(2S,R_S)-6-Phenyl-1-(p-tolyl­sulfinyl)­hexa-3(E),5(E)-dien-2-ol

The mol­ecule of the title compound, C₁₉H₂₀O₂S, corresponds to a chiral sulfinyldienol with two stereogenic centres, viz. the C atom susbtituted by the hydr­oxy group and the sulfinyl S atom. The mol­ecule displays a V-shape in the solid state. The dihedral angle defined by the least-squares planes of the aromatic rings is 72.9 (1)°. The packing pattern exhibits the following inter­molecular hydrogen bonds: one O—H...O [H...O = 1.98 Å, O...O = 2.785 (4) Å and O—H...O = 166°] and two C—H...O [H...O = 2.58 and 2.60 Å, C...O = 3.527 (5) and 3.347 (5) Å, and C—H...O = 164 and 134°]. These define a chain along b.

S1. Comment

Continuing our search for supramolecular synthons for the crystal engineering of substituted aromatic compounds (Araya-Maturana et al., 2005), our group has focused on the crystalline properties of chiral sulfinyl dienols, particularly in the packing patterns obtained by hydrogen bonding. Sulfinyl dienes have been used as an ideal substrate in Diels–Alder cycloadditions, where the presence of the sulfinyl group provides an extra element of stereocontrol (Carreño, 1995). The introduction of an hydroxyl group, bound next to the sulfinyl, to form the so-called sulfinyl dienols, provides a new stereogenic centre which can be coordinated by a suitable dienophile through intermolecular hydrogen bonding in the transition state of Diels–Alder cycloadditions, thus providing a new diastereoselectivity control in the reaction, since the role of intermolecular hydrogen bonding in the regio- and stereochemical outcome of Diels–Alder reactions of dienes with hydroxyl groups has been well recognized (Araya-Maturana et al., 1999; Fernández de la Pradilla et al., 2005). The crystal structures of sulfinyl dienols are unknown, but the X-ray crystal structure of the β-hydroxidesulfoxide moiety of 2-(p-tolylsulfinyl)cyclohexanol previously has been established (Garcia Ruano et al., 1996). We now present the crystal structure of the title sulfinyl dienol, (I).

The molecule of (I) has a seven-atom chain connecting the phenyl and p-tolyl groups (Fig. 1). The chain contains two adjacent C═C double bonds (C12═C13 and C10═C11) and an S atom. It is important to note that both double bonds exhibit a trans arrangment. The chain is not planar but contains two planar segments of atoms, C9–C14 and C9/C8/S/C1, including the aromatic ring C atom and with C9 as the common atom. In both cases, the atoms show small deviations from the corresponding least-squares planes. The chain is twisted at C9, with a dihedral angle of 56.8° between the two segments. Consequently, the C8—C9—C10—C11 torsion angle is −127.2 (4)° and the molecule is asymmetrically V-shaped, with one arm longer than the other. This is also reflected in the angle defined by the C17···C9 and C9···C4 vectors, with a value of 50.0°. The phenyl ring is not completely coplanar with the C14–C9 segment, with a dihedral angle of 19.6 (3)° between the two least-square planes. The opposite is observed with the p-tolyl ring, which is almost perpendicular to the C9/C8/S/C1 segment, with a dihedral angle of 87.5 (1)°. The bent shape of the molecule is also reflected in the dihedral angle between the aromatic rings of 72.9 (1)°.

The packing structure of the molecule displays an intermolecular hydrogen-bonded chain along the b axis, in a `concave–convex' arrangement (Fig. 2). Two adjacent molecules have their arms pointing towards opposite sides of the central C9 atom and they are separated by b/2 as they are related by the 2₁ screw axis of the space group. The hydrogen bond is then defined between the hydroxy atom H2A and the sulfinyl atom O1, with a distance of 1.724 Å. Thus, the molecular conformation precludes intramolecular H2A···O1 bonding, favouring the intermolecular interaction. This kind of intramolecular hydrogen bonding has previously been described for sulfinyl alcohols (Broutin & Colobert, 2003, 2005; Loughlin et al., 2002; Satoh et al., 2002). It has been pointed out (Fernández de la Pradilla et al., 2005) that intermolecular hydrogen bonding plays a key role in the stereoselectivity of the Diels–Alders reaction of this type of diene.

