3-Acetyl­benzoic acid

Fixler, D.E.; Newman, J.M.; Lalancette, R.A.; Thompson, H.W.

doi:10.1107/S1600536810021094

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1595

doi:10.1107/S1600536810021094

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3-Acetylbenzoic acid

David E. Fixler,^a Jacob M. Newman,^a Roger A. Lalancette ^a ^* and Hugh W. Thompson ^a

^aCarl A. Olson Memorial Laboratories, Department of Chemistry, Rutgers University, Newark, NJ 07102, USA
^*Correspondence e-mail: rogerlal@andromeda.rutgers.edu

(Received 19 May 2010; accepted 2 June 2010; online 5 June 2010)

In the crystal structure of the title compound, C₉H₈O₃, essentially planar molecules [the carboxyl group makes a dihedral angle of 4.53 (7)° with the plane of the ring, while the acid group forms a dihedral angle of 3.45 (8)° to the ring] aggregate by centrosymmetric hydrogen-bond pairing of ordered carboxyl groups. This yields dimers which have two orientations in a unit cell, creating a herringbone pattern. In addition, two close C—H⋯O intermolecular contacts exist: one is between a methyl H atom and the ketone of a symmetry-related molecule and the other involves a benzene H atom and the carboxyl group O atom of another molecule. The crystal studied was a non-merohedral twin with twin law [100, 0 $[\overline1]$ 0, $[\overline1]$ 0 $[\overline1]$ ] and a domain ratio of 0.8104(14): 0.1896(14).

Related literature

For a discussion of highly ordered carboxyl bond distances and angles, see: Borthwick (1980 ). For the use of the twin law, see: Cooper et al. (2002 ). For the structure of the ortho-isomer, see: Dobson & Gerkin (1996 ). For the structure of the para-isomer, see: Lalancette et al. (2007 ).

Experimental

Crystal data

C₉H₈O₃
M_r = 164.15
Monoclinic, P 2₁ /c
a = 3.8202 (1) Å
b = 15.6478 (3) Å
c = 12.9282 (3) Å
β = 98.508 (1)°
V = 764.31 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.90 mm⁻¹
T = 100 K
0.20 × 0.18 × 0.11 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer
Absorption correction: numerical (SADABS; Sheldrick, 2008a ) T_min = 0.840, T_max = 0.907
7201 measured reflections
1386 independent reflections
1351 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.085
S = 1.06
1386 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 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
O3—H3⋯O2ⁱ	0.931 (19)	1.69 (2)	2.6124 (13)	173.4 (17)
C9—H9A⋯O1ⁱⁱ	0.98	2.57	3.5283 (17)	167
C4—H4⋯O2ⁱⁱⁱ	0.95	2.59	3.3153 (16)	133
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+2, -y+1, -z+1; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2005 ); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021094/lh5054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021094/lh5054Isup2.hkl

checkCIF report

Comment top

Since keto carboxylic acids can crystallize in five different hydrogen-bonding modes, these types of compounds always present a challenge to predict a priori what the H-bonding mode will be. Three of these modes are either relatively rare or have geometries which preclude some structures. Racemates crystallize with a center of symmetry and generally produce an H-bonded dimer between the acid groups.

Fig. 1 presents a view of the asymmetric unit of the title compound (I) with its numbering scheme. The conjugation in this δ-keto acid requires that both the acid and ketone groups are close to the ring plane; the carboxyl (C3—C8—C9—O1) makes a dihedral angle of 4.53 (7)° with the plane of the ring, while the acid (C1—C7—O2—O3) forms a dihedral angle of 3.45 (8)° to the ring (in the same direction). The molecule adopts a chiral conformation by the flexing of both the methyl group and the hydroxyl group away from the plane of the rest of the atoms in the same direction; this induced chirality is due to the packing of the molecules. This flexing then generates a total dihedral angle between the carboxyl and the acetyl groups of 6.19 (8)°.

