[4-(Methyl­sulfon­yl)phen­yl]acetic acid

Yuan, Y.-Q.; Guo, S.-R.; Wang, L.-J.

doi:10.1107/S160053680803660X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2435

doi:10.1107/S160053680803660X

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[4-(Methylsulfonyl)phenyl]acetic acid

Yan-Qin Yuan,^a Sheng-Rong Guo ^a ^* and Li-Jin Wang ^a

^aDepartment of Chemistry, Lishui University, 323000 Lishui, Zhejiang Province, People's Republic of China
^*Correspondence e-mail: guosr9608@163.com

(Received 23 October 2008; accepted 7 November 2008; online 26 November 2008)

In the crystal structure of the title compound, C₉H₁₀O₄S, centrosymmetrically related molecules are linked into dimers by intermolecular O—H⋯O hydrogen bonds. Unconventional C—H⋯O hydrogen-bond interactions are also present, connecting dimers into a three-dimensional network.

Related literature

For general background on the properties of the title compound and its derivatives, see: Parimalan et al. (2008 ); Giridhar et al. (2006 ). For the crystal structures of related compounds, see: Guo & Yuan (2006 ); Hartung et al. (2004 ); Hodgson & Asplund (1991 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₁₀O₄S
M_r = 214.23
Monoclinic, P 2₁ /c
a = 19.086 (7) Å
b = 4.9711 (18) Å
c = 10.724 (4) Å
β = 106.102 (6)°
V = 977.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 (2) K
0.52 × 0.30 × 0.24 mm

Data collection

Bruker SMART APEX area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.853, T_max = 0.928
4462 measured reflections
1638 independent reflections
1502 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.140
S = 1.11
1638 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3ⁱ	0.82	1.87	2.693 (3)	175
C3—H3⋯O2ⁱⁱ	0.93	2.53	3.287 (3)	139
C1—H1B⋯O1ⁱⁱⁱ	0.96	2.45	3.365 (4)	160
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803660X/rz2263sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803660X/rz2263Isup2.hkl

checkCIF report

Comment top

The title compound, C₉H₁₀O₄S, and its substituted derivatives have been found to possess an auxin-like activity (Parimalan et al., 2008; Giridhar et al., 2006). These compounds, which are predominantly found in fruits, can be used in the synthesis of pharmaceutical intermediates, some perfumes and non-steroidal anti-inflammatory drugs.

In the molecule of the title compound (Fig. 1), bond lengths and angles agree well with those observed in similar compounds (Guo & Yuan, 2006; Hartung et al., 2004; Hodgson & Asplund, 1991). The S═O bond lengths within the SO₂Me group are not significantly different, with an average value of 1.4366 (10) Å. The average bond length for the two C—S bonds is 1.762 (3) Å. In the crystal packing, centrosymmetrically related molecules are linked into dimers by intermolecular O—H···O hydrogen bonds (Table 1) generating an eight-membered ring of graph set R²₂(8) (Bernstein et al., 1995). The dimers are further linked into a three-dimensional network by unconventional C—H···O hydrogen bonding interactions. The corresponding phenylacetic acid derive without the SO₂Me group (Hartung et al., 2004) forms helical columns of single enantiomers linked by hydrogen bonds between the acidic proton of one molecule and the methoxy O atom of a neighbouring molecule, to give an overall racemic structure.

Related literature top

For general background on the properties of the title compound and it derivatives, see: Parimalan et al. (2008); Giridhar et al. (2006). For the crystal structures of related compounds, see: Guo & Yuan (2006); Hartung et al. (2004); Hodgson & Asplund (1991). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

1-(4-Methanesulfonyl-phenyl)-ethanone (20 mmol), morpholine (60 mmol) and elemental sulfur (40 mmol) were added in a round-bottom flask and refluxed for 2 h at 398 K. A 3N solution of NaOH (20 ml) was then added, and the reaction mixture refluxed for an additional 30 min. After cooling, the mixture was filtered and the filtrate was acidified with HCl to pH 6. The solution was again filtered off and washed with ethyl acetate. The resulting aqueous fraction was finally acidified with diluted HCl, to yield the pure product as a white solid. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol/water (1:1 v/v) solution.

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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with the atom-labeling scheme and 50% probability displacement ellipsoids.

