(Acetoxy)(2-methylphenyl)methyl acetate

Kanchanadevi, J.; Anbalagan, G.; Saravanan, V.; Mohanakrishnan, A.K.; Manivannan, V.

doi:10.1107/S1600536811028625

organic compounds

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Volume 67| Part 8| August 2011| Page o2111

doi:10.1107/S1600536811028625

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(Acetoxy)(2-methylphenyl)methyl acetate

J. Kanchanadevi,^a G. Anbalagan,^b V. Saravanan,^c A. K. Mohanakrishnan ^c and V. Manivannan ^d ^*

^aDepartment of Physics, Velammal Institute of Technology, Panchetty, Chennai 601204, India, ^bDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^dDepartment of Research and Development, PRIST University, Vallam, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: crystallography2010@gmail.com, phdguna@gmail.com

(Received 3 July 2011; accepted 16 July 2011; online 23 July 2011)

In the title compound, C₁₂H₁₄O₄, the two acetoxy groups are inclined by 57.92 (5)° and 62.71 (6)° to the benzene ring. An intermolecular C—H⋯O interaction involving the two acetoxy groups generates a centrosymmetric dimer via an R²₂(16) ring motif.

Related literature

For the structure of the 4-methyl isomer, see: Rajnikant et al. (2009 ). For graph-set notation, see: Bernstein et al. (1995 )

Experimental

Crystal data

C₁₂H₁₄O₄
M_r = 222.23
Monoclinic, C 2/c
a = 15.757 (5) Å
b = 7.564 (5) Å
c = 19.886 (5) Å
β = 99.17 (5)°
V = 2339.8 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.950, T_max = 0.975
12571 measured reflections
2414 independent reflections
1856 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.125
S = 1.05
2414 reflections
149 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O4ⁱ	0.96	2.50	3.425 (3)	161
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S1600536811028625/gk2393sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811028625/gk2393Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811028625/gk2393Isup3.cml

checkCIF report

Comment top

The geometric parameters of the title molecule (Fig. 1) agree well with similar structure (Rajnikant et al., 2009). Intermolecular C—H···O interaction involving the two acetoxy groups generates a centrosymmetric dimer via R²₂(16) ring motif, Fig. 2 (Bernstein et al., 1995).

Related literature top

For the structure of 4-methyl isomer, see: Rajnikant et al. (2009). For graph-set notation, see: Bernstein et al. (1995)

Experimental top

To a solution of 2-methylbenzaldehyde (5 g, 41.61 mmol) in dry acetic anhydride (25 ml) anhydrous indium bromide (0.147 g, 0.416 mmol) was added. It was then stirred at room temperature for 4 h under nitrogen atmosphere. The reaction mixture was then poured over crushed ice (300 g). The solid obtained was filtered and washed thoroughly with water and the product was recrystallized from methanol to give pure product as a colorless solid with a yield of 82% and melting point 333 K.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The R²₂(16) ring set motif of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines (hydrogen atoms have been omitted).

(Acetoxy)(2-methylphenyl)methyl acetate top

Crystal data top

C₁₂H₁₄O₄	F(000) = 944
M_r = 222.23	D_x = 1.262 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7598 reflections
a = 15.757 (5) Å	θ = 2.1–26.5°
b = 7.564 (5) Å	µ = 0.10 mm⁻¹
c = 19.886 (5) Å	T = 295 K
β = 99.17 (5)°	Block, colourless
V = 2339.8 (18) Å³	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	2414 independent reflections
Radiation source: fine-focus sealed tube	1856 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→19
T_min = 0.950, T_max = 0.975	k = −9→8
12571 measured reflections	l = −24→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0609P)² + 0.9232P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2414 reflections	Δρ_max = 0.20 e Å⁻³
149 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0066 (8)

