionic acids and esters are important intermediates in heterocyclic chemistry and have been used for the synthesis of various biologically active five-membered heterocyles such as butenolides, pyrrolones (Husain et al., 2005), oxadiazoles and triazoles (Hashem et al., 2007). In view of the versatility of these compounds, we synthesized the title compound and reported herein its crystal structure.

The asymmetric unit of the title compound contains two crystallographically independent molecules of similar geometry (Fig.1). The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable with the corresponding values in 3-(4-methoxybenzoyl)propionic acid (Ali et al., 2008). Rings A (C2-C7) and B (C14-C19) are, of course, planar and they are oriented at a dihedral angle of 72.08 (3)°.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers (Fig. 2), in which they may be effective in the stabilization of the structure. There also exist C—H···π contacts (Table 1) between the aromatic CH groups and the benzene rings.

Experimental

For the preparation of the title compound, the mixture of 3-(4-methoxybenzoyl) propionic acid (2.08 g, 10 mmol) and absolute methanol (50 ml) in the presence of a few drops of suphuric acid was refluxed for 5 h. The excess of solvent was removed by distillation. The solid residue for filltered off, washed with water and recystallized from ethanol (30%) to give the title compound. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (yield; 83%, m.p. 308-309 K).

Refinement

H atoms were positioned geometrically, with C-H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme.
Fig. 2.
A partial packing diagram. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H14O3F000 = 1760
Mr = 206.23Dx = 1.208 Mg m3
Monoclinic, C2/cMelting point: 308(1) K
Hall symbol: -C 2ycMo Kα radiation λ = 0.71073 Å
a = 34.762 (4) ÅCell parameters from 2335 reflections
b = 5.2861 (7) Åθ = 5.3–18.6º
c = 27.752 (3) ŵ = 0.09 mm1
β = 117.182 (2)ºT = 294 (2) K
V = 4536.5 (9) Å3Block, colorless
Z = 160.28 × 0.26 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer5456 independent reflections
Radiation source: fine-focus sealed tube3364 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 294(2) Kθmax = 28.3º
ω and [var phi] scansθmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 1998)h = −37→45
Tmin = 0.798, Tmax = 0.980k = −6→6
13099 measured reflectionsl = −37→27

