(3,4-Dihy­droxy­oxolan-2-yl)methyl 4-methyl­benzene­sulfonate

Dibrov, S.; Carnevali, M.; Hermann, T.

doi:10.1107/S1600536810044788

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3088

https://doi.org/10.1107/S1600536810044788

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(3,4-Dihydroxyoxolan-2-yl)methyl 4-methylbenzenesulfonate

Sergey Dibrov,^a Maia Carnevali ^a and Thomas Hermann ^a ^*

^aDepartment of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0358, USA
^*Correspondence e-mail: tch@ucsd.edu

(Received 28 October 2010; accepted 2 November 2010; online 6 November 2010)

The racemic title compound, C₁₂H₁₆O₆S, possesses a five-membered ring that adopts an envelope-shaped conformation; the two hydroxy groups occupy quasi-axial positions. Adjacent molecules are linked by O—H⋯O hydrogen bonds to generate a ribbon that runs along the a axis of the orthorhombic unit cell. The crystal studied was an inversion twin.

Related literature

For the synthesis of the title compound, see: Kapitan & Grazca (2008 ); Park et al. (2005 ). For the use of xylitol tosylates in the synthesis of bicyclic oxetanes, see: Köll & Oetling (1987 ).

Experimental

Crystal data

C₁₂H₁₆O₆S
M_r = 288.31
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.414 (4) Å
b = 10.172 (8) Å
c = 24.080 (18) Å
V = 1326.0 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 173 K
0.50 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.879, T_max = 0.949
14329 measured reflections
3154 independent reflections
2333 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.110
S = 1.02
3154 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ), 1174 Friedel pairs
Flack parameter: 0.47 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.84	2.03	2.834 (4)	160
O3—H3⋯O3ⁱⁱ	0.84	2.17	2.931 (2)	151
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810044788/ng5055sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044788/ng5055Isup2.hkl

checkCIF report

Comment top

The title compound is the product of the cyclization of xylitol in the presence of p-toluenesulfonyl chloride. The synthetic procedure is described below. We report here the single-crystal X-ray structure.

Asymmetric unit of the title compound is composed of molecule 1 (Fig. 1). Molecules are linked together into infinite chains by the intermolecular O2—H2···O1ⁱ (Fig. 2) that form dimers by the O3—H3···O3ⁱⁱ hydrogen bonds. These dimeric chains propagate along the a axis (Fig. 3).

Related literature top

For the synthesis of the title compound, see: Kapitan & Grazca (2008); Park et al. (2005). For the use of xylitol tosylates in the synthesis of bicyclic oxetanes, see: Köll & Oetling (1987).

Experimental top

In our attempt to make 2,3,4-trihydroxypentane-1,5-diyl bis(4-methylbenzenesulfonate) we have obtained (3,4-dihydroxytetrahydrofuran-2-yl)methyl 4-methylbenzenesulfonate as a major product. The title compound has been synthesized by modification of procedures described by Park et al. (2005) and Kapitan & Grazca (2008). To a solution of racemic Xylitol (33 mmol) in pyridine (40 ml), p-toluenesulfonylchloride (69 mmol) in pyridine was added drop wise at -10°C. The reaction mixture was kept at 4°C overnight, resulting in formation of white precipitate which was removed by filtration. The filtrate was poured over 300 ml of water and kept in an ice bath for 20 minutes. Extraction with dichloromethane, followed by washing of the organic layer with saturated NaCl solution, drying over sodium sulfate, filtration and evaporation yielded the title compound which was finally purified by flash chromatography. In a sample vial, 20 mg of compound was taken and dissolved in MeOH. Upon slow evaporation at 273 K the crystals are formed as colorless blocks.

Structure description top

For the synthesis of the title compound, see: Kapitan & Grazca (2008); Park et al. (2005). For the use of xylitol tosylates in the synthesis of bicyclic oxetanes, see: Köll & Oetling (1987).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SMART (Bruker, 2005); data reduction: SMART (Bruker, 2005); 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 title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Hydrogen bonding showing the formation of dimeric chains. Intermolecular hydrogen bonds are shown as dashed lines. Symmetry codes: (i) x - 1, y, z; (ii) x - 1/2, -y + 3/2, -z.
	Fig. 3. The crystal packing of the title compound, viewed down the a axis.

(3,4-Dihydroxyoxolan-2-yl)methyl 4-methylbenzenesulfonate top

Crystal data top

C₁₂H₁₆O₆S	F(000) = 608
M_r = 288.31	D_x = 1.444 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2ac2ab	Cell parameters from 3862 reflections
a = 5.414 (4) Å	θ = 2.6–23.4°
b = 10.172 (8) Å	µ = 0.26 mm⁻¹
c = 24.080 (18) Å	T = 173 K
V = 1326.0 (17) Å³	Block, colourless
Z = 4	0.50 × 0.30 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	3154 independent reflections
Radiation source: fine-focus sealed tube	2333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
φ and ω scans	θ_max = 28.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −7→7
T_min = 0.879, T_max = 0.949	k = −13→13
14329 measured reflections	l = −31→26

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0413P)² + 0.5008P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.110	(Δ/σ)_max = 0.003
S = 1.02	Δρ_max = 0.26 e Å⁻³
3154 reflections	Δρ_min = −0.19 e Å⁻³
177 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0054 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1174 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.47 (12)

Crystal data top

C₁₂H₁₆O₆S	V = 1326.0 (17) Å³
M_r = 288.31	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.414 (4) Å	µ = 0.26 mm⁻¹
b = 10.172 (8) Å	T = 173 K
c = 24.080 (18) Å	0.50 × 0.30 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	3154 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2333 reflections with I > 2σ(I)
T_min = 0.879, T_max = 0.949	R_int = 0.056
14329 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H-atom parameters constrained
wR(F²) = 0.110	Δρ_max = 0.26 e Å⁻³
S = 1.02	Δρ_min = −0.19 e Å⁻³
3154 reflections	Absolute structure: Flack (1983), with 1174 Friedel pairs
177 parameters	Absolute structure parameter: 0.47 (12)
0 restraints

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	0.49846 (15)	0.83391 (7)	0.19055 (3)	0.03938 (19)
O4	0.3443 (4)	0.9149 (2)	0.14690 (8)	0.0403 (5)
O3	−0.1096 (4)	0.7717 (2)	0.02146 (9)	0.0522 (6)
H3	−0.2351	0.7308	0.0104	0.063*
O5	0.6954 (4)	0.9196 (2)	0.20441 (10)	0.0558 (6)
O1	0.1981 (4)	0.9922 (2)	0.03798 (8)	0.0452 (5)
O6	0.5516 (4)	0.7081 (2)	0.16814 (8)	0.0533 (6)
C3	−0.1840 (5)	0.8929 (3)	0.04656 (12)	0.0393 (7)
H3A	−0.3360	0.8827	0.0698	0.047*
C5	0.1566 (5)	0.8449 (3)	0.11540 (12)	0.0397 (6)
H5A	0.0364	0.8031	0.1409	0.048*
H5B	0.2338	0.7755	0.0924	0.048*
