4-(Methyl­sulfon­yl)benzaldehyde

Qian, S.-S.; Cui, H.-Y.

doi:10.1107/S1600536809046406

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3029

doi:10.1107/S1600536809046406

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4-(Methylsulfonyl)benzaldehyde

Shao-Song Qian ^a ^* and Hong-You Cui ^b

^aSchool of Life Sciences, ShanDong University of Technology, ZiBo 255049, People's Republic of China, and ^bSchool of Chemical Engineering, ShanDong University of Technology, ZiBo 255049, People's Republic of China.
^*Correspondence e-mail: njuqss@yahoo.com.cn

(Received 31 October 2009; accepted 4 November 2009; online 7 November 2009)

In the crystal of the title compound, C₈H₈O₃S, the molecules are linked into a three-dimensional array by intermolecular C—H⋯O hydrogen bonds.

Related literature

For reference bond-length data, see: Allen et al. (1987 ). For a related structure, see: Ma (2008 ). For synthetic details, see: Rivett et al. (1979 ).

Experimental

Crystal data

C₈H₈O₃S
M_r = 184.20
Monoclinic, P 2₁ /c
a = 6.1280 (12) Å
b = 8.0400 (16) Å
c = 16.734 (3) Å
β = 90.07 (3)°
V = 824.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.902, T_max = 0.933
1643 measured reflections
1495 independent reflections
1310 reflections with I > 2σ(I)
R_int = 0.013
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.126
S = 1.00
1495 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O3ⁱ	0.93	2.57	3.457 (3)	159
C1—H1D⋯O1ⁱⁱ	0.96	2.56	3.518 (3)	176
Symmetry codes: (i) -x-1, -y, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046406/wn2364sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046406/wn2364Isup2.hkl

checkCIF report

Comment top

The title compound has been of great of interest for many years. It acts as an important precursor for the synthesis of amino alcohols with applications to the synthesis of the antibiotics chloramphenicol, fluoramphenicol and thiamphenicol. Here we report its crystal structure.

In the title compound (Fig. 1), all bond lengths are within normal ranges (Allen et al., 1987) and comparable to the values observed in a closely related compound (Ma, 2008). The C1—S—C2—C3 torsion angle is 75.07 (17)°.

In the crystal structure, molecules are linked through intermolecular C—H···O hydrogen bonds (Table 1; Fig. 2).

Related literature top

For reference bond-length data, see: Allen et al. (1987). For a related structure, see: Ma (2008). For synthetic details, see: Rivett et al. (1979).

Experimental top

The title compound was synthesized according to a literature method (Rivett et al., 1979). 0.1 g of the title compound was dissolved in acetonitrile (20 ml). Single crystals suitable for X-ray diffraction were obtained by spontaneous evaporation of the solvent.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius 1989); cell refinement: CAD-4 Software (Enraf–Nonius 1989); data reduction: XCAD4 (Harms & Wocadlo,1995); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. Hydrogen atoms are shown as small spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound. Dashed lines indicate hydrogen bonds.

4-(Methylsulfonyl)benzaldehyde top

Crystal data top

C₈H₈O₃S	F(000) = 384
M_r = 184.20	D_x = 1.484 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1280 (12) Å	Cell parameters from 25 reflections
b = 8.0400 (16) Å	θ = 9–13°
c = 16.734 (3) Å	µ = 0.35 mm⁻¹
β = 90.07 (3)°	T = 293 K
V = 824.5 (3) Å³	Block, yellow
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1310 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.013
Graphite monochromator	θ_max = 25.2°, θ_min = 2.4°
ω/2θ scans	h = −7→0
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→0
T_min = 0.902, T_max = 0.933	l = −20→20
1643 measured reflections	3 standard reflections every 200 reflections
1495 independent reflections	intensity decay: 1%

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.1P)² + 0.095P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1495 reflections	Δρ_max = 0.22 e Å⁻³
110 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (6)