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.049  w = 1/[σ2(Fo2) + (0.0886P)2 + 0.985P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.174(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.25 e Å3
5456 reflectionsΔρmin = −0.18 e Å3
272 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0021 (4)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
O10.17237 (4)0.1342 (3)0.28466 (5)0.0856 (4)
O20.07042 (4)0.0750 (3)0.24528 (5)0.0908 (4)
O30.08802 (4)−0.0612 (3)0.32828 (5)0.0849 (4)
O40.07570 (4)0.7301 (3)−0.03309 (5)0.0848 (4)
O50.17800 (5)0.7032 (3)0.00217 (5)0.0987 (5)
O60.16293 (5)0.6067 (3)−0.08206 (5)0.0923 (5)
C10.23566 (7)0.1919 (5)0.09882 (8)0.0915 (6)
H1A0.22590.06840.07030.137*
H1B0.26650.18190.11960.137*
H1C0.22770.35790.08340.137*
C20.21493 (5)0.1408 (3)0.13526 (6)0.0633 (4)
C30.22438 (5)0.2949 (3)0.17972 (6)0.0633 (4)
H3A0.24270.43260.18600.076*
C40.20724 (5)0.2485 (3)0.21467 (6)0.0592 (4)
H4A0.21440.35370.24440.071*
C50.17922 (4)0.0452 (3)0.20601 (6)0.0527 (3)
C60.16911 (5)−0.1061 (3)0.16102 (6)0.0622 (4)
H6A0.1502−0.24130.15410.075*
C70.18676 (6)−0.0588 (3)0.12648 (6)0.0683 (4)
H7A0.1796−0.16330.09660.082*
C80.16253 (5)−0.0046 (3)0.24590 (6)0.0584 (4)
C90.13441 (6)−0.2324 (3)0.23814 (7)0.0695 (4)
H9A0.1499−0.38230.23670.083*
H9B0.1087−0.21760.20360.083*
C100.12090 (6)−0.2663 (4)0.28236 (8)0.0749 (5)
H10A0.1070−0.42960.27790.090*
H10B0.1465−0.26590.31720.090*
C110.09074 (5)−0.0647 (3)0.28213 (7)0.0645 (4)
C120.05918 (7)0.1240 (5)0.33221 (9)0.0975 (7)
H12A0.05970.11090.36700.146*
H12B0.03030.09420.30430.146*
H12C0.06830.29040.32800.146*
C130.01362 (6)0.5636 (5)0.15220 (8)0.0921 (6)
H13A−0.00640.70160.14350.138*
H13B0.03600.58200.18870.138*
H13C−0.00130.40680.14880.138*
C140.03334 (5)0.5641 (3)0.11394 (7)0.0663 (4)
C150.02252 (6)0.7474 (4)0.07450 (7)0.0760 (5)
H15A0.00300.87350.07190.091*
C160.04011 (5)0.7474 (3)0.03875 (7)0.0717 (5)
H16A0.03210.87260.01240.086*
C170.06942 (5)0.5640 (3)0.04171 (6)0.0572 (4)
C180.08110 (6)0.3822 (3)0.08218 (7)0.0708 (5)
H18A0.10110.25820.08550.085*
C190.06326 (6)0.3842 (4)0.11747 (7)0.0750 (5)
H19A0.07160.26120.14430.090*
C200.08610 (5)0.5643 (3)0.00094 (6)0.0631 (4)
C210.11550 (6)0.3537 (4)0.00230 (8)0.0770 (5)
H21A0.10110.1937−0.00010.092*
H21B0.14130.35770.03690.092*
C220.12873 (7)0.3661 (4)−0.04260 (9)0.0868 (6)