Crystal data top

C₁₂H₁₄O₄	V = 2339.8 (18) Å³
M_r = 222.23	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 15.757 (5) Å	µ = 0.10 mm⁻¹
b = 7.564 (5) Å	T = 295 K
c = 19.886 (5) Å	0.25 × 0.20 × 0.15 mm
β = 99.17 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2414 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1856 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.975	R_int = 0.027
12571 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
2414 reflections	Δρ_min = −0.19 e Å⁻³
149 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.70247 (11)	−0.0332 (2)	0.68559 (8)	0.0539 (4)
C2	0.77083 (15)	−0.0812 (3)	0.73557 (9)	0.0703 (6)
H2	0.7592	−0.1354	0.7751	0.084*
C3	0.85476 (14)	−0.0510 (3)	0.72841 (10)	0.0744 (6)
H3	0.8990	−0.0842	0.7628	0.089*
C4	0.87350 (12)	0.0281 (3)	0.67050 (10)	0.0670 (5)
H4	0.9303	0.0492	0.6654	0.080*
C5	0.80723 (10)	0.0760 (2)	0.61999 (9)	0.0530 (4)
H5	0.8196	0.1295	0.5806	0.064*
C6	0.72234 (10)	0.04578 (19)	0.62698 (7)	0.0447 (4)
C7	0.65391 (10)	0.10316 (19)	0.56986 (7)	0.0434 (4)
H7	0.5963	0.0783	0.5802	0.052*
C8	0.60492 (10)	0.3993 (2)	0.57295 (8)	0.0513 (4)
C9	0.61840 (14)	0.5811 (2)	0.54922 (12)	0.0794 (6)
H9A	0.5646	0.6435	0.5424	0.119*
H9B	0.6407	0.5762	0.5071	0.119*
H9C	0.6586	0.6416	0.5828	0.119*
C10	0.60738 (10)	0.0292 (2)	0.45432 (8)	0.0494 (4)
C11	0.62941 (13)	−0.0747 (3)	0.39646 (10)	0.0717 (5)
H11A	0.5777	−0.1068	0.3666	0.108*
H11B	0.6598	−0.1798	0.4133	0.108*
H11C	0.6651	−0.0050	0.3719	0.108*
C12	0.61143 (13)	−0.0643 (3)	0.69723 (10)	0.0740 (6)
H12A	0.6119	−0.1331	0.7379	0.111*
H12B	0.5804	−0.1269	0.6591	0.111*
H12C	0.5840	0.0472	0.7022	0.111*
O1	0.66431 (6)	0.28750 (13)	0.55632 (5)	0.0477 (3)
O2	0.54980 (9)	0.35382 (19)	0.60388 (8)	0.0794 (4)
O3	0.66880 (7)	0.01209 (13)	0.51011 (5)	0.0469 (3)
O4	0.54496 (8)	0.11891 (18)	0.45344 (6)	0.0649 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0757 (11)	0.0441 (9)	0.0415 (9)	0.0013 (8)	0.0083 (8)	0.0000 (7)
C2	0.1023 (16)	0.0611 (11)	0.0444 (10)	0.0105 (11)	0.0019 (9)	0.0072 (8)
C3	0.0860 (14)	0.0725 (13)	0.0567 (12)	0.0227 (11)	−0.0132 (10)	−0.0030 (10)
C4	0.0614 (10)	0.0700 (12)	0.0659 (12)	0.0116 (9)	−0.0017 (9)	−0.0120 (10)
C5	0.0596 (10)	0.0499 (9)	0.0496 (9)	0.0049 (7)	0.0089 (7)	−0.0031 (7)
C6	0.0590 (9)	0.0351 (7)	0.0394 (8)	0.0033 (6)	0.0060 (6)	−0.0028 (6)
C7	0.0533 (8)	0.0358 (8)	0.0423 (8)	0.0010 (6)	0.0119 (6)	0.0014 (6)
C8	0.0531 (9)	0.0507 (9)	0.0482 (9)	0.0113 (7)	0.0023 (7)	−0.0071 (7)
C9	0.0886 (14)	0.0432 (10)	0.1066 (17)	0.0173 (10)	0.0163 (12)	0.0014 (10)
C10	0.0558 (9)	0.0470 (9)	0.0445 (9)	−0.0060 (7)	0.0055 (7)	0.0033 (7)
C11	0.0824 (13)	0.0797 (13)	0.0508 (10)	−0.0020 (10)	0.0039 (9)	−0.0145 (9)
C12	0.0912 (14)	0.0805 (13)	0.0538 (11)	−0.0122 (11)	0.0222 (10)	0.0127 (10)
O1	0.0520 (6)	0.0355 (6)	0.0573 (7)	0.0054 (4)	0.0135 (5)	0.0036 (5)
O2	0.0832 (9)	0.0732 (9)	0.0908 (10)	0.0161 (7)	0.0418 (8)	−0.0052 (8)
O3	0.0573 (6)	0.0417 (6)	0.0407 (6)	0.0042 (4)	0.0053 (5)	−0.0033 (4)
O4	0.0595 (7)	0.0741 (9)	0.0586 (7)	0.0104 (6)	0.0021 (6)	0.0037 (6)

