2-(2-Hydro­xy­phenyl)-1,3-di­thia­ne

In the title compound, C₁₀H₁₂OS₂, the di­thia­ne ring adopts a chair conformation. An intramolecular C—H...O interaction forms an S(5) graph-set ring. Intermolecular O—H...S and C—H...O hydrogen bonds link the mol­ecules into sheet-like assemblies parallel to the ab plane.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.063
• wR factor = 0.137
• Data-to-parameter ratio = 15.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Protection of carbonyl compounds as cyclic S and S-acetals, such as 1,3-dithianes and dithiolanes, and regeneration of parent carbonyl compounds from these derivatives are of considerable contemporary interest of organic chemists in view of the central importance of carbonyl compounds in organic synthesis (Greene & Wuts, 1991). Derivatives of 1,3-dithiane are particularly important as versatile intermediates in organic sythesis because they are utilized as acyl anion equivalents via temporary inversion of electrophilic carbonyl carbon. This is through metallation thereby allowing carbon–carbon-forming reaction through electrophiles (Grobel & Seebeck, 1977). These derivatives are easy to form and display remarkable stability towards acid as well as acidic hydrolysis. The presence of electron-donor and electron-withdrawing groups in the aromatic ring is a crucial factor which determines the ease of cleavage of C—S bond using soft electrophiles as reagents (Corey & Erickson, 1971). However, the presence of dithiane moiety together with another functional group capable of forming hydrogen bonds in the solid state is of special interest to get an insight into the orientation and hydrogen bonding of the dithiane ring (Jeffrey & Saenger, 1991; Desiraju, 1996). In view of this important factor, the crystal structure determination of the title compound, (I), was undertaken, and the results are reported here.

The bond lengths observed in (I) (Fig. 1) have normal values (Allen et al., 1987) and the bond lengths and angles are comparable to those in the related structure 2-(2,6-difluorophenyl)-1,3-dithiane, (II) (Adamson et al., 1995). As observed in (II), the dithiane ring adopts a chair conformation. The conformation about the C6—C7 bond joining the dithiane and phenyl rings is better described by the torsion angles C1—C6—C7—S1 [−97.1 (2)°] and C5—C6—C7—S1 [80.2 (3)°]. An intramolecular C7—H7···O1 interaction forms an S(5) graph-set ring (Etter et al., 1990). In the solid state, intermolecular hydrogen bonds involving the hydroxy group and the dithiane ring, O1—H11···S2ⁱ and C10—H10A···O1ⁱⁱ, interconnect the molecules into sheet-like assemblies parallel to the ab plane (Fig. 2). The symmetry codes are as in Table 2.

S2. Experimental

To a solution of salicylaldehyde (18.7 mmol) in 1,3-propanedithiol (39.9 mmol), boron trifluoride etherate (2 ml) was added with stirring at 273 K for 15 min. After completion of the reaction, the mixture was poured into a saturated solution of sodium hydrogen carbonate (50 ml) and was extracted three times with ethyl acetate. The organic layer was washed repeatedly with sodium hydrogen carbonate and water. Finally, the organiclayer was dried over anhydrous sodium sulfate. The solvent was removed under vacuum and the title compound was isolated using column chromatography with petroleum ether as eluant. Single crystals suitable for X-ray analysis were obtained from a solution in petroleum ether.

S3. Refinement

All H atoms were located from a difference Fourier map and were refined isotropically. The C—H distances ranged from 0.89 (4) to 1.00 (4) Å and the O—H distance is 0.73 (3) Å. The highest peak was 0.89 Å from S1.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme, with ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of (I), showing molecular sheets parallel to the ab plane.