Crystal data top

C₈H₈O₃S	V = 824.5 (3) Å³
M_r = 184.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1280 (12) Å	µ = 0.35 mm⁻¹
b = 8.0400 (16) Å	T = 293 K
c = 16.734 (3) Å	0.30 × 0.20 × 0.20 mm
β = 90.07 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1310 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	R_int = 0.013
T_min = 0.902, T_max = 0.933	3 standard reflections every 200 reflections
1643 measured reflections	intensity decay: 1%
1495 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.00	Δρ_max = 0.22 e Å⁻³
1495 reflections	Δρ_min = −0.26 e Å⁻³
110 parameters

Special details top

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 > 2sigma(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
S	0.25890 (8)	0.43803 (6)	0.17148 (3)	0.0397 (3)
O1	0.1031 (3)	0.5283 (2)	0.21856 (10)	0.0647 (5)
O2	0.4429 (3)	0.5269 (2)	0.13956 (10)	0.0590 (5)
C1	0.3533 (4)	0.2698 (3)	0.22913 (12)	0.0479 (5)
H1B	0.4308	0.3111	0.2749	0.072*
H1C	0.4492	0.2022	0.1975	0.072*
H1D	0.2314	0.2041	0.2465	0.072*
C2	0.1206 (3)	0.3429 (2)	0.09056 (10)	0.0338 (4)
C3	−0.0839 (3)	0.2728 (3)	0.10317 (12)	0.0436 (5)
H3A	−0.1484	0.2768	0.1534	0.052*
O3	−0.3837 (3)	0.0537 (2)	−0.10080 (11)	0.0631 (5)
C4	−0.1897 (3)	0.1971 (3)	0.04005 (12)	0.0427 (5)
H4A	−0.3256	0.1482	0.0477	0.051*
C5	−0.0929 (3)	0.1941 (2)	−0.03484 (11)	0.0373 (5)
C6	0.1115 (4)	0.2644 (3)	−0.04627 (12)	0.0432 (5)
H6A	0.1757	0.2613	−0.0966	0.052*
C7	0.2200 (3)	0.3388 (2)	0.01639 (11)	0.0392 (5)
H7A	0.3575	0.3854	0.0090	0.047*
C8	−0.2049 (4)	0.1147 (3)	−0.10336 (13)	0.0504 (6)
H8A	−0.1315	0.1119	−0.1520	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0415 (4)	0.0387 (4)	0.0387 (4)	−0.00006 (19)	−0.0065 (2)	−0.00429 (18)
O1	0.0675 (11)	0.0680 (11)	0.0586 (10)	0.0206 (9)	−0.0087 (9)	−0.0250 (8)
O2	0.0628 (10)	0.0582 (9)	0.0560 (9)	−0.0261 (8)	−0.0096 (8)	0.0025 (8)
C1	0.0512 (12)	0.0505 (12)	0.0421 (11)	0.0021 (10)	−0.0120 (9)	0.0027 (9)
C2	0.0330 (9)	0.0330 (9)	0.0352 (9)	0.0010 (7)	−0.0039 (7)	0.0013 (7)
C3	0.0365 (10)	0.0567 (12)	0.0374 (10)	−0.0024 (9)	0.0051 (8)	−0.0022 (9)
O3	0.0617 (11)	0.0626 (10)	0.0649 (11)	−0.0178 (8)	−0.0167 (8)	−0.0050 (8)
C4	0.0331 (10)	0.0461 (11)	0.0488 (11)	−0.0050 (8)	−0.0015 (8)	0.0001 (8)
C5	0.0398 (10)	0.0323 (9)	0.0396 (10)	0.0018 (8)	−0.0072 (8)	0.0008 (7)
C6	0.0472 (11)	0.0486 (11)	0.0338 (10)	−0.0028 (9)	0.0041 (8)	0.0009 (8)
C7	0.0352 (10)	0.0432 (10)	0.0391 (10)	−0.0045 (8)	0.0005 (8)	0.0030 (8)
C8	0.0595 (14)	0.0469 (12)	0.0448 (11)	−0.0042 (11)	−0.0090 (10)	−0.0014 (9)

