Methyl 4-methyl­benzoate

Saeed, A.; Rafique, H.; Flörke, U.

doi:10.1107/S1600536808008738

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o821

doi:10.1107/S1600536808008738

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Methyl 4-methylbenzoate

Aamer Saeed,^a Hummera Rafique ^a and Ulrich Flörke ^b ^*

^aDepartment of Chemistry, Quaid-i-Azam University Islamabad, Pakistan, and ^bDepartment Chemie, Fakultät für Naturwissenschaften, Universität Paderborn, Warburgerstrasse 100, D-33098 Paderborn, Germany
^*Correspondence e-mail: aamersaeed@yahoo.com

(Received 29 March 2008; accepted 1 April 2008; online 10 April 2008)

The structure of the title compound, C₉H₁₀O₂, is related to that of 4-methylphenyl 4-methylbenzoate and ethylene di-4-methylbenzoate showing similar bond parameters. The molecule is planar, the dihedral angle between the aromatic ring and the –COOMe group being 0.95 (6)°. The cystal structure exhibits intermolecular C—H⋯O contacts that link molecules into infinite chains extended in the [001] direction.

Related literature

For related literature, see: Deguire & Brisse (1988 ); Gowda et al. (2007 ; Gray & Whalley (1971 ); Harris & Mantle (2001 ); Saeed & Rama (1994 ); Simpson (1978 ).

Experimental

Crystal data

C₉H₁₀O₂
M_r = 150.17
Monoclinic, P 2₁ /c
a = 5.9134 (11) Å
b = 7.6048 (14) Å
c = 17.484 (3) Å
β = 97.783 (4)°
V = 779.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 (2) K
0.45 × 0.43 × 0.39 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.961, T_max = 0.967
6617 measured reflections
1855 independent reflections
1482 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.124
S = 1.06
1855 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O2ⁱ	0.98	2.51	3.4930 (16)	177
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808008738/sg2231sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808008738/sg2231Isup2.hkl

checkCIF report

Comment top

The title ester is an important intermediate in the synthesis of a variety of natural products. These include the sclerotiorin group of fungal metabolites (Gray & Whalley, 1971), isochromans related to sclerotiorin pigments (Saeed & Rama, 1994) and isocoumarins like the 7-methylmellein (Harris & Mantle, 2001) and stellatin (Simpson, 1978).

Related literature top

For related literature, see: Deguire & Brisse (1988); Gowda et al. (2007; Gray & Whalley (1971); Harris & Mantle (2001); Saeed & Rama (1994); Simpson (1978).

Experimental top

The title ester was prepared from commercial p-toluic acid according to standard procedure.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along [100] with intermolecular hydrogen bonding pattern indicated as dashed lines. H-atoms not involved in hydrogen bonding are omitted.

Methyl 4-methylbenzoate top

Crystal data top

C₉H₁₀O₂	F(000) = 320
M_r = 150.17	D_x = 1.280 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 806 reflections
a = 5.9134 (11) Å	θ = 2.4–27.8°
b = 7.6048 (14) Å	µ = 0.09 mm⁻¹
c = 17.484 (3) Å	T = 120 K
β = 97.783 (4)°	Block, colourless
V = 779.0 (2) Å³	0.45 × 0.43 × 0.39 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1855 independent reflections
Radiation source: sealed tube	1482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −7→7
T_min = 0.961, T_max = 0.967	k = −10→9
6617 measured reflections	l = −23→23

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F²) = 0.124	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0752P)² + 0.0208P] where P = (F_o² + 2F_c²)/3
1855 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₉H₁₀O₂	V = 779.0 (2) Å³
M_r = 150.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.9134 (11) Å	µ = 0.09 mm⁻¹
b = 7.6048 (14) Å	T = 120 K
c = 17.484 (3) Å	0.45 × 0.43 × 0.39 mm
β = 97.783 (4)°