O2	−0.3312 (4)	1.1107 (2)	0.02581 (11)	0.0574 (6)
H2	−0.4753	1.0904	0.0355	0.069*
C9	−0.0409 (6)	0.8029 (3)	0.33240 (11)	0.0477 (8)
C11	0.2748 (6)	0.9224 (3)	0.28326 (13)	0.0469 (8)
H11	0.3752	0.9984	0.2793	0.056*
C4	0.0298 (5)	0.9430 (3)	0.07931 (11)	0.0354 (6)
H4	−0.0271	1.0181	0.1029	0.042*
C10	0.1045 (7)	0.9131 (3)	0.32584 (12)	0.0518 (9)
H10	0.0872	0.9842	0.3511	0.062*
C7	0.1562 (6)	0.7062 (3)	0.25310 (12)	0.0431 (7)
H7	0.1760	0.6342	0.2284	0.052*
C2	−0.2121 (6)	0.9991 (3)	0.00288 (13)	0.0429 (7)
H2A	−0.2984	0.9661	−0.0311	0.051*
C6	0.2955 (5)	0.8185 (3)	0.24657 (11)	0.0359 (6)
C12	−0.2297 (8)	0.7949 (4)	0.37844 (14)	0.0703 (11)
H12A	−0.3449	0.7228	0.3708	0.105*
H12B	−0.3211	0.8779	0.3806	0.105*
H12C	−0.1457	0.7788	0.4138	0.105*
C1	0.0535 (5)	1.0362 (3)	−0.00883 (12)	0.0458 (8)
H1A	0.1114	0.9932	−0.0433	0.055*
H1B	0.0689	1.1325	−0.0134	0.055*
C8	−0.0126 (7)	0.6997 (3)	0.29599 (11)	0.0478 (7)
H8	−0.1106	0.6229	0.3004	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0386 (3)	0.0384 (4)	0.0411 (3)	0.0040 (4)	−0.0029 (4)	0.0060 (3)
O4	0.0423 (11)	0.0401 (11)	0.0385 (10)	0.0032 (10)	−0.0059 (9)	0.0067 (9)
O3	0.0547 (13)	0.0456 (13)	0.0562 (13)	−0.0053 (11)	−0.0067 (12)	−0.0107 (11)
O5	0.0423 (12)	0.0619 (15)	0.0633 (14)	−0.0097 (12)	−0.0080 (11)	0.0074 (12)
O1	0.0308 (11)	0.0596 (14)	0.0452 (12)	−0.0038 (10)	−0.0002 (9)	0.0146 (10)
O6	0.0641 (15)	0.0438 (12)	0.0518 (12)	0.0142 (11)	0.0056 (11)	0.0022 (10)
C3	0.0351 (15)	0.0448 (18)	0.0381 (14)	−0.0006 (14)	0.0023 (13)	0.0003 (13)
C5	0.0376 (15)	0.0412 (16)	0.0404 (14)	−0.0025 (14)	−0.0027 (13)	−0.0007 (14)
O2	0.0416 (12)	0.0519 (14)	0.0788 (16)	0.0049 (11)	0.0027 (13)	0.0074 (12)
C9	0.059 (2)	0.0514 (19)	0.0331 (13)	0.0089 (17)	0.0039 (14)	0.0064 (14)
C11	0.061 (2)	0.0351 (17)	0.0441 (16)	0.0009 (15)	−0.0106 (15)	0.0002 (14)
C4	0.0322 (15)	0.0393 (15)	0.0347 (13)	−0.0035 (13)	0.0008 (12)	0.0030 (11)
C10	0.075 (2)	0.0412 (18)	0.0396 (16)	0.0087 (17)	−0.0040 (16)	−0.0052 (15)
C7	0.0569 (19)	0.0326 (15)	0.0397 (15)	−0.0016 (15)	0.0018 (15)	0.0015 (13)
C2	0.0352 (16)	0.0484 (19)	0.0452 (16)	−0.0016 (14)	−0.0071 (14)	0.0028 (15)
C6	0.0396 (15)	0.0337 (15)	0.0345 (13)	0.0022 (13)	−0.0036 (12)	0.0031 (12)
C12	0.084 (3)	0.076 (3)	0.0504 (19)	0.009 (2)	0.023 (2)	0.001 (2)
C1	0.0361 (18)	0.061 (2)	0.0401 (15)	0.0023 (14)	−0.0006 (13)	0.0114 (15)
C8	0.0600 (18)	0.0426 (16)	0.0407 (14)	−0.0031 (18)	0.0032 (16)	0.0053 (12)