2-(2-hydroxyphenyl)-1,3-dithiane

Crystal data

C10H12OS2	F(000) = 896
Mr = 212.32	Dx = 1.383 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4761 reflections
a = 10.4039 (7) Å	θ = 2.3–28.3°
b = 11.0435 (8) Å	µ = 0.48 mm^−1
c = 17.7471 (12) Å	T = 293 K
V = 2039.1 (2) Å^3	Block, colorless
Z = 8	0.46 × 0.40 × 0.24 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2524 independent reflections
Radiation source: fine-focus sealed tube	2080 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.3°
ω scans	h = −13→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.810, Tmax = 0.894	l = −23→19
10961 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	All H-atom parameters refined
S = 1.24	w = 1/[σ^2(Fo^2) + (0.0449P)^2 + 2.164P] where P = (Fo^2 + 2Fc^2)/3
2524 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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	0.10966 (7)	0.79030 (7)	0.46299 (4)	0.0403 (2)
S2	0.13055 (7)	0.99695 (7)	0.35365 (5)	0.0413 (2)
O1	−0.0336 (2)	0.6495 (2)	0.29253 (13)	0.0410 (5)
C1	−0.1188 (2)	0.7343 (2)	0.31748 (15)	0.0283 (5)
C2	−0.2502 (3)	0.7219 (3)	0.30661 (17)	0.0348 (6)
C3	−0.3335 (3)	0.8100 (3)	0.33361 (18)	0.0402 (7)
C4	−0.2859 (3)	0.9099 (3)	0.37124 (18)	0.0405 (7)
C5	−0.1547 (3)	0.9214 (3)	0.38268 (17)	0.0350 (6)
C6	−0.0688 (2)	0.8344 (2)	0.35539 (14)	0.0268 (5)
C7	0.0734 (2)	0.8437 (2)	0.36868 (14)	0.0262 (5)
C8	0.2837 (3)	0.7982 (4)	0.4598 (2)	0.0497 (8)
C9	0.3369 (3)	0.9215 (3)	0.4407 (2)	0.0452 (8)
C10	0.3011 (3)	0.9682 (4)	0.3640 (2)	0.0459 (8)
H2	−0.281 (3)	0.655 (3)	0.2812 (16)	0.035 (8)*
H3	−0.421 (4)	0.800 (3)	0.3251 (19)	0.046 (9)*
H4	−0.340 (4)	0.967 (3)	0.388 (2)	0.049 (10)*
H5	−0.123 (3)	0.985 (3)	0.4076 (17)	0.026 (7)*
H7	0.117 (3)	0.796 (3)	0.331 (2)	0.045 (9)*
H8A	0.306 (4)	0.772 (4)	0.512 (3)	0.068 (12)*
H8B	0.309 (4)	0.744 (4)	0.423 (2)	0.058 (12)*
H9A	0.308 (3)	0.985 (3)	0.4737 (19)	0.043 (9)*
H9B	0.423 (4)	0.916 (3)	0.443 (2)	0.058 (11)*
H10A	0.341 (4)	1.044 (4)	0.351 (2)	0.068 (12)*
H10B	0.322 (4)	0.914 (3)	0.327 (2)	0.053 (11)*
H11	−0.062 (3)	0.603 (3)	0.2681 (19)	0.036 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0288 (4)	0.0503 (5)	0.0419 (4)	−0.0060 (3)	−0.0061 (3)	0.0178 (3)
S2	0.0372 (4)	0.0352 (4)	0.0515 (5)	−0.0111 (3)	−0.0074 (3)	0.0132 (3)
O1	0.0274 (10)	0.0365 (11)	0.0592 (14)	0.0010 (9)	−0.0053 (9)	−0.0180 (11)
C1	0.0253 (12)	0.0301 (13)	0.0293 (13)	0.0013 (10)	−0.0024 (10)	0.0001 (10)
C2	0.0268 (13)	0.0383 (16)	0.0392 (15)	−0.0050 (12)	−0.0053 (12)	−0.0030 (12)
C3	0.0226 (13)	0.0574 (19)	0.0406 (16)	−0.0015 (13)	−0.0052 (12)	0.0024 (14)
C4	0.0326 (15)	0.0476 (18)	0.0413 (16)	0.0126 (13)	0.0015 (12)	−0.0023 (14)
C5	0.0325 (14)	0.0358 (15)	0.0367 (15)	0.0025 (12)	−0.0013 (12)	−0.0051 (12)
C6	0.0243 (12)	0.0303 (13)	0.0257 (12)	−0.0012 (10)	−0.0002 (10)	0.0027 (10)
C7	0.0240 (12)	0.0268 (12)	0.0278 (12)	−0.0037 (10)	−0.0011 (10)	−0.0011 (10)
C8	0.0283 (15)	0.057 (2)	0.064 (2)	0.0002 (14)	−0.0109 (15)	0.0114 (19)
C9	0.0252 (14)	0.057 (2)	0.0536 (19)	−0.0070 (14)	−0.0050 (14)	−0.0072 (16)
C10	0.0315 (15)	0.054 (2)	0.052 (2)	−0.0175 (14)	0.0040 (14)	0.0029 (16)

