(Benzyl­sulfonyl)­methanol

The structure of the title compound, C₈H₁₀O₃S, (I), has been determined as part of an investigation into the synthesis and characterization of α-hydroxy sulfones. Compound (I) is novel and its X-ray structure is the first recorded for a simple α-hydroxy sulfone. In the crystals of (I), pairs of mol­ecules are linked by intermolecular O—H...O_sulfonyl hydrogen bonds around a centre of symmetry to form a dimer.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.036
• wR factor = 0.101
• Data-to-parameter ratio = 14.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-2001); program(s) used to solve structure: TEXSAN for Windows; program(s) used to refine structure: TEXSAN for Windows and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows and PLATON.

[(phenylmethyl)sulfonyl]methanol

Crystal data

C8H10O3S	F(000) = 392
Mr = 186.23	Dx = 1.401 Mg m^−3
Monoclinic, P21/n	Melting point = 403–405 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71069 Å
a = 22.758 (11) Å	Cell parameters from 25 reflections
b = 7.160 (7) Å	θ = 12.6–17.4°
c = 5.422 (2) Å	µ = 0.33 mm^−1
β = 91.88 (3)°	T = 295 K
V = 883.0 (10) Å^3	Prismatic, colourless
Z = 4	0.30 × 0.20 × 0.15 mm

Data collection

Rigaku AFC7R diffractometer	Rint = 0.022
Radiation source: Rigaku rotating anode	θmax = 25.0°, θmin = 3.0°
Graphite monochromator	h = −13→27
ω/2θ scans	k = 0→8
1795 measured reflections	l = −6→6
1565 independent reflections	3 standard reflections every 150 reflections
1155 reflections with I > 2σ(I)	intensity decay: 3.3%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0419P)^2 + 0.1986P] where P = (Fo^2 + 2Fc^2)/3
1565 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. Crystallography - the scan width was (1.31 + 0.30tanθ)° with an ω scan speed of 32° per minute (up to 5 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Synthesis and characterization of (I) - Benzylmagnesium chloride was generated from benzyl chloride (5.75 ml, 50 mmol) in ether (40 ml) and magnesium turnings (1.50 g, 61.65 mmol) in ether (20 ml) at 25°C under a nitrogen atmosphere. Upon cooling to -78°C, sulfur dioxide (21.8 ml, 500 mmol) was bubbled through the reaction mixture. After stirring for 30 minutes at -78°C, the reaction mixture was allowed to warm to 0°C and formaldehyde (12.5 ml, 150 mmol) and sulfuric acid (6M, 24 ml, 150 mmol) were added. The mixture was heated at reflux for 4 h and saturated aqueous ammonium chloride (65 ml) was added. The aqueous layer was extracted with ether (3 x 30 ml). The combined organic layers were washed with brine (50 ml), dried (anhydrous magnesium sulfate), filtered and the solvent removed under a stream of nitrogen. Recrystallization of the residue from ether gave (I) as colorless needle-like crystals (1.4 g, 15%, from benzyl chloride). mp 130 - 132°C. (Found: C 51.40, H 5.42, S 17.13%. C₈H₁₀O₃S requires C 51.60, H 5.41, S 17.22%). υ_max (KBr)/cm_-1 2922 (br,s), 1376 (m), 1155(m); δ_H (200 MHz, d₆ DMSO) 3.38 (1H, brs, W_h/2 = 21 Hz), 4.39 (2H, s, CH₂Ph), 4.44 (2H, d, J = 6.6 Hz, CH₂OH), 7.34 - 7.48 (5H, m, –C₆H₅); δ_C (100 MHz) 54.7 (CH₂Ph), 76.6 (CH₂OH), 128.4 (i-C₆H₅), 129.2 (m-C₆H₅), 131.0 (p-C₆H₅), 131.7 (o-C₆H₅); (ESMS -ve) 155 (M—CH₂OH 30%).