Geometric parameters (Å, º) top

C1—C6	1.389 (2)	C8—O2	1.192 (2)
C1—C2	1.392 (3)	C8—O1	1.3413 (19)
C1—C12	1.508 (3)	C8—C9	1.480 (3)
C2—C3	1.372 (3)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—C4	1.371 (3)	C9—H9C	0.9600
C3—H3	0.9300	C10—O4	1.1929 (19)
C4—C5	1.377 (2)	C10—O3	1.3572 (19)
C4—H4	0.9300	C10—C11	1.480 (3)
C5—C6	1.386 (2)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—C7	1.500 (2)	C11—H11C	0.9600
C7—O3	1.4248 (18)	C12—H12A	0.9600
C7—O1	1.434 (2)	C12—H12B	0.9600
C7—H7	0.9800	C12—H12C	0.9600

C6—C1—C2	117.32 (17)	O2—C8—C9	125.89 (16)
C6—C1—C12	122.91 (15)	O1—C8—C9	111.48 (16)
C2—C1—C12	119.76 (17)	C8—C9—H9A	109.5
C3—C2—C1	122.11 (18)	C8—C9—H9B	109.5
C3—C2—H2	118.9	H9A—C9—H9B	109.5
C1—C2—H2	118.9	C8—C9—H9C	109.5
C4—C3—C2	120.01 (17)	H9A—C9—H9C	109.5
C4—C3—H3	120.0	H9B—C9—H9C	109.5
C2—C3—H3	120.0	O4—C10—O3	123.03 (15)
C3—C4—C5	119.19 (19)	O4—C10—C11	125.86 (16)
C3—C4—H4	120.4	O3—C10—C11	111.10 (15)
C5—C4—H4	120.4	C10—C11—H11A	109.5
C4—C5—C6	121.02 (17)	C10—C11—H11B	109.5
C4—C5—H5	119.5	H11A—C11—H11B	109.5
C6—C5—H5	119.5	C10—C11—H11C	109.5
C5—C6—C1	120.36 (15)	H11A—C11—H11C	109.5
C5—C6—C7	117.72 (14)	H11B—C11—H11C	109.5
C1—C6—C7	121.92 (14)	C1—C12—H12A	109.5
O3—C7—O1	105.94 (11)	C1—C12—H12B	109.5
O3—C7—C6	107.31 (12)	H12A—C12—H12B	109.5
O1—C7—C6	109.49 (12)	C1—C12—H12C	109.5
O3—C7—H7	111.3	H12A—C12—H12C	109.5
O1—C7—H7	111.3	H12B—C12—H12C	109.5
C6—C7—H7	111.3	C8—O1—C7	117.51 (13)
O2—C8—O1	122.63 (16)	C10—O3—C7	116.42 (12)

C6—C1—C2—C3	0.7 (3)	C1—C6—C7—O3	−121.51 (15)
C12—C1—C2—C3	−178.03 (19)	C5—C6—C7—O1	−55.29 (17)
C1—C2—C3—C4	−0.3 (3)	C1—C6—C7—O1	123.95 (15)
C2—C3—C4—C5	−0.1 (3)	O2—C8—O1—C7	7.3 (2)
C3—C4—C5—C6	0.1 (3)	C9—C8—O1—C7	−173.66 (14)
C4—C5—C6—C1	0.3 (2)	O3—C7—O1—C8	134.50 (12)
C4—C5—C6—C7	179.53 (15)	C6—C7—O1—C8	−110.08 (14)
C2—C1—C6—C5	−0.7 (2)	O4—C10—O3—C7	2.1 (2)
C12—C1—C6—C5	177.99 (17)	C11—C10—O3—C7	−178.64 (14)
C2—C1—C6—C7	−179.89 (15)	O1—C7—O3—C10	−71.00 (15)
C12—C1—C6—C7	−1.2 (2)	C6—C7—O3—C10	172.10 (12)
C5—C6—C7—O3	59.25 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O4ⁱ	0.96	2.50	3.425 (3)	161

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₄
M_r	222.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	15.757 (5), 7.564 (5), 19.886 (5)
β (°)	99.17 (5)
V (Å³)	2339.8 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.950, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	12571, 2414, 1856
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.627

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.125, 1.05
No. of reflections	2414
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O4ⁱ	0.96	2.50	3.425 (3)	161

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Rajnikant, Sarmal, L., Dinesh, K. & Deshmukh, M. B. (2009). J. Chem. Crystallogr. 39, 835–837. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2111

doi:10.1107/S1600536811028625

Open

access