H22A0.14240.2072−0.04350.104*
H22B0.10290.3841−0.07690.104*
C230.15891 (6)0.5766 (4)−0.03702 (7)0.0709 (5)
C240.19204 (7)0.8028 (5)−0.08167 (9)0.1000 (7)
H24A0.19230.8066−0.11610.150*
H24B0.22070.7686−0.05360.150*
H24C0.18250.9635−0.07510.150*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.1036 (9)0.0928 (10)0.0726 (8)−0.0206 (8)0.0509 (7)−0.0246 (7)
O20.1021 (9)0.1002 (11)0.0765 (8)0.0355 (8)0.0462 (7)0.0253 (7)
O30.0976 (9)0.0987 (10)0.0740 (8)0.0180 (8)0.0528 (7)0.0146 (7)
O40.1052 (9)0.0775 (9)0.0786 (8)0.0147 (7)0.0478 (7)0.0208 (7)
O50.1186 (11)0.1140 (12)0.0730 (8)−0.0327 (9)0.0522 (8)−0.0226 (8)
O60.1053 (10)0.1139 (12)0.0700 (8)−0.0022 (9)0.0507 (7)−0.0093 (8)
C10.0910 (13)0.1117 (17)0.0855 (13)0.0006 (12)0.0522 (11)0.0034 (12)
C20.0589 (9)0.0697 (10)0.0598 (9)0.0106 (7)0.0259 (7)0.0069 (8)
C30.0572 (8)0.0606 (9)0.0672 (9)−0.0006 (7)0.0242 (7)0.0019 (8)
C40.0594 (8)0.0547 (9)0.0586 (8)0.0005 (7)0.0225 (7)−0.0069 (7)
C50.0541 (7)0.0487 (8)0.0509 (7)0.0080 (6)0.0201 (6)0.0019 (6)
C60.0713 (9)0.0529 (9)0.0595 (9)−0.0035 (7)0.0273 (7)−0.0051 (7)
C70.0822 (10)0.0653 (10)0.0573 (9)−0.0004 (8)0.0316 (8)−0.0091 (7)
C80.0605 (8)0.0548 (9)0.0576 (8)0.0072 (7)0.0249 (7)−0.0006 (7)
C90.0812 (11)0.0573 (10)0.0812 (11)0.0029 (8)0.0466 (9)−0.0008 (8)
C100.0902 (12)0.0629 (10)0.0844 (12)0.0094 (9)0.0510 (10)0.0145 (9)
C110.0683 (9)0.0653 (10)0.0650 (9)−0.0016 (8)0.0348 (8)0.0059 (8)
C120.1033 (15)0.1157 (18)0.0954 (15)0.0148 (14)0.0644 (13)−0.0035 (13)
C130.0812 (12)0.1145 (18)0.0849 (13)−0.0088 (12)0.0416 (10)0.0061 (12)
C140.0616 (9)0.0695 (11)0.0609 (9)−0.0118 (8)0.0219 (7)−0.0007 (8)
C150.0741 (10)0.0726 (12)0.0813 (12)0.0137 (9)0.0355 (9)0.0095 (9)
C160.0768 (10)0.0646 (11)0.0719 (10)0.0135 (8)0.0324 (9)0.0178 (8)
C170.0585 (8)0.0463 (8)0.0573 (8)−0.0045 (6)0.0182 (7)0.0001 (6)
C180.0784 (10)0.0547 (9)0.0737 (11)0.0096 (8)0.0301 (9)0.0094 (8)
C190.0878 (12)0.0652 (11)0.0684 (10)0.0022 (9)0.0324 (9)0.0167 (8)
C200.0691 (9)0.0529 (9)0.0616 (9)−0.0059 (7)0.0250 (7)−0.0015 (7)
C210.0949 (12)0.0555 (10)0.0905 (13)0.0031 (9)0.0510 (11)0.0012 (9)
C220.1103 (14)0.0699 (12)0.0914 (13)−0.0015 (11)0.0560 (12)−0.0178 (10)
C230.0805 (11)0.0753 (12)0.0622 (10)0.0100 (9)0.0372 (9)−0.0041 (8)
C240.1055 (15)0.1219 (19)0.0944 (15)0.0072 (14)0.0645 (13)0.0115 (14)