Geometric parameters (Å, º)

S1—C8	1.814 (3)	C4—H4	0.89 (4)
S1—C7	1.814 (3)	C5—C6	1.399 (4)
S2—C10	1.812 (3)	C5—H5	0.89 (3)
S2—C7	1.813 (3)	C6—C7	1.502 (4)
O1—C1	1.364 (3)	C7—H7	0.96 (4)
O1—H11	0.73 (3)	C8—C9	1.509 (5)
C1—C2	1.387 (4)	C8—H8A	1.00 (4)
C1—C6	1.394 (4)	C8—H8B	0.92 (4)
C2—C3	1.388 (4)	C9—C10	1.502 (5)
C2—H2	0.92 (3)	C9—H9A	0.96 (3)
C3—C4	1.381 (5)	C9—H9B	0.90 (4)
C3—H3	0.93 (4)	C10—H10A	0.97 (5)
C4—C5	1.386 (4)	C10—H10B	0.92 (4)
C8—S1—C7	99.4 (2)	S2—C7—S1	111.8 (1)
C10—S2—C7	98.2 (2)	C6—C7—H7	108 (2)
C1—O1—H11	114 (3)	S2—C7—H7	105 (2)
O1—C1—C2	121.8 (2)	S1—C7—H7	111 (2)
O1—C1—C6	117.3 (2)	C9—C8—S1	114.6 (2)
C2—C1—C6	120.9 (2)	C9—C8—H8A	113 (2)
C1—C2—C3	119.9 (3)	S1—C8—H8A	101 (2)
C1—C2—H2	119.6 (19)	C9—C8—H8B	109 (3)
C3—C2—H2	120.6 (19)	S1—C8—H8B	106 (2)
C4—C3—C2	120.2 (3)	H8A—C8—H8B	114 (4)
C4—C3—H3	122 (2)	C10—C9—C8	115.0 (3)
C2—C3—H3	118 (2)	C10—C9—H9A	103 (2)
C3—C4—C5	119.8 (3)	C8—C9—H9A	114 (2)
C3—C4—H4	120 (2)	C10—C9—H9B	108 (2)
C5—C4—H4	121 (2)	C8—C9—H9B	107 (2)
C4—C5—C6	121.1 (3)	H9A—C9—H9B	109 (3)
C4—C5—H5	120.3 (18)	C9—C10—S2	113.2 (2)
C6—C5—H5	118.6 (19)	C9—C10—H10A	114 (2)
C1—C6—C5	118.2 (2)	S2—C10—H10A	104 (3)
C1—C6—C7	119.9 (2)	C9—C10—H10B	112 (2)
C5—C6—C7	121.9 (2)	S2—C10—H10B	106 (2)
C6—C7—S2	111.3 (2)	H10A—C10—H10B	107 (3)
C6—C7—S1	109.1 (2)
O1—C1—C2—C3	179.4 (3)	C5—C6—C7—S2	−43.6 (3)
C6—C1—C2—C3	0.1 (4)	C1—C6—C7—S1	−97.1 (2)
C1—C2—C3—C4	0.0 (5)	C5—C6—C7—S1	80.2 (3)
C2—C3—C4—C5	−0.7 (5)	C10—S2—C7—C6	−174.0 (2)
C3—C4—C5—C6	1.3 (5)	C10—S2—C7—S1	63.72 (18)
O1—C1—C6—C5	−178.8 (2)	C8—S1—C7—C6	174.9 (2)
C2—C1—C6—C5	0.5 (4)	C8—S1—C7—S2	−61.5 (2)
O1—C1—C6—C7	−1.4 (4)	C7—S1—C8—C9	56.7 (3)
C2—C1—C6—C7	178.0 (2)	S1—C8—C9—C10	−62.6 (4)
C4—C5—C6—C1	−1.2 (4)	C8—C9—C10—S2	65.5 (4)
C4—C5—C6—C7	−178.6 (3)	C7—S2—C10—C9	−61.9 (3)
C1—C6—C7—S2	139.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.96 (3)	2.35 (3)	2.769 (3)	105 (2)
O1—H11···S2^i	0.73 (3)	2.56 (3)	3.254 (2)	159 (3)
C10—H10A···O1^ii	0.96 (4)	2.54 (4)	3.387 (4)	147 (3)

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