Data collection top

Bruker SMART APEX diffractometer	1855 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1482 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.967	R_int = 0.039
6617 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
1855 reflections	Δρ_min = −0.20 e Å⁻³
102 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	0.39091 (14)	0.28701 (11)	0.44793 (5)	0.0280 (2)
O2	0.68910 (15)	0.15425 (13)	0.51751 (5)	0.0325 (3)
C1	0.2956 (2)	0.31740 (17)	0.51874 (7)	0.0320 (3)
H1A	0.2793	0.2050	0.5448	0.048*
H1B	0.1456	0.3732	0.5068	0.048*
H1C	0.3974	0.3946	0.5526	0.048*
C2	0.59091 (19)	0.20144 (15)	0.45593 (6)	0.0234 (3)
C3	0.67753 (18)	0.17434 (15)	0.38071 (6)	0.0223 (3)
C4	0.55841 (19)	0.23124 (15)	0.31083 (7)	0.0247 (3)
H4A	0.4154	0.2888	0.3098	0.030*
C5	0.6496 (2)	0.20350 (15)	0.24261 (7)	0.0262 (3)
H5A	0.5675	0.2426	0.1952	0.031*
C6	0.8588 (2)	0.11953 (15)	0.24239 (7)	0.0244 (3)
C7	0.97615 (19)	0.06389 (15)	0.31291 (7)	0.0253 (3)
H7A	1.1195	0.0068	0.3140	0.030*
C8	0.88716 (19)	0.09050 (15)	0.38126 (7)	0.0242 (3)
H8A	0.9693	0.0515	0.4287	0.029*
C9	0.9593 (2)	0.08897 (17)	0.16858 (7)	0.0312 (3)
H9A	1.1213	0.1213	0.1764	0.047*
H9B	0.8782	0.1613	0.1273	0.047*
H9C	0.9438	−0.0355	0.1542	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0268 (5)	0.0322 (5)	0.0260 (4)	0.0042 (3)	0.0071 (3)	0.0018 (3)
O2	0.0343 (5)	0.0389 (5)	0.0234 (5)	0.0042 (4)	0.0004 (4)	0.0016 (3)
C1	0.0340 (7)	0.0342 (7)	0.0299 (7)	0.0024 (5)	0.0121 (5)	−0.0009 (5)
C2	0.0249 (6)	0.0201 (6)	0.0248 (6)	−0.0033 (4)	0.0022 (5)	0.0003 (4)
C3	0.0236 (6)	0.0203 (6)	0.0232 (6)	−0.0031 (4)	0.0031 (4)	0.0006 (4)
C4	0.0214 (5)	0.0252 (6)	0.0271 (6)	0.0008 (4)	0.0022 (4)	0.0024 (4)
C5	0.0271 (6)	0.0281 (6)	0.0222 (6)	−0.0019 (5)	−0.0006 (5)	0.0029 (4)
C6	0.0275 (6)	0.0210 (6)	0.0251 (6)	−0.0058 (4)	0.0049 (4)	−0.0010 (4)
C7	0.0231 (6)	0.0215 (6)	0.0316 (6)	0.0008 (4)	0.0042 (5)	0.0002 (4)
C8	0.0245 (6)	0.0221 (6)	0.0251 (6)	−0.0017 (4)	0.0000 (4)	0.0032 (4)
C9	0.0355 (7)	0.0320 (7)	0.0271 (6)	−0.0005 (5)	0.0079 (5)	−0.0018 (5)

Geometric parameters (Å, º) top

O1—C2	1.3405 (14)	C5—C6	1.3927 (17)
O1—C1	1.4468 (14)	C5—H5A	0.9500
O2—C2	1.2065 (14)	C6—C7	1.3962 (17)
C1—H1A	0.9800	C6—C9	1.5101 (16)
C1—H1B	0.9800	C7—C8	1.3843 (16)
C1—H1C	0.9800	C7—H7A	0.9500
C2—C3	1.4890 (16)	C8—H8A	0.9500
C3—C8	1.3929 (16)	C9—H9A	0.9800
C3—C4	1.3940 (16)	C9—H9B	0.9800
C4—C5	1.3899 (16)	C9—H9C	0.9800
C4—H4A	0.9500