Geometric parameters (Å, °)

C1—C21.510 (2)C13—C141.504 (2)
C1—H1A0.9600C13—H13A0.9600
C1—H1B0.9600C13—H13B0.9600
C1—H1C0.9600C13—H13C0.9600
C2—C71.384 (2)C14—C151.379 (2)
C2—C31.387 (2)C14—C191.379 (2)
C3—C41.373 (2)C15—C161.383 (2)
C3—H3A0.9300C15—H15A0.9300
C4—C51.396 (2)C16—C171.382 (2)
C4—H4A0.9300C16—H16A0.9300
C5—C61.386 (2)C17—C181.390 (2)
C5—C81.489 (2)C17—C201.489 (2)
C6—C71.377 (2)C18—C191.378 (2)
C6—H6A0.9300C18—H18A0.9300
C7—H7A0.9300C19—H19A0.9300
C8—O11.2151 (19)C20—O41.2159 (19)
C8—C91.503 (2)C20—C211.500 (2)
C9—C101.511 (2)C21—C221.514 (3)
C9—H9A0.9700C21—H21A0.9700
C9—H9B0.9700C21—H21B0.9700
C10—C111.493 (2)C22—C231.488 (3)
C10—H10A0.9700C22—H22A0.9700
C10—H10B0.9700C22—H22B0.9700
C11—O21.1955 (19)C23—O51.188 (2)
C11—O31.3268 (19)C23—O61.329 (2)
C12—O31.440 (2)C24—O61.445 (3)
C12—H12A0.9600C24—H24A0.9600
C12—H12B0.9600C24—H24B0.9600
C12—H12C0.9600C24—H24C0.9600
C2—C1—H1A109.5C14—C13—H13B109.5
C2—C1—H1B109.5H13A—C13—H13B109.5
H1A—C1—H1B109.5C14—C13—H13C109.5
C2—C1—H1C109.5H13A—C13—H13C109.5
H1A—C1—H1C109.5H13B—C13—H13C109.5
H1B—C1—H1C109.5C15—C14—C19117.67 (16)
C7—C2—C3117.74 (15)C15—C14—C13120.96 (17)
C7—C2—C1122.31 (17)C19—C14—C13121.37 (17)
C3—C2—C1119.94 (17)C14—C15—C16121.32 (17)
C4—C3—C2121.40 (15)C14—C15—H15A119.3
C4—C3—H3A119.3C16—C15—H15A119.3
C2—C3—H3A119.3C17—C16—C15120.85 (16)
C3—C4—C5120.66 (14)C17—C16—H16A119.6
C3—C4—H4A119.7C15—C16—H16A119.6
C5—C4—H4A119.7C16—C17—C18117.93 (15)
C6—C5—C4117.99 (14)C16—C17—C20119.12 (14)
C6—C5—C8122.87 (14)C18—C17—C20122.93 (15)
C4—C5—C8119.11 (13)C19—C18—C17120.59 (16)
C7—C6—C5120.80 (15)C19—C18—H18A119.7
C7—C6—H6A119.6C17—C18—H18A119.7
C5—C6—H6A119.6C18—C19—C14121.61 (16)
C6—C7—C2121.38 (15)C18—C19—H19A119.2
C6—C7—H7A119.3C14—C19—H19A119.2
C2—C7—H7A119.3O4—C20—C17120.69 (15)
O1—C8—C5120.22 (15)O4—C20—C21120.79 (16)
O1—C8—C9120.82 (15)C17—C20—C21118.51 (14)
C5—C8—C9118.94 (13)C20—C21—C22114.01 (16)
C8—C9—C10113.66 (15)C20—C21—H21A108.7
C8—C9—H9A108.8C22—C21—H21A108.7
C10—C9—H9A108.8C20—C21—H21B108.7
C8—C9—H9B108.8C22—C21—H21B108.7
C10—C9—H9B108.8H21A—C21—H21B107.6
H9A—C9—H9B107.7C23—C22—C21114.28 (16)
C11—C10—C9112.96 (14)C23—C22—H22A108.7
C11—C10—H10A109.0C21—C22—H22A108.7
C9—C10—H10A109.0C23—C22—H22B108.7
C11—C10—H10B109.0C21—C22—H22B108.7
C9—C10—H10B109.0H22A—C22—H22B107.6
H10A—C10—H10B107.8O5—C23—O6122.60 (19)
O2—C11—O3122.84 (16)O5—C23—C22126.08 (17)
O2—C11—C10125.71 (16)O6—C23—C22111.31 (16)
O3—C11—C10111.44 (14)O6—C24—H24A109.5
O3—C12—H12A109.5O6—C24—H24B109.5
O3—C12—H12B109.5H24A—C24—H24B109.5
H12A—C12—H12B109.5O6—C24—H24C109.5
O3—C12—H12C109.5H24A—C24—H24C109.5
H12A—C12—H12C109.5H24B—C24—H24C109.5
H12B—C12—H12C109.5C11—O3—C12116.21 (15)
C14—C13—H13A109.5C23—O6—C24116.92 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C24—H24A···O1i0.962.533.467 (3)164
C4—H4A···Cg1ii0.933.173.858 (4)133
C6—H6A···Cg2iii0.933.264.051 (3)144
C18—H18A···Cg10.933.203.940 (3)138

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2571).

References

  • Ali, S., Rama, N. H., Qadeer, G. & Ruzicka, A. (2008). Acta Cryst. E64, o2197. [PMC free article] [PubMed]
  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (1998). SMART and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (1999). SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hashem, A. I., Youssef, A. S. A., Kandeel, K. A. & Abou-Elmangd, W. S. I. (2007). Eur. J. Med. Chem.42, 934–939. [PubMed]
  • Husain, A., Khan, M. S. Y., Hasan, S. M. & Alam, M. M. (2005). Eur. J. Med. Chem.40, 1394–1404. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography