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Acta Cryst. (2008). E64, o1971    [ doi:10.1107/S160053680802802X ]

(4-tert-Butylphenyl)acetic acid

B.-X. Liu, Y.-P. Yu and D.-J. Xu

Abstract top

In the title compound, C12H16O2, the plane of the carboxylic acid group is almost perpendicular to the benzene ring [dihedral angle 80.9 (3)°] and the tert-butyl unit is disordered over two sets of sites in a 0.503 (6):0.497 (6) ratio. In the crystal structure, centrosymmetric dimers arise from pairs of O-H...O hydrogen bonds involving the carboxylic acid groups.

Comment top

As part of investigation on the nature of aromatic stacking (Liu et al., 2006), the title compound, (I), has recently been prepared in Prof. Liu's laboratory by the hydrolization reaction of 2-(4-tert-butylphenyl)-1-morpholinoethanethione. Herein we present its X-ray structure (Fig. 1).

The C8—O1 bond distance of 1.309 (3) Å is significantly longer than the C8—O2 bond distance of 1.191 (3) Å. The carboxyl group is nearly perpendicular to the benzene plane, the dihedral angle being 80.9 (3)°. The adjacent molecules are linked together via O—H···O hydrogen bonding (Table 1) to form a centrosymmetric supramolecular dimer as shown in Fig. 2, which is comparable to that found in 4-tert-butylbenzoic acid (van Koningsveld, 1982).

Related literature top

For general background, see: Liu et al. (2006). For a related structure, see: van Koningsveld (1982).

Experimental top

The title compound was prepared by a hydrolization reaction of 2-(4-tert-butylphenyl)-1-morpholinoethanethione (55 g) in a solution containing CH3COOH (150 ml), H2SO4 (25 ml, 98%) and water (30 ml) at 390 K until the reaction mixture changed colour to dark-green. After cooling to room temperature, the solid product was separated from the reaction mixture, and colourless prisms of (I) were obtained by recrystallization of the solid product from an ethanol–water solution (1:1 v/v) after 2 months.