S2. Experimental

The stereoselective synthesis of compound (I) was carried out as follows. To a cooled solution (195 K, dry ice–acetone) of (R_S)-6-phenyl-1-(p-tolylsulfinyl)-3(E),5(E)-hexadien-2-one (0.55 mmol) dissolved in dry tetrahydrofuran (5 ml), diisobutyl aluminium hydride (DIBALH; 1.4 ml) was added dropwise. After 60 min, methanol (1.5 ml) was added and the reaction mixture was allowed to reach ambient temperature. The solvent was then evaporated completely at reduced pressure and the resulting solid was resuspended and stirred into 5% sulfuric acid for 15 min. The mixture was then extracted with ethyl acetate. Concentration of the solution and purification by column chromatography (ethyl acetate–hexane 1:0.7 v/v) afforded a white solid (60% yield), which was recrystallized from a mixture of ethyl acetate and hexane (Ratio?) (m.p. = 398–400 K).

S3. Refinement

The H atoms of the organic skeleton were introduced in calculated positions and then refined using a riding model, with C—H distances of 0.93, 0.96 or 0.98 Å. The hydroxy atom H2A was located in a difference synthesis during the final stages of the structure completion. Its coordinates were not subsequently refined but the isotropic displacement parameter [Text missing?].

Computing details

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT; program(s) used to solve structure: SHELXTL-NT (Bruker, 1999); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing view of (I), showing the unit cell. [Symmetry codes: (A) 1 − x, y − 1/2, 1 − z; (B) 1 − x, y + 1/2, 1 − z.]

(2S,R_S)-6-Phenyl-1-(p-tolylsulfinyl)hexa-3(E),5(E)-dien-2-ol

Crystal data

C19H20O2S	F(000) = 332
Mr = 312.41	Dx = 1.212 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1065 reflections
a = 5.9765 (12) Å	θ = 4.5–36.3°
b = 7.9484 (16) Å	µ = 0.19 mm^−1
c = 18.130 (4) Å	T = 273 K
β = 96.439 (4)°	Plate, colourless
V = 855.8 (3) Å^3	0.50 × 0.23 × 0.06 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	2977 independent reflections
Radiation source: fine-focus sealed tube	2232 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 25.1°, θmin = 2.3°
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999)	h = −7→7
Tmin = 0.910, Tmax = 0.989	k = −9→9
5368 measured reflections	l = −21→21

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.063	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0401P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2977 reflections	Δρmax = 0.32 e Å^−3
201 parameters	Δρmin = −0.13 e Å^−3
1 restraint	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.05 (12)

Special details

Experimental. Each frame was mesured during 30 s, using 0.3 /% between frames.

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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

2.2914 (0.0105) x + 6.0239 (0.0086) y − 10.2894 (0.0255) z = 0.9052 (0.0051)

* −0.0097 (0.0029) C14 * 0.0025 (0.0030) C15 * 0.0065 (0.0035) C16 * −0.0083 (0.0037) C17 * 0.0010 (0.0036) C18 * 0.0080 (0.0033) C19

Rms deviation of fitted atoms = 0.0068

0.4228 (0.0304) x + 6.9705 (0.0034) y − 8.7071 (0.0151) z = 0.6067 (0.0152)

Angle to previous plane (with approximate e.s.d.) = 19.50 (0.26)

* −0.0563 (0.0026) C14 * 0.0003 (0.0026) C13 * 0.0580 (0.0030) C12 * 0.0625 (0.0031) C11 * −0.0166 (0.0025) C10 * −0.0479 (0.0024) C9

Rms deviation of fitted atoms = 0.0466

− 4.6888 (0.0101) x + 4.7466 (0.0181) y − 1.4136 (0.0224) z = 0.6202 (0.0192)

Angle to previous plane (with approximate e.s.d.) = 56.80 (0.30)

* 0.0120 (0.0020) C9 * −0.0134 (0.0022) C8 * −0.0085 (0.0014) S1 * 0.0100 (0.0017) C1

Rms deviation of fitted atoms = 0.0111

2.4174 (0.0092) x + 5.0845 (0.0099) y + 10.9529 (0.0232) z = 10.1611 (0.0136)