[4-(Methylsulfonyl)phenyl]acetic acid top

Crystal data top

C₉H₁₀O₄S	F(000) = 448
M_r = 214.23	D_x = 1.456 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2824 reflections
a = 19.086 (7) Å	θ = 2.2–27.7°
b = 4.9711 (18) Å	µ = 0.32 mm⁻¹
c = 10.724 (4) Å	T = 298 K
β = 106.102 (6)°	Block, colourless
V = 977.5 (6) Å³	0.52 × 0.30 × 0.24 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	1638 independent reflections
Radiation source: fine-focus sealed tube	1502 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −22→22
T_min = 0.853, T_max = 0.928	k = −5→5
4462 measured reflections	l = −11→12

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0848P)² + 0.3788P] where P = (F_o² + 2F_c²)/3
1638 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₉H₁₀O₄S	V = 977.5 (6) Å³
M_r = 214.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 19.086 (7) Å	µ = 0.32 mm⁻¹
b = 4.9711 (18) Å	T = 298 K
c = 10.724 (4) Å	0.52 × 0.30 × 0.24 mm
β = 106.102 (6)°

Data collection top

Bruker APEX area-detector diffractometer	1638 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1502 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.928	R_int = 0.020
4462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.11	Δρ_max = 0.24 e Å⁻³
1638 reflections	Δρ_min = −0.43 e Å⁻³
129 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
S1	0.38734 (3)	0.64558 (12)	1.01463 (5)	0.0408 (3)
O1	0.41630 (11)	0.5716 (4)	0.90951 (18)	0.0609 (6)
O2	0.36962 (11)	0.4358 (4)	1.09321 (19)	0.0575 (5)
O3	0.07977 (10)	0.9489 (5)	0.6087 (2)	0.0694 (7)
O4	0.00360 (10)	1.2830 (5)	0.6090 (2)	0.0677 (6)
H4	−0.0197	1.2097	0.5418	0.102*
C1	0.44823 (14)	0.8670 (5)	1.1176 (3)	0.0487 (6)
H1A	0.4947	0.7807	1.1501	0.073*
H1B	0.4296	0.9159	1.1889	0.073*
H1C	0.4537	1.0256	1.0701	0.073*
C2	0.30708 (12)	0.8358 (4)	0.9483 (2)	0.0361 (5)
C3	0.30404 (13)	1.0060 (5)	0.8448 (2)	0.0425 (6)
H3	0.3440	1.0226	0.8117	0.051*
C4	0.24133 (14)	1.1507 (5)	0.7913 (2)	0.0481 (6)
H4A	0.2393	1.2662	0.7221	0.058*
C5	0.18090 (13)	1.1260 (5)	0.8396 (2)	0.0434 (6)
C6	0.18554 (13)	0.9570 (6)	0.9437 (3)	0.0491 (6)
H6	0.1458	0.9413	0.9775	0.059*
C7	0.24791 (13)	0.8111 (5)	0.9986 (2)	0.0457 (6)
H7	0.2502	0.6975	1.0685	0.055*
C8	0.11162 (14)	1.2792 (6)	0.7781 (3)	0.0571 (7)
H8A	0.0838	1.2955	0.8410	0.069*
H8B	0.1244	1.4594	0.7574	0.069*
C9	0.06426 (13)	1.1525 (5)	0.6574 (3)	0.0451 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0481 (4)	0.0392 (4)	0.0331 (4)	0.0129 (2)	0.0079 (3)	−0.0027 (2)
O1	0.0635 (11)	0.0752 (13)	0.0449 (11)	0.0256 (10)	0.0164 (9)	−0.0110 (10)
O2	0.0767 (13)	0.0387 (10)	0.0564 (12)	0.0120 (9)	0.0176 (10)	0.0082 (8)
O3	0.0530 (11)	0.0703 (14)	0.0648 (13)	0.0194 (10)	−0.0170 (9)	−0.0235 (11)
O4	0.0509 (11)	0.0665 (13)	0.0667 (14)	0.0203 (10)	−0.0155 (9)	−0.0117 (11)
C1	0.0470 (13)	0.0516 (15)	0.0415 (14)	0.0117 (11)	0.0024 (11)	−0.0031 (11)
C2	0.0381 (11)	0.0374 (12)	0.0294 (11)	0.0036 (9)	0.0038 (9)	−0.0038 (9)
C3	0.0420 (12)	0.0509 (14)	0.0338 (13)	0.0017 (10)	0.0090 (10)	0.0022 (10)
C4	0.0541 (14)	0.0492 (15)	0.0349 (13)	0.0037 (11)	0.0022 (11)	0.0066 (10)
C5	0.0387 (12)	0.0450 (14)	0.0378 (13)	0.0031 (10)	−0.0038 (10)	−0.0110 (10)
C6	0.0386 (12)	0.0585 (15)	0.0499 (15)	0.0000 (11)	0.0116 (11)	−0.0038 (13)
C7	0.0486 (13)	0.0489 (14)	0.0401 (14)	0.0013 (11)	0.0132 (11)	0.0062 (11)
C8	0.0487 (14)	0.0545 (16)	0.0557 (17)	0.0130 (13)	−0.0061 (12)	−0.0132 (13)
C9	0.0364 (12)	0.0471 (15)	0.0449 (14)	0.0044 (10)	−0.0001 (10)	0.0002 (11)