Complete or partial averaging of C—O bond lengths and C—C—O angles due to disorder in carboxyl dimers was not found in (I), where these lengths and angles (Table 1) are similar to those in other highly ordered carboxyl situations (Borthwick, 1980).

This meta-acetylbenzoic acid has centrosymmetric H-bonded dimer pairs across two different cell edges in the chosen cell, at (0,0,1/2) & at (0,1/2,0). The parallel planes making up the dimer pair are offset from each other by 0.36 Å. Two sets of these dimers are screw-related and form a herringbone angle of 46.15 (3)° between them in the chosen cell (see Fig 2). Two close C—H···O intermolecular contacts exist: one is between a methyl H atom and the ketone of the adjacent molecule, and the 2nd one is from a phenyl H atom to the carboxyl O atom of another molecule.

Compound (I) crystallizes as a centrosymmetric dimer, just as its isomer 4-acetylbenzoic acid (Lalancette et al., 2007). Unlike both the 3-acetyl and the 4-acetylbenzoic acids, 2-acetylbenzoic acid crystallizes in the phthalide form with a single H-bond betwen the hydroxyl of one molecule and the ketone of the adjacent molecule (Dobson & Gerkin, 1996).

This monoclinic crystal is non-merohedrally twinned; the program ROTAX was used to find the twin law, which was [100, 0-10, -10-1] (Cooper et al., 2002). The final refinement resulted in a ratio of 0.8104 (14): 0.1896 (14) for the two domains, with a final wR2 = 0.085 and R1 = 0.031.

Related literature top

For a discussion of highly ordered carboxyl bond distances and angles, see: Borthwick (1980). For the use of the twin law, see: Cooper et al. (2002). For the structure of the ortho-isomer, see: Dobson & Gerkin (1996). For the structure of the para-isomer, see: Lalancette et al. (2007).

Experimental top

Compound (I) was purchased from Acros Organics, Geel, Belgium. X-ray quality crystals were obtained by evaporation from formic acid at room temperature. The solid-state (KBr) infrared spectrum of (I) features a single broad asymmetric peak at 1686 cm^-1 for both C=O functions, typical of unstrained carboxyl-paired keto acids. In CHCl₃ solution, this combined absorption is seen at the same wavenumber.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top

	Fig. 1. A view of the asymmetric unit of (I) with its numbering scheme. Displacement ellipsoids are drawn at the 40% probability level for non-H atoms.
	Fig. 2. A partial packing diagram showing the herringbone pattern of the two sets of dimers making up this structure. Displacement ellipsoids are drawn at the 40% probability level for non-H atoms. Hydrogen bonds are shown as dashed lines.

3-Acetylbenzoic acid top

Crystal data top

C₉H₈O₃	F(000) = 344
M_r = 164.15	D_x = 1.427 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 438 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 3.8202 (1) Å	Cell parameters from 6415 reflections
b = 15.6478 (3) Å	θ = 4.5–70.3°
c = 12.9282 (3) Å	µ = 0.90 mm⁻¹
β = 98.508 (1)°	T = 100 K
V = 764.31 (3) Å³	Rod, colourless
Z = 4	0.20 × 0.18 × 0.11 mm

Data collection top

Bruker SMART CCD APEXII area-detector diffractometer	1386 independent reflections
Radiation source: fine-focus sealed tube	1351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 71.0°, θ_min = 2.8°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −4→4
T_min = 0.840, T_max = 0.907	k = −18→18
7201 measured reflections	l = −15→15

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0497P)² + 0.2254P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1386 reflections	Δρ_max = 0.18 e Å⁻³
115 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (9)

Crystal data top

C₉H₈O₃	V = 764.31 (3) Å³
M_r = 164.15	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 3.8202 (1) Å	µ = 0.90 mm⁻¹
b = 15.6478 (3) Å	T = 100 K
c = 12.9282 (3) Å	0.20 × 0.18 × 0.11 mm
β = 98.508 (1)°