C2—O1—C1	115.38 (9)	C4—C5—H5A	119.3
O1—C1—H1A	109.5	C6—C5—H5A	119.3
O1—C1—H1B	109.5	C5—C6—C7	118.16 (10)
H1A—C1—H1B	109.5	C5—C6—C9	121.71 (11)
O1—C1—H1C	109.5	C7—C6—C9	120.13 (11)
H1A—C1—H1C	109.5	C8—C7—C6	121.10 (10)
H1B—C1—H1C	109.5	C8—C7—H7A	119.5
O2—C2—O1	123.28 (10)	C6—C7—H7A	119.5
O2—C2—C3	124.43 (11)	C7—C8—C3	120.20 (10)
O1—C2—C3	112.28 (9)	C7—C8—H8A	119.9
C8—C3—C4	119.46 (10)	C3—C8—H8A	119.9
C8—C3—C2	118.00 (10)	C6—C9—H9A	109.5
C4—C3—C2	122.54 (10)	C6—C9—H9B	109.5
C5—C4—C3	119.76 (11)	H9A—C9—H9B	109.5
C5—C4—H4A	120.1	C6—C9—H9C	109.5
C3—C4—H4A	120.1	H9A—C9—H9C	109.5
C4—C5—C6	121.33 (10)	H9B—C9—H9C	109.5

C1—O1—C2—O2	−1.07 (16)	C3—C4—C5—C6	0.00 (17)
C1—O1—C2—C3	179.72 (9)	C4—C5—C6—C7	−0.20 (17)
O2—C2—C3—C8	−0.70 (18)	C4—C5—C6—C9	−179.94 (10)
O1—C2—C3—C8	178.50 (10)	C5—C6—C7—C8	0.28 (17)
O2—C2—C3—C4	−179.94 (11)	C9—C6—C7—C8	−179.98 (10)
O1—C2—C3—C4	−0.74 (16)	C6—C7—C8—C3	−0.16 (17)
C8—C3—C4—C5	0.12 (17)	C4—C3—C8—C7	−0.05 (17)
C2—C3—C4—C5	179.36 (10)	C2—C3—C8—C7	−179.32 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.98	2.51	3.4930 (16)	177

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₀O₂
M_r	150.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	5.9134 (11), 7.6048 (14), 17.484 (3)
β (°)	97.783 (4)
V (Å³)	779.0 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.45 × 0.43 × 0.39

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.961, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	6617, 1855, 1482
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.124, 1.06
No. of reflections	1855
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.20

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

O1—C2	1.3405 (14)	C2—C3	1.4890 (16)
O1—C1	1.4468 (14)	C6—C9	1.5101 (16)
O2—C2	1.2065 (14)

C2—O1—C1	115.38 (9)	O2—C2—C3	124.43 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O2ⁱ	0.98	2.51	3.4930 (16)	176.8

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

AS gratefully acknowledges a research grant from Quaid-I-Azam University, Islamabad.

References

Bruker (2002). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deguire, S. & Brisse, F. (1988). Can. J. Chem. 66, 2545–2552. CrossRef CAS Web of Science Google Scholar
Gowda, B. T., Foro, S., Babitha, K. S. & Fuess, H. (2007). Acta Cryst. E63, o3867. Web of Science CSD CrossRef IUCr Journals Google Scholar
Gray, R. W. & Whalley, W. B. (1971). J. Chem. Soc. C, pp. 3575–3577. Google Scholar
Harris, J. P. & Mantle, P. G. (2001). Phytochemistry, 58, 709–716. Web of Science CrossRef PubMed CAS Google Scholar
Saeed, A. & Rama, N. H. (1994). J. Sci. I. R. Iran, 5, 173–175. CAS Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Simpson, T. J. (1978). J. Chem. Soc. Chem. Commun. pp. 627–628. CrossRef Web of Science Google Scholar