[4-(Methyl­sulfon­yl)phen­yl]acetic acid

Abstract

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,

• a = 19.086 (7) Å

• b = 4.9711 (18) Å

• c = 10.724 (4) Å

• β = 106.102 (6)°

• V = 977.5 (6) ų

• 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[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 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

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.

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
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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed at calculated positions and constrained to ride on their parent atoms, with O—H = 0.82 Å, C—H = 0.93-0.97 Å and with U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C, O) for hydroxy and methyl H atoms.

Figures

Fig. 1.

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

Crystal data

C9H10O4S	F000 = 448
Mr = 214.23	Dx = 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 = 2.2–27.7º
b = 4.9711 (18) Å	µ = 0.32 mm−1
c = 10.724 (4) Å	T = 298 (2) K
β = 106.102 (6)º	Block, colourless
V = 977.5 (6) Å3	0.52 × 0.30 × 0.24 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	1638 independent reflections
Radiation source: fine-focus sealed tube	1502 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.020
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 1.1º
Absorption correction: Multi-scan(SADABS; Sheldrick, 2004)	h = −22→22
Tmin = 0.853, Tmax = 0.928	k = −5→5
4462 measured reflections	l = −11→12

Refinement

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)] = 0.048	H-atom parameters constrained
wR(F2) = 0.140	w = 1/[σ2(Fo2) + (0.0848P)2 + 0.3788P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
1638 reflections	Δρmax = 0.24 e Å−3
129 parameters	Δρmin = −0.43 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
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 (Ų)

	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, °)

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, °)

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.