Data collection top

Bruker SMART CCD APEXII area-detector diffractometer	1386 independent reflections
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	1351 reflections with I > 2σ(I)
T_min = 0.840, T_max = 0.907	R_int = 0.023
7201 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.18 e Å⁻³
1386 reflections	Δρ_min = −0.20 e Å⁻³
115 parameters

Special details top

Experimental. 'crystal mounted on a Cryoloop using Paratone-N'

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.7469 (3)	0.37754 (6)	0.50800 (7)	0.0258 (3)
C1	0.1930 (4)	0.17156 (8)	0.35852 (10)	0.0167 (3)
O2	0.2316 (3)	0.09082 (6)	0.51488 (7)	0.0272 (3)
C2	0.3766 (3)	0.23971 (8)	0.41031 (10)	0.0166 (3)
H2	0.4582	0.2359	0.4832	0.020*
O3	−0.0709 (3)	0.03570 (6)	0.36893 (7)	0.0249 (3)
H3	−0.127 (5)	−0.0066 (12)	0.4144 (14)	0.037*
C3	0.4409 (3)	0.31325 (8)	0.35589 (10)	0.0161 (3)
C4	0.3245 (4)	0.31730 (8)	0.24841 (10)	0.0187 (3)
H4	0.3691	0.3671	0.2104	0.022*
C5	0.1437 (4)	0.24901 (9)	0.19657 (10)	0.0193 (3)
H5	0.0667	0.2524	0.1234	0.023*
C6	0.0753 (4)	0.17637 (8)	0.25067 (10)	0.0176 (3)
H6	−0.0505	0.1300	0.2152	0.021*
C7	0.1179 (4)	0.09528 (8)	0.41951 (11)	0.0187 (3)
C8	0.6344 (4)	0.38585 (8)	0.41580 (11)	0.0178 (3)
C9	0.6809 (4)	0.46813 (8)	0.35915 (10)	0.0215 (3)
H9A	0.8271	0.5075	0.4062	0.032*
H9B	0.4487	0.4941	0.3364	0.032*
H9C	0.7972	0.4564	0.2980	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0343 (6)	0.0221 (5)	0.0188 (5)	−0.0065 (5)	−0.0033 (5)	0.0005 (4)
C1	0.0180 (6)	0.0156 (7)	0.0169 (7)	0.0015 (5)	0.0044 (6)	−0.0002 (5)
O2	0.0430 (7)	0.0222 (5)	0.0149 (5)	−0.0086 (5)	−0.0009 (5)	0.0019 (4)
C2	0.0175 (6)	0.0192 (6)	0.0131 (6)	0.0018 (5)	0.0026 (5)	−0.0007 (5)
O3	0.0356 (6)	0.0180 (5)	0.0199 (5)	−0.0088 (5)	0.0001 (5)	−0.0002 (4)
C3	0.0151 (6)	0.0159 (6)	0.0174 (6)	0.0019 (5)	0.0026 (5)	−0.0004 (5)
C4	0.0198 (7)	0.0168 (6)	0.0195 (7)	0.0005 (5)	0.0029 (6)	0.0029 (5)
C5	0.0210 (7)	0.0228 (7)	0.0134 (6)	0.0014 (6)	0.0005 (6)	−0.0003 (5)
C6	0.0177 (7)	0.0176 (6)	0.0172 (7)	−0.0011 (5)	0.0013 (6)	−0.0033 (5)
C7	0.0218 (7)	0.0164 (6)	0.0180 (7)	−0.0007 (5)	0.0031 (6)	−0.0021 (5)
C8	0.0166 (6)	0.0178 (7)	0.0190 (7)	0.0015 (5)	0.0026 (6)	−0.0011 (5)
C9	0.0230 (7)	0.0166 (7)	0.0241 (7)	−0.0033 (6)	0.0012 (6)	0.0007 (5)