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.03929 (2)	0.26416 (8)	0.80615 (11)	0.0442 (2)
O1	0.10432 (7)	0.4820 (3)	0.5304 (4)	0.0710 (7)
O2	0.03073 (8)	0.2398 (3)	1.0662 (3)	0.0621 (6)
O3	−0.01270 (7)	0.2939 (2)	0.6498 (3)	0.0559 (6)
C1	0.08772 (11)	0.4602 (3)	0.7704 (5)	0.0598 (10)
C2	0.07699 (10)	0.0692 (3)	0.6835 (4)	0.0469 (8)
C3	0.13247 (9)	0.0222 (3)	0.8261 (4)	0.0408 (7)
C4	0.18619 (10)	0.0891 (3)	0.7528 (5)	0.0526 (8)
C5	0.23723 (11)	0.0476 (4)	0.8868 (6)	0.0664 (10)
C6	0.23492 (12)	−0.0604 (4)	1.0945 (6)	0.0700 (11)
C7	0.18192 (13)	−0.1290 (4)	1.1695 (5)	0.0637 (10)
C8	0.13114 (10)	−0.0874 (3)	1.0365 (5)	0.0519 (8)
H1	0.07730	0.53080	0.44910	0.0840*
H1A	0.06810	0.57030	0.82040	0.0720*
H1B	0.12190	0.44170	0.87250	0.0720*
H2A	0.08650	0.09660	0.51820	0.0570*
H2B	0.05160	−0.03620	0.68560	0.0570*
H4	0.18800	0.16430	0.60890	0.0640*
H5	0.27390	0.09400	0.83470	0.0800*
H6	0.27000	−0.08820	1.18720	0.0850*
H7	0.18040	−0.20490	1.31280	0.0770*
H8	0.09460	−0.13450	1.08960	0.0630*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0384 (3)	0.0453 (3)	0.0489 (3)	0.0012 (3)	0.0021 (2)	−0.0018 (3)
O1	0.0426 (9)	0.0801 (14)	0.0905 (14)	−0.0003 (9)	0.0040 (9)	0.0308 (11)
O2	0.0643 (11)	0.0745 (12)	0.0480 (10)	0.0095 (9)	0.0103 (8)	−0.0016 (9)
O3	0.0389 (9)	0.0607 (11)	0.0677 (11)	0.0035 (8)	−0.0059 (8)	0.0060 (9)
C1	0.0474 (15)	0.0447 (15)	0.087 (2)	−0.0024 (11)	−0.0014 (14)	−0.0070 (14)
C2	0.0471 (13)	0.0431 (13)	0.0504 (14)	0.0001 (11)	−0.0004 (11)	−0.0086 (11)
C3	0.0399 (12)	0.0377 (12)	0.0449 (12)	0.0006 (9)	0.0008 (9)	−0.0095 (10)
C4	0.0481 (14)	0.0507 (14)	0.0594 (15)	−0.0005 (12)	0.0073 (12)	−0.0058 (12)
C5	0.0429 (14)	0.0724 (19)	0.084 (2)	−0.0010 (14)	0.0047 (14)	−0.0185 (17)
C6	0.0565 (17)	0.075 (2)	0.077 (2)	0.0220 (15)	−0.0227 (14)	−0.0214 (17)
C7	0.0744 (18)	0.0594 (17)	0.0566 (15)	0.0165 (15)	−0.0077 (14)	0.0009 (13)
C8	0.0513 (14)	0.0474 (14)	0.0571 (14)	0.0027 (12)	0.0038 (11)	−0.0032 (12)

Geometric parameters (Å, º)