Refinement top

The carboxyl H atom was located in a difference Fourier map and refined as riding in its as-found relative position with Uiso(H) = 1.5Ueq(O). The methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angles were refined to fit the electron density with Uiso(H) = 1.5Ueq(C). The other H atoms were placed in calculated positions with C—H = 0.97 Å (methylene) or 0.93 Å (aromatic), and refined in riding mode with Uiso(H) = 1.2Ueq(C). The tert-butyl group is disordered over two positions. Occupancies were initially refined and converged to 0.503 (6) and 0.497 (6), respectively; in the final cycles of refinement, the occupancies were fixed at 0.5, and displacement parameters for the disordered carbon atoms were constrained to be identical.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Ortep-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Double dashed lines indicate one of disordered components.
[Figure 2] Fig. 2. The unit cell packing diagram showing the supra-molecular dimeric structure linked by the hydrogen bonding (dashed lines).
(4-tert-Butylphenyl)acetic acid top
Crystal data top
C12H16O2F(000) = 832
Mr = 192.25Dx = 1.097 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2180 reflections
a = 11.209 (2) Åθ = 2.8–25.0°
b = 12.442 (3) ŵ = 0.07 mm−1
c = 17.250 (5) ÅT = 295 K
β = 104.625 (12)°Prism, colourless
V = 2327.8 (10) Å30.30 × 0.23 × 0.16 mm
Z = 8
Data collection top
Bruker APEXII CCD
diffractometer		1375 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.025
graphiteθmax = 25.0°, θmin = 2.4°
Detector resolution: 10 pixels mm-1h = −13→12
φ and ω scansk = −11→14
5829 measured reflectionsl = −20→17
2047 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.220H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0943P)2 + 2.2585P]
where P = (Fo2 + 2Fc2)/3
2047 reflections(Δ/σ)max = 0.003
131 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C12H16O2V = 2327.8 (10) Å3
Mr = 192.25Z = 8
Monoclinic, C2/cMo Kα radiation
a = 11.209 (2) ŵ = 0.07 mm−1
b = 12.442 (3) ÅT = 295 K
c = 17.250 (5) Å0.30 × 0.23 × 0.16 mm
β = 104.625 (12)°
Data collection top
Bruker APEXII CCD
diffractometer		1375 reflections with I > 2σ(I)
5829 measured reflectionsRint = 0.025
2047 independent reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.075H-atom parameters constrained
wR(F2) = 0.220Δρmax = 0.30 e Å−3
S = 1.06Δρmin = −0.25 e Å−3
2047 reflectionsAbsolute structure: ?
131 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
O10.3924 (2)0.7974 (2)0.56682 (15)0.1086 (10)
H10.30880.79590.56070.163*
O20.35115 (18)0.70221 (19)0.45614 (13)0.0801 (7)
C10.6042 (2)0.6780 (3)0.45859 (19)0.0733 (9)
C20.6468 (3)0.5756 (3)0.4707 (2)0.0904 (11)
H20.64480.54030.51790.108*
C30.6930 (3)0.5233 (3)0.41409 (19)0.0838 (10)
H30.72160.45320.42440.101*
C40.6984 (2)0.5702 (2)0.34325 (15)0.0582 (7)
C50.6512 (3)0.6719 (3)0.33048 (18)0.0714 (9)
H50.64980.70600.28230.086*
C60.6056 (3)0.7253 (3)0.3870 (2)0.0819 (10)
H60.57530.79480.37640.098*
C70.5608 (3)0.7390 (4)0.5219 (2)0.1051 (14)
H7A0.59710.70620.57350.126*
H7B0.59170.81200.52370.126*
C80.4244 (3)0.7432 (3)0.51024 (17)0.0653 (8)
C90.7547 (3)0.5128 (3)0.28348 (18)0.0732 (9)
C10A0.8271 (11)0.6028 (9)0.2430 (6)0.1125 (15)0.497 (6)
H10A0.85750.56980.20150.169*0.497 (6)
H10B0.89500.63150.28330.169*0.497 (6)
H10C0.77130.65980.22070.169*0.497 (6)
C11A0.8538 (13)0.4343 (11)0.3166 (9)0.1125 (15)0.497 (6)
H11A0.81870.37140.33440.169*0.497 (6)
H11B0.91240.46600.36110.169*0.497 (6)
H11C0.89440.41470.27590.169*0.497 (6)
C12A0.6605 (9)0.4711 (9)0.2153 (6)0.1125 (15)0.497 (6)
H12A0.62060.52990.18290.169*0.497 (6)
H12B0.60060.43090.23440.169*0.497 (6)
H12C0.69850.42510.18380.169*0.497 (6)
C10B0.7561 (11)0.5733 (9)0.2101 (6)0.1125 (15)0.503 (6)
H10D0.79230.52970.17610.169*0.503 (6)
H10E0.80370.63770.22430.169*0.503 (6)
H10F0.67320.59170.18230.169*0.503 (6)
C11B0.8802 (13)0.4692 (11)0.3269 (8)0.1125 (15)0.503 (6)