Angle to previous plane (with approximate e.s.d.) = 87.45 (0.13)

* 0.0122 (0.0027) C1 * −0.0104 (0.0030) C2 * 0.0003 (0.0031) C3 * 0.0081 (0.0030) C4 * −0.0064 (0.0031) C5 * −0.0038 (0.0030) C6

Rms deviation of fitted atoms = 0.0079

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	0.33494 (15)	0.63215 (14)	0.57893 (5)	0.0644 (3)
O1	0.2172 (4)	0.7979 (3)	0.56769 (16)	0.0774 (8)
C1	0.1962 (7)	0.5186 (5)	0.6448 (2)	0.0637 (10)
C2	−0.0082 (7)	0.5698 (5)	0.6641 (2)	0.0770 (13)
H2	−0.0853	0.6573	0.6384	0.092*
C3	−0.0992 (8)	0.4917 (6)	0.7215 (3)	0.0874 (14)
H3	−0.2367	0.5293	0.7346	0.105*
C4	0.0065 (9)	0.3597 (5)	0.7601 (2)	0.0737 (12)
C5	0.2066 (8)	0.3082 (6)	0.7385 (3)	0.0842 (13)
H5	0.2814	0.2179	0.7628	0.101*
C6	0.3012 (7)	0.3861 (5)	0.6816 (2)	0.0768 (13)
H6	0.4381	0.3479	0.6683	0.092*
C7	−0.0907 (9)	0.2817 (6)	0.8244 (3)	0.1095 (18)
H7A	−0.0827	0.3604	0.8647	0.164*
H7B	−0.0068	0.1823	0.8398	0.164*
H7C	−0.2451	0.2521	0.8098	0.164*
C8	0.2427 (6)	0.5155 (5)	0.4972 (2)	0.0672 (11)
H8A	0.2938	0.3999	0.5026	0.081*
H8B	0.0795	0.5157	0.4886	0.081*
C9	0.3417 (7)	0.5992 (5)	0.4320 (2)	0.0679 (11)
H9	0.2855	0.7151	0.4293	0.081*
O2	0.5767 (4)	0.6089 (4)	0.44554 (16)	0.0752 (7)
H2A	0.6297	0.5137	0.4488	0.113*
C10	0.2616 (7)	0.5178 (5)	0.3594 (2)	0.0703 (11)
H10	0.1070	0.5062	0.3473	0.084*
C11	0.3924 (8)	0.4620 (5)	0.3120 (2)	0.0708 (11)
H11	0.5462	0.4778	0.3244	0.085*
C12	0.3257 (8)	0.3787 (5)	0.2427 (2)	0.0706 (11)
H12	0.1723	0.3741	0.2269	0.085*
C13	0.4627 (7)	0.3078 (5)	0.1991 (2)	0.0716 (11)
H13	0.6158	0.3175	0.2148	0.086*
C14	0.4045 (7)	0.2167 (5)	0.1299 (2)	0.0644 (11)
C15	0.1949 (8)	0.2295 (5)	0.0896 (2)	0.0754 (12)
H15	0.0878	0.3001	0.1067	0.090*
C16	0.1406 (7)	0.1410 (8)	0.0252 (2)	0.0928 (13)
H16	−0.0015	0.1524	−0.0010	0.111*
C17	0.2956 (10)	0.0360 (7)	−0.0003 (3)	0.1024 (16)
H17	0.2592	−0.0265	−0.0433	0.123*
C18	0.5053 (10)	0.0238 (7)	0.0384 (3)	0.1059 (17)
H18	0.6123	−0.0464	0.0210	0.127*
C19	0.5599 (7)	0.1139 (7)	0.1025 (3)	0.0836 (12)
H19	0.7038	0.1050	0.1277	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0580 (5)	0.0619 (6)	0.0714 (6)	−0.0003 (6)	−0.0013 (4)	−0.0086 (6)
O1	0.0787 (19)	0.0555 (15)	0.097 (2)	0.0028 (15)	0.0047 (15)	−0.0030 (15)
C1	0.060 (2)	0.065 (2)	0.064 (3)	0.003 (2)	−0.001 (2)	−0.012 (2)
C2	0.070 (3)	0.065 (3)	0.096 (3)	0.019 (2)	0.009 (2)	0.001 (2)
C3	0.086 (3)	0.076 (3)	0.104 (4)	0.011 (3)	0.032 (3)	−0.011 (3)
C4	0.102 (4)	0.057 (3)	0.064 (3)	−0.007 (3)	0.016 (3)	−0.016 (2)
C5	0.104 (4)	0.068 (3)	0.080 (3)	0.010 (3)	0.008 (3)	−0.001 (3)
C6	0.078 (3)	0.069 (3)	0.083 (3)	0.018 (2)	0.009 (3)	−0.010 (3)
C7	0.152 (5)	0.095 (4)	0.086 (4)	−0.009 (4)	0.033 (3)	−0.012 (3)
C8	0.070 (3)	0.055 (2)	0.076 (3)	0.001 (2)	0.006 (2)	0.001 (2)
C9	0.084 (3)	0.045 (2)	0.074 (3)	0.007 (2)	0.005 (2)	0.002 (2)
O2	0.0818 (18)	0.0563 (16)	0.0879 (18)	−0.0108 (16)	0.0110 (14)	−0.0020 (19)
C10	0.082 (3)	0.058 (2)	0.069 (3)	0.004 (2)	0.003 (2)	0.009 (2)
C11	0.087 (3)	0.060 (2)	0.064 (3)	−0.003 (2)	0.006 (2)	0.010 (2)
C12	0.079 (3)	0.069 (3)	0.062 (3)	−0.005 (2)	0.002 (2)	0.010 (2)
C13	0.076 (3)	0.072 (3)	0.066 (3)	−0.008 (3)	0.008 (2)	0.008 (2)
C14	0.067 (3)	0.066 (2)	0.062 (3)	−0.004 (2)	0.013 (2)	0.007 (2)
C15	0.079 (3)	0.080 (3)	0.069 (3)	0.007 (2)	0.017 (3)	0.000 (3)
C16	0.088 (3)	0.119 (4)	0.071 (3)	0.001 (4)	0.009 (2)	−0.002 (4)
C17	0.121 (5)	0.105 (4)	0.084 (4)	−0.018 (4)	0.023 (4)	−0.019 (3)
C18	0.113 (5)	0.101 (4)	0.110 (4)	0.014 (4)	0.044 (4)	−0.012 (4)
C19	0.076 (3)	0.086 (3)	0.091 (3)	0.010 (3)	0.018 (2)	−0.003 (3)