Geometric parameters (Å, º) top

O1—C8	1.2128 (17)	C3—C8	1.5057 (18)
C1—C2	1.3922 (19)	C4—C5	1.3897 (19)
C1—C6	1.4022 (18)	C4—H4	0.9500
C1—C7	1.4818 (18)	C5—C6	1.3797 (19)
O2—C7	1.2471 (17)	C5—H5	0.9500
C2—C3	1.3896 (19)	C6—H6	0.9500
C2—H2	0.9500	C8—C9	1.5047 (18)
O3—C7	1.2952 (17)	C9—H9A	0.9800
O3—H3	0.931 (19)	C9—H9B	0.9800
C3—C4	1.3963 (19)	C9—H9C	0.9800

C2—C1—C6	120.11 (12)	C5—C6—C1	119.43 (12)
C2—C1—C7	118.98 (11)	C5—C6—H6	120.3
C6—C1—C7	120.89 (12)	C1—C6—H6	120.3
C3—C2—C1	120.34 (12)	O2—C7—O3	123.04 (12)
C3—C2—H2	119.8	O2—C7—C1	120.31 (12)
C1—C2—H2	119.8	O3—C7—C1	116.64 (12)
C7—O3—H3	110.9 (12)	O1—C8—C9	121.32 (12)
C2—C3—C4	119.16 (12)	O1—C8—C3	120.02 (12)
C2—C3—C8	118.33 (11)	C9—C8—C3	118.66 (11)
C4—C3—C8	122.51 (12)	C8—C9—H9A	109.5
C5—C4—C3	120.50 (12)	C8—C9—H9B	109.5
C5—C4—H4	119.8	H9A—C9—H9B	109.5
C3—C4—H4	119.8	C8—C9—H9C	109.5
C6—C5—C4	120.46 (12)	H9A—C9—H9C	109.5
C6—C5—H5	119.8	H9B—C9—H9C	109.5
C4—C5—H5	119.8

C6—C1—C2—C3	0.7 (2)	C7—C1—C6—C5	178.73 (12)
C7—C1—C2—C3	−177.89 (12)	C2—C1—C7—O2	−3.2 (2)
C1—C2—C3—C4	−1.1 (2)	C6—C1—C7—O2	178.21 (13)
C1—C2—C3—C8	178.83 (12)	C2—C1—C7—O3	176.16 (12)
C2—C3—C4—C5	0.6 (2)	C6—C1—C7—O3	−2.4 (2)
C8—C3—C4—C5	−179.34 (13)	C2—C3—C8—O1	4.06 (19)
C3—C4—C5—C6	0.3 (2)	C4—C3—C8—O1	−176.04 (14)
C4—C5—C6—C1	−0.7 (2)	C2—C3—C8—C9	−175.43 (12)
C2—C1—C6—C5	0.1 (2)	C4—C3—C8—C9	4.47 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.931 (19)	1.69 (2)	2.6124 (13)	173.4 (17)
C9—H9A···O1ⁱⁱ	0.98	2.57	3.5283 (17)	167
C4—H4···O2ⁱⁱⁱ	0.95	2.59	3.3153 (16)	133

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

Experimental details

Crystal data
Chemical formula	C₉H₈O₃
M_r	164.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	3.8202 (1), 15.6478 (3), 12.9282 (3)
β (°)	98.508 (1)
V (Å³)	764.31 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.20 × 0.18 × 0.11

Data collection
Diffractometer	Bruker SMART CCD APEXII area-detector diffractometer
Absorption correction	Numerical (SADABS; Sheldrick, 2008a)
T_min, T_max	0.840, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	7201, 1386, 1351
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.085, 1.06
No. of reflections	1386
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.931 (19)	1.69 (2)	2.6124 (13)	173.4 (17)
C9—H9A···O1ⁱⁱ	0.98	2.57	3.5283 (17)	167
C4—H4···O2ⁱⁱⁱ	0.95	2.59	3.3153 (16)	133

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

Acknowledgements

The authors acknowledge support by NSF–CRIF grant No. 0443538. This paper is dedicated to the memory of HWT; he was a wonderful mentor, teacher and friend at Rutgers University-Newark for over 44 years.

References

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