Methyl 4-methyl­benzoate

Abstract

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,

• a = 5.9134 (11) Å

• b = 7.6048 (14) Å

• c = 17.484 (3) Å

• β = 97.783 (4)°

• V = 779.0 (2) ų

• 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[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 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

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.

Supplementary Material

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
C9—H9B⋯O2i	0.98	2.51	3.4930 (16)	177

Symmetry code: (i) .

supplementary crystallographic information

Comment

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).

Experimental

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

Refinement

Hydrogen atoms were located in difference syntheses, refined at idealized positions riding on the carbon or nitrogen atoms (C–H = 0.88–0.99 Å) with isotropic displacement parameters U_iso(H) = 1.2U(C_eq).

Figures

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.

Crystal data

C9H10O2	F000 = 320
Mr = 150.17	Dx = 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 = 2.4–27.8º
b = 7.6048 (14) Å	µ = 0.09 mm−1
c = 17.484 (3) Å	T = 120 (2) K
β = 97.783 (4)º	Block, colourless
V = 779.0 (2) Å3	0.45 × 0.43 × 0.39 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	1855 independent reflections
Radiation source: sealed tube	1482 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.039
T = 120(2) K	θmax = 27.9º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Sheldrick, 2004)	h = −7→7
Tmin = 0.961, Tmax = 0.967	k = −10→9
6617 measured reflections	l = −23→23

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	H-atom parameters constrained
wR(F2) = 0.124	w = 1/[σ2(Fo2) + (0.0752P)2 + 0.0208P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1855 reflections	Δρmax = 0.31 e Å−3
102 parameters	Δρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) x, −y+1/2, z−1/2.