H11D0.87170.42320.36980.169*0.503 (6)
H11E0.93420.52790.34820.169*0.503 (6)
H11F0.91420.42890.29000.169*0.503 (6)
C12B0.6679 (9)0.4091 (9)0.2531 (6)0.1125 (15)0.503 (6)
H12D0.58360.43180.23480.169*0.503 (6)
H12E0.67560.35920.29650.169*0.503 (6)
H12F0.69310.37500.20990.169*0.503 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0599 (14)0.172 (3)0.0991 (17)−0.0057 (14)0.0303 (12)−0.0708 (17)
O20.0532 (12)0.1151 (18)0.0758 (14)−0.0020 (11)0.0231 (10)−0.0310 (12)
C10.0408 (15)0.112 (3)0.0682 (19)0.0018 (15)0.0160 (13)−0.0220 (18)
C20.098 (3)0.114 (3)0.068 (2)0.007 (2)0.0381 (19)0.0096 (19)
C30.105 (3)0.078 (2)0.078 (2)0.0180 (19)0.0417 (19)0.0145 (17)
C40.0506 (15)0.0689 (17)0.0574 (15)0.0100 (13)0.0178 (12)0.0069 (13)
C50.0659 (18)0.084 (2)0.0675 (18)0.0235 (16)0.0221 (14)0.0174 (15)
C60.064 (2)0.086 (2)0.094 (2)0.0292 (16)0.0180 (17)−0.0029 (18)
C70.0542 (19)0.171 (4)0.091 (2)0.003 (2)0.0214 (17)−0.053 (3)
C80.0546 (17)0.086 (2)0.0594 (16)0.0042 (14)0.0218 (14)−0.0110 (15)
C90.0687 (19)0.091 (2)0.0630 (17)0.0215 (16)0.0231 (15)0.0022 (16)
C10A0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
C11A0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
C12A0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
C10B0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
C11B0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
C12B0.116 (3)0.136 (4)0.098 (3)0.029 (3)0.050 (3)−0.008 (2)
Geometric parameters (Å, °) top
O1—C81.309 (3)C9—C11B1.517 (15)
O1—H10.9169C9—C12B1.621 (11)
O2—C81.191 (3)C9—C10A1.639 (11)
C1—C21.358 (5)C10A—H10A0.9600
C1—C61.371 (5)C10A—H10B0.9600
C1—C71.508 (4)C10A—H10C0.9600
C2—C31.379 (4)C11A—H11A0.9600
C2—H20.9300C11A—H11B0.9600
C3—C41.369 (4)C11A—H11C0.9600
C3—H30.9300C12A—H12A0.9600
C4—C51.368 (4)C12A—H12B0.9600
C4—C91.517 (4)C12A—H12C0.9600
C5—C61.381 (4)C10B—H10D0.9600
C5—H50.9300C10B—H10E0.9600
C6—H60.9300C10B—H10F0.9600
C7—C81.491 (4)C11B—H11D0.9600
C7—H7A0.9700C11B—H11E0.9600
C7—H7B0.9700C11B—H11F0.9600
C9—C12A1.463 (10)C12B—H12D0.9600
C9—C10B1.476 (10)C12B—H12E0.9600
C9—C11A1.480 (15)C12B—H12F0.9600
C8—O1—H1111.6C10B—C9—C12B105.3 (5)
C2—C1—C6117.3 (3)C4—C9—C12B106.0 (4)
C2—C1—C7121.7 (3)C11B—C9—C12B106.3 (6)
C6—C1—C7121.0 (4)C12A—C9—C10A103.5 (6)
C1—C2—C3120.9 (3)C11A—C9—C10A102.2 (7)
C1—C2—H2119.5C4—C9—C10A107.7 (4)
C3—C2—H2119.5C9—C10A—H10A109.5
C4—C3—C2122.7 (3)C9—C10A—H10B109.5
C4—C3—H3118.7C9—C10A—H10C109.5
C2—C3—H3118.7C9—C11A—H11A109.5
C5—C4—C3115.8 (3)C9—C11A—H11B109.5
C5—C4—C9122.4 (3)C9—C11A—H11C109.5
C3—C4—C9121.7 (3)C9—C12A—H12A109.5
C4—C5—C6121.9 (3)C9—C12A—H12B109.5
C4—C5—H5119.0C9—C12A—H12C109.5
C6—C5—H5119.0C9—C10B—H10D109.5
C1—C6—C5121.3 (3)C9—C10B—H10E109.5
C1—C6—H6119.4H10D—C10B—H10E109.5
C5—C6—H6119.4C9—C10B—H10F109.5
C8—C7—C1115.3 (3)H10D—C10B—H10F109.5
C8—C7—H7A108.5H10E—C10B—H10F109.5
C1—C7—H7A108.5C9—C11B—H11D109.5
C8—C7—H7B108.5C9—C11B—H11E109.5
C1—C7—H7B108.5H11D—C11B—H11E109.5
H7A—C7—H7B107.5C9—C11B—H11F109.5
O2—C8—O1122.7 (3)H11D—C11B—H11F109.5
O2—C8—C7124.9 (3)H11E—C11B—H11F109.5
O1—C8—C7112.4 (3)C9—C12B—H12D109.5
C12A—C9—C11A113.3 (6)C9—C12B—H12E109.5
C12A—C9—C4112.0 (4)H12D—C12B—H12E109.5
C10B—C9—C4116.0 (4)C9—C12B—H12F109.5
C11A—C9—C4116.6 (6)H12D—C12B—H12F109.5
C10B—C9—C11B113.3 (7)H12E—C12B—H12F109.5
C4—C9—C11B109.0 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.921.742.659 (3)176
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.921.742.659 (3)176
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1.
Acknowledgements top

This project was supported by the Educational Development Foundation of Shanghai Educational Committee, China (No. AB0448).

references
References top

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Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Koningsveld, H. van (1982). Cryst. Struct. Commun. 11, 1423–1433.

Liu, B.-X., Nie, J.-J. & Xu, D.-J. (2006). Acta Cryst. E62, m2122–m2124.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.