Geometric parameters (Å, º)

S1—O1	1.497 (3)	C9—H9	0.9800
S1—C1	1.775 (4)	O2—H2A	0.8200
S1—C8	1.782 (4)	C10—C11	1.304 (5)
C1—C6	1.362 (5)	C10—H10	0.9300
C1—C2	1.370 (5)	C11—C12	1.437 (5)
C2—C3	1.375 (6)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.325 (5)
C3—C4	1.375 (6)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.457 (5)
C4—C5	1.363 (6)	C13—H13	0.9300
C4—C7	1.494 (6)	C14—C19	1.372 (5)
C5—C6	1.377 (6)	C14—C15	1.381 (5)
C5—H5	0.9300	C15—C16	1.371 (6)
C6—H6	0.9300	C15—H15	0.9300
C7—H7A	0.9600	C16—C17	1.366 (6)
C7—H7B	0.9600	C16—H16	0.9300
C7—H7C	0.9600	C17—C18	1.369 (6)
C8—C9	1.531 (5)	C17—H17	0.9300
C8—H8A	0.9700	C18—C19	1.374 (6)
C8—H8B	0.9700	C18—H18	0.9300
C9—O2	1.400 (4)	C19—H19	0.9300
C9—C10	1.496 (5)
O1—S1—C1	106.92 (18)	C10—C9—C8	112.2 (3)
O1—S1—C8	104.34 (17)	O2—C9—H9	106.7
C1—S1—C8	99.82 (18)	C10—C9—H9	106.7
C6—C1—C2	118.6 (4)	C8—C9—H9	106.7
C6—C1—S1	119.9 (3)	C9—O2—H2A	109.5
C2—C1—S1	121.2 (3)	C11—C10—C9	124.8 (4)
C1—C2—C3	120.0 (4)	C11—C10—H10	117.6
C1—C2—H2	120.0	C9—C10—H10	117.6
C3—C2—H2	120.0	C10—C11—C12	127.3 (4)
C2—C3—C4	122.1 (4)	C10—C11—H11	116.3
C2—C3—H3	119.0	C12—C11—H11	116.3
C4—C3—H3	119.0	C13—C12—C11	126.0 (4)
C5—C4—C3	116.8 (4)	C13—C12—H12	117.0
C5—C4—C7	122.0 (5)	C11—C12—H12	117.0
C3—C4—C7	121.2 (5)	C12—C13—C14	128.3 (4)
C4—C5—C6	121.8 (4)	C12—C13—H13	115.8
C4—C5—H5	119.1	C14—C13—H13	115.8
C6—C5—H5	119.1	C19—C14—C15	117.6 (4)
C1—C6—C5	120.6 (4)	C19—C14—C13	120.1 (4)
C1—C6—H6	119.7	C15—C14—C13	122.3 (4)
C5—C6—H6	119.7	C16—C15—C14	121.8 (4)
C4—C7—H7A	109.5	C16—C15—H15	119.1
C4—C7—H7B	109.5	C14—C15—H15	119.1
H7A—C7—H7B	109.5	C17—C16—C15	119.8 (4)
C4—C7—H7C	109.5	C17—C16—H16	120.1
H7A—C7—H7C	109.5	C15—C16—H16	120.1
H7B—C7—H7C	109.5	C16—C17—C18	119.2 (5)
C9—C8—S1	107.8 (3)	C16—C17—H17	120.4
C9—C8—H8A	110.2	C18—C17—H17	120.4
S1—C8—H8A	110.2	C17—C18—C19	120.9 (5)
C9—C8—H8B	110.2	C17—C18—H18	119.6
S1—C8—H8B	110.2	C19—C18—H18	119.6
H8A—C8—H8B	108.5	C14—C19—C18	120.8 (4)
O2—C9—C10	113.2 (3)	C14—C19—H19	119.6
O2—C9—C8	110.9 (3)	C18—C19—H19	119.6
O1—S1—C1—C6	−161.4 (3)	S1—C8—C9—C10	−176.1 (3)
C8—S1—C1—C6	90.2 (3)	O2—C9—C10—C11	−0.7 (6)
O1—S1—C1—C2	13.2 (4)	C8—C9—C10—C11	−127.0 (4)
C8—S1—C1—C2	−95.2 (3)	C9—C10—C11—C12	178.1 (4)
C6—C1—C2—C3	2.4 (6)	C10—C11—C12—C13	−172.5 (4)
S1—C1—C2—C3	−172.3 (3)	C11—C12—C13—C14	177.5 (4)
C1—C2—C3—C4	−1.3 (7)	C12—C13—C14—C19	−162.4 (4)
C2—C3—C4—C5	−0.5 (7)	C12—C13—C14—C15	17.6 (7)
C2—C3—C4—C7	177.3 (4)	C19—C14—C15—C16	1.2 (6)
C3—C4—C5—C6	1.1 (7)	C13—C14—C15—C16	−178.8 (4)
C7—C4—C5—C6	−176.6 (4)	C14—C15—C16—C17	0.4 (7)
C2—C1—C6—C5	−1.7 (6)	C15—C16—C17—C18	−1.4 (8)
S1—C1—C6—C5	172.9 (3)	C16—C17—C18—C19	0.8 (8)
C4—C5—C6—C1	0.0 (7)	C15—C14—C19—C18	−1.8 (6)
O1—S1—C8—C9	68.0 (3)	C13—C14—C19—C18	178.3 (4)
C1—S1—C8—C9	178.4 (3)	C17—C18—C19—C14	0.8 (8)
S1—C8—C9—O2	56.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^i	0.82	1.98	2.785 (4)	166
C8—H8A···O2^i	0.97	2.58	3.527 (5)	164
C8—H8B···O1^ii	0.97	2.60	3.347 (5)	134

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