S1—O2	1.440 (2)	C6—C7	1.376 (4)
S1—O3	1.448 (2)	C7—C8	1.375 (4)
S1—C1	1.799 (3)	C1—H1A	0.9499
S1—C2	1.779 (3)	C1—H1B	0.9491
O1—C1	1.376 (4)	C2—H2A	0.9494
O1—H1	0.8226	C2—H2B	0.9508
C2—C3	1.497 (3)	C4—H4	0.9500
C3—C8	1.386 (4)	C5—H5	0.9498
C3—C4	1.383 (3)	C6—H6	0.9504
C4—C5	1.382 (4)	C7—H7	0.9497
C5—C6	1.369 (5)	C8—H8	0.9507
O1···O3	3.072 (4)	C6···H4^viii	2.8820
O1···O3^i	2.783 (4)	C8···H1A^ix	3.0541
O2···C8	3.280 (4)	H1···O3	2.8987
O3···O1	3.072 (4)	H1···O3^i	1.9931
O3···C1^i	3.309 (4)	H1A···C8^x	3.0541
O3···O1^i	2.783 (4)	H1A···O2^ii	2.7159
O1···H2A	2.7896	H1B···C3	3.0244
O2···H1A^ii	2.7159	H1B···C4	2.9997
O2···H2B^iii	2.7590	H2A···O1	2.7896
O2···H2A^iv	2.9093	H2A···O2^vi	2.9093
O3···H1	2.8987	H2A···H4	2.3954
O3···H1^i	1.9931	H2B···H8	2.4720
O3···H2B^v	2.7184	H2B···O2^iii	2.7590
O3···H8^iii	2.6355	H2B···O3^v	2.7184
C1···C4	3.479 (5)	H4···H2A	2.3954
C1···O3^i	3.309 (4)	H4···C6^xi	2.8820
C4···C1	3.479 (5)	H4···H6^xi	2.5946
C4···C7^vi	3.526 (5)	H5···H7^vii	2.5841
C7···C4^iv	3.526 (5)	H6···H4^viii	2.5946
C8···O2	3.280 (4)	H7···C5^xii	3.0178
C3···H1B	3.0244	H7···H5^xii	2.5841
C4···H1B	2.9997	H8···H2B	2.4720
C5···H7^vii	3.0178	H8···O3^iii	2.6355
O2—S1—O3	117.17 (11)	O1—C1—H1A	108.79
O2—S1—C1	107.64 (13)	O1—C1—H1B	108.80
O2—S1—C2	110.69 (12)	H1A—C1—H1B	109.47
O3—S1—C1	108.29 (11)	S1—C2—H2A	108.57
O3—S1—C2	106.94 (10)	S1—C2—H2B	108.52
C1—S1—C2	105.50 (11)	C3—C2—H2A	108.63
C1—O1—H1	109.35	C3—C2—H2B	108.54
S1—C1—O1	112.25 (18)	H2A—C2—H2B	109.44
S1—C2—C3	113.10 (16)	C3—C4—H4	119.65
C2—C3—C4	120.8 (2)	C5—C4—H4	119.69
C4—C3—C8	118.4 (2)	C4—C5—H5	120.00
C2—C3—C8	120.77 (19)	C6—C5—H5	120.02
C3—C4—C5	120.7 (2)	C5—C6—H6	119.95
C4—C5—C6	120.0 (2)	C7—C6—H6	119.88
C5—C6—C7	120.2 (3)	C6—C7—H7	120.12
C6—C7—C8	119.8 (3)	C8—C7—H7	120.04
C3—C8—C7	120.9 (2)	C3—C8—H8	119.55
S1—C1—H1A	108.75	C7—C8—H8	119.53
S1—C1—H1B	108.76
O2—S1—C1—O1	172.83 (17)	C2—C3—C4—C5	179.1 (2)
O3—S1—C1—O1	−59.60 (19)	C8—C3—C4—C5	−0.1 (4)
C2—S1—C1—O1	54.61 (19)	C2—C3—C8—C7	−179.2 (2)
O2—S1—C2—C3	−51.77 (19)	C4—C3—C8—C7	0.0 (3)
O3—S1—C2—C3	179.53 (15)	C3—C4—C5—C6	−0.1 (4)
C1—S1—C2—C3	64.39 (19)	C4—C5—C6—C7	0.5 (4)
S1—C2—C3—C4	−95.6 (2)	C5—C6—C7—C8	−0.6 (4)
S1—C2—C3—C8	83.6 (2)	C6—C7—C8—C3	0.4 (4)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) −x, −y, −z+2; (iv) x, y, z+1; (v) −x, −y, −z+1; (vi) x, y, z−1; (vii) −x+1/2, y+1/2, −z+5/2; (viii) −x+1/2, y−1/2, −z+3/2; (ix) x, y−1, z; (x) x, y+1, z; (xi) −x+1/2, y+1/2, −z+3/2; (xii) −x+1/2, y−1/2, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.82	1.99	2.783 (4)	161

Symmetry code: (i) −x, −y+1, −z+1.