Geometric parameters (Å, º) top

S—O1	1.4355 (17)	C3—H3A	0.9300
S—O2	1.4385 (17)	O3—C8	1.201 (3)
S—C1	1.759 (2)	C4—C5	1.387 (3)
S—C2	1.7703 (18)	C4—H4A	0.9300
C1—H1B	0.9600	C5—C6	1.388 (3)
C1—H1C	0.9600	C5—C8	1.480 (3)
C1—H1D	0.9600	C6—C7	1.377 (3)
C2—C7	1.384 (3)	C6—H6A	0.9300
C2—C3	1.390 (3)	C7—H7A	0.9300
C3—C4	1.380 (3)	C8—H8A	0.9300

O1—S—O2	118.34 (12)	C2—C3—H3A	120.5
O1—S—C1	107.85 (11)	C3—C4—C5	119.86 (18)
O2—S—C1	109.17 (11)	C3—C4—H4A	120.1
O1—S—C2	108.66 (10)	C5—C4—H4A	120.1
O2—S—C2	107.77 (9)	C4—C5—C6	120.28 (18)
C1—S—C2	104.13 (9)	C4—C5—C8	120.61 (18)
S—C1—H1B	109.5	C6—C5—C8	119.11 (19)
S—C1—H1C	109.5	C7—C6—C5	120.46 (18)
H1B—C1—H1C	109.5	C7—C6—H6A	119.8
S—C1—H1D	109.5	C5—C6—H6A	119.8
H1B—C1—H1D	109.5	C6—C7—C2	118.71 (17)
H1C—C1—H1D	109.5	C6—C7—H7A	120.6
C7—C2—C3	121.62 (17)	C2—C7—H7A	120.6
C7—C2—S	119.04 (14)	O3—C8—C5	124.8 (2)
C3—C2—S	119.34 (14)	O3—C8—H8A	117.6
C4—C3—C2	119.05 (18)	C5—C8—H8A	117.6
C4—C3—H3A	120.5

O1—S—C2—C7	140.91 (17)	C3—C4—C5—C6	1.1 (3)
O2—S—C2—C7	11.52 (19)	C3—C4—C5—C8	−179.47 (18)
C1—S—C2—C7	−104.34 (17)	C4—C5—C6—C7	−0.4 (3)
O1—S—C2—C3	−39.78 (18)	C8—C5—C6—C7	−179.85 (18)
O2—S—C2—C3	−169.16 (16)	C5—C6—C7—C2	−0.4 (3)
C1—S—C2—C3	74.97 (17)	C3—C2—C7—C6	0.6 (3)
C7—C2—C3—C4	0.1 (3)	S—C2—C7—C6	179.91 (14)
S—C2—C3—C4	−179.23 (15)	C4—C5—C8—O3	2.4 (3)
C2—C3—C4—C5	−0.9 (3)	C6—C5—C8—O3	−178.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O3ⁱ	0.93	2.57	3.457 (3)	159
C1—H1D···O1ⁱⁱ	0.96	2.56	3.518 (3)	176

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

Experimental details

Crystal data
Chemical formula	C₈H₈O₃S
M_r	184.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.1280 (12), 8.0400 (16), 16.734 (3)
β (°)	90.07 (3)
V (Å³)	824.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.902, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	1643, 1495, 1310
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.126, 1.00
No. of reflections	1495
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.26

Computer programs: CAD-4 Software (Enraf–Nonius 1989), XCAD4 (Harms & Wocadlo,1995), 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
C4—H4A···O3ⁱ	0.93	2.57	3.457 (3)	159.3
C1—H1D···O1ⁱⁱ	0.96	2.56	3.518 (3)	175.6

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

Acknowledgements

This project was sponsored by ShanDong Province Science & Technology Innovation Foundation (People's Republic of China).

References

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