4-(Methyl­sulfon­yl)benzaldehyde

Abstract

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,

• a = 6.1280 (12) Å

• b = 8.0400 (16) Å

• c = 16.734 (3) Å

• β = 90.07 (3)°

• V = 824.5 (3) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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.

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
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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were placed in geometrical positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.96 Å, They were treated as riding atoms, with U_iso(H) = kU_eq(C), where k = 1.5 for methyl and 1.2 for all other H atoms.

Figures

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.

Crystal data

C8H8O3S	F(000) = 384
Mr = 184.20	Dx = 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

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

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)] = 0.034	H-atom parameters constrained
wR(F2) = 0.126	w = 1/[σ2(Fo2) + (0.1P)2 + 0.095P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
1495 reflections	Δρmax = 0.22 e Å−3
110 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.