Geometric parameters (Å, º) top

S1—O5	1.417 (2)	C9—C10	1.379 (5)
S1—O6	1.418 (2)	C9—C12	1.510 (4)
S1—O4	1.575 (2)	C11—C10	1.382 (5)
S1—C6	1.747 (3)	C11—C6	1.382 (4)
O4—C5	1.454 (3)	C11—H11	0.9500
O3—C3	1.430 (4)	C4—H4	1.0000
O3—H3	0.8400	C10—H10	0.9500
O1—C4	1.439 (3)	C7—C6	1.378 (4)
O1—C1	1.443 (3)	C7—C8	1.381 (4)
C3—C4	1.491 (4)	C7—H7	0.9500
C3—C2	1.516 (4)	C2—C1	1.513 (4)
C3—H3A	1.0000	C2—H2A	1.0000
C5—C4	1.491 (4)	C12—H12A	0.9800
C5—H5A	0.9900	C12—H12B	0.9800
C5—H5B	0.9900	C12—H12C	0.9800
O2—C2	1.418 (4)	C1—H1A	0.9900
O2—H2	0.8400	C1—H1B	0.9900
C9—C8	1.376 (4)	C8—H8	0.9500

O5—S1—O6	119.47 (15)	C5—C4—H4	108.8
O5—S1—O4	103.55 (13)	C3—C4—H4	108.8
O6—S1—O4	109.01 (12)	C9—C10—C11	121.4 (3)
O5—S1—C6	110.27 (14)	C9—C10—H10	119.3
O6—S1—C6	109.91 (14)	C11—C10—H10	119.3
O4—S1—C6	103.24 (13)	C6—C7—C8	119.2 (3)
C5—O4—S1	117.54 (17)	C6—C7—H7	120.4
C3—O3—H3	109.5	C8—C7—H7	120.4
C4—O1—C1	107.7 (2)	O2—C2—C1	107.8 (3)
O3—C3—C4	107.4 (2)	O2—C2—C3	110.3 (3)
O3—C3—C2	110.4 (2)	C1—C2—C3	102.2 (2)
C4—C3—C2	101.6 (2)	O2—C2—H2A	112.0
O3—C3—H3A	112.3	C1—C2—H2A	112.0
C4—C3—H3A	112.3	C3—C2—H2A	112.0
C2—C3—H3A	112.3	C7—C6—C11	121.1 (3)
O4—C5—C4	107.3 (2)	C7—C6—S1	120.5 (2)
O4—C5—H5A	110.2	C11—C6—S1	118.4 (2)
C4—C5—H5A	110.2	C9—C12—H12A	109.5
O4—C5—H5B	110.2	C9—C12—H12B	109.5
C4—C5—H5B	110.2	H12A—C12—H12B	109.5
H5A—C5—H5B	108.5	C9—C12—H12C	109.5
C2—O2—H2	109.5	H12A—C12—H12C	109.5
C8—C9—C10	118.9 (3)	H12B—C12—H12C	109.5
C8—C9—C12	120.1 (3)	O1—C1—C2	107.0 (2)
C10—C9—C12	121.0 (3)	O1—C1—H1A	110.3
C10—C11—C6	118.4 (3)	C2—C1—H1A	110.3
C10—C11—H11	120.8	O1—C1—H1B	110.3
C6—C11—H11	120.8	C2—C1—H1B	110.3
O1—C4—C5	110.1 (2)	H1A—C1—H1B	108.6
O1—C4—C3	104.2 (2)	C9—C8—C7	120.9 (3)
C5—C4—C3	115.9 (2)	C9—C8—H8	119.5
O1—C4—H4	108.8	C7—C8—H8	119.5

O5—S1—O4—C5	167.5 (2)	C4—C3—C2—C1	36.7 (3)
O6—S1—O4—C5	39.3 (2)	C8—C7—C6—C11	2.2 (4)
C6—S1—O4—C5	−77.5 (2)	C8—C7—C6—S1	−176.4 (2)
S1—O4—C5—C4	177.38 (18)	C10—C11—C6—C7	−2.1 (4)
C1—O1—C4—C5	154.6 (2)	C10—C11—C6—S1	176.5 (2)
C1—O1—C4—C3	29.6 (3)	O5—S1—C6—C7	−152.8 (2)
O4—C5—C4—O1	66.7 (3)	O6—S1—C6—C7	−19.1 (3)
O4—C5—C4—C3	−175.4 (2)	O4—S1—C6—C7	97.1 (3)
O3—C3—C4—O1	74.7 (3)	O5—S1—C6—C11	28.5 (3)
C2—C3—C4—O1	−41.3 (3)	O6—S1—C6—C11	162.3 (2)
O3—C3—C4—C5	−46.5 (3)	O4—S1—C6—C11	−81.6 (2)
C2—C3—C4—C5	−162.5 (2)	C4—O1—C1—C2	−5.7 (3)
C8—C9—C10—C11	0.8 (5)	O2—C2—C1—O1	96.4 (3)
C12—C9—C10—C11	−178.9 (3)	C3—C2—C1—O1	−19.8 (3)
C6—C11—C10—C9	0.6 (5)	C10—C9—C8—C7	−0.7 (5)
O3—C3—C2—O2	168.6 (2)	C12—C9—C8—C7	178.9 (3)
C4—C3—C2—O2	−77.6 (3)	C6—C7—C8—C9	−0.7 (5)
O3—C3—C2—C1	−77.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.84	2.03	2.834 (4)	160
O3—H3···O3ⁱⁱ	0.84	2.17	2.931 (2)	151

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆O₆S
M_r	288.31
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	5.414 (4), 10.172 (8), 24.080 (18)
V (Å³)	1326.0 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.879, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	14329, 3154, 2333
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.672

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.110, 1.02
No. of reflections	3154
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.19
Absolute structure	Flack (1983), with 1174 Friedel pairs
Absolute structure parameter	0.47 (12)

Computer programs: APEX2 (Bruker, 2005), SMART (Bruker, 2005), 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
O2—H2···O1ⁱ	0.84	2.03	2.834 (4)	159.6
O3—H3···O3ⁱⁱ	0.84	2.17	2.931 (2)	151.0

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

Acknowledgements

This work was supported in part by the National Institutes of Health (grant No. R01 AI72012).

References

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