Geometric parameters (Å, º) top

S1—O1	1.4342 (19)	C3—C4	1.378 (4)
S1—O2	1.439 (2)	C3—H3	0.9300
S1—C1	1.752 (3)	C4—C5	1.394 (4)
S1—C2	1.773 (2)	C4—H4A	0.9300
O3—C9	1.212 (3)	C5—C6	1.380 (4)
O4—C9	1.303 (3)	C5—C8	1.510 (3)
O4—H4	0.8200	C6—C7	1.379 (4)
C1—H1A	0.9600	C6—H6	0.9300
C1—H1B	0.9600	C7—H7	0.9300
C1—H1C	0.9600	C8—C9	1.497 (4)
C2—C3	1.384 (3)	C8—H8A	0.9700
C2—C7	1.386 (3)	C8—H8B	0.9700

O1—S1—O2	118.61 (12)	C3—C4—H4A	119.6
O1—S1—C1	108.87 (13)	C5—C4—H4A	119.6
O2—S1—C1	107.99 (13)	C6—C5—C4	118.7 (2)
O1—S1—C2	107.44 (11)	C6—C5—C8	120.8 (2)
O2—S1—C2	107.72 (12)	C4—C5—C8	120.5 (2)
C1—S1—C2	105.44 (11)	C7—C6—C5	121.3 (2)
C9—O4—H4	109.5	C7—C6—H6	119.3
S1—C1—H1A	109.5	C5—C6—H6	119.3
S1—C1—H1B	109.5	C6—C7—C2	119.2 (2)
H1A—C1—H1B	109.5	C6—C7—H7	120.4
S1—C1—H1C	109.5	C2—C7—H7	120.4
H1A—C1—H1C	109.5	C9—C8—C5	114.3 (2)
H1B—C1—H1C	109.5	C9—C8—H8A	108.7
C3—C2—C7	120.6 (2)	C5—C8—H8A	108.7
C3—C2—S1	119.18 (17)	C9—C8—H8B	108.7
C7—C2—S1	120.22 (18)	C5—C8—H8B	108.7
C4—C3—C2	119.5 (2)	H8A—C8—H8B	107.6
C4—C3—H3	120.3	O3—C9—O4	122.7 (2)
C2—C3—H3	120.3	O3—C9—C8	124.2 (2)
C3—C4—C5	120.8 (2)	O4—C9—C8	113.0 (2)

O1—S1—C2—C3	−35.3 (2)	C3—C4—C5—C8	−178.3 (2)
O2—S1—C2—C3	−164.15 (19)	C4—C5—C6—C7	−1.0 (4)
C1—S1—C2—C3	80.7 (2)	C8—C5—C6—C7	178.4 (2)
O1—S1—C2—C7	143.9 (2)	C5—C6—C7—C2	0.2 (4)
O2—S1—C2—C7	15.0 (2)	C3—C2—C7—C6	0.5 (4)
C1—S1—C2—C7	−100.1 (2)	S1—C2—C7—C6	−178.71 (19)
C7—C2—C3—C4	−0.3 (4)	C6—C5—C8—C9	−98.9 (3)
S1—C2—C3—C4	178.84 (19)	C4—C5—C8—C9	80.5 (3)
C2—C3—C4—C5	−0.4 (4)	C5—C8—C9—O3	−2.1 (4)
C3—C4—C5—C6	1.1 (4)	C5—C8—C9—O4	177.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.87	2.693 (3)	175
C3—H3···O2ⁱⁱ	0.93	2.53	3.287 (3)	139
C1—H1B···O1ⁱⁱⁱ	0.96	2.45	3.365 (4)	160

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₀O₄S
M_r	214.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	19.086 (7), 4.9711 (18), 10.724 (4)
β (°)	106.102 (6)
V (Å³)	977.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.52 × 0.30 × 0.24

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.853, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	4462, 1638, 1502
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.140, 1.11
No. of reflections	1638
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.43

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.82	1.87	2.693 (3)	175.4
C3—H3···O2ⁱⁱ	0.93	2.53	3.287 (3)	138.6
C1—H1B···O1ⁱⁱⁱ	0.96	2.45	3.365 (4)	159.5

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank Zhengjiang Natural Science Foundation for financial support (Y407240).

References

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