1,2-Dimeth­oxy-4-methyl-3-[(S)-p-tolyl­sulfin­yl]benzene

Mastranzo, V.M.; Olivares, J.L.; Sánchez-Obregón, R.; Yuste, F.; Toscano, R.A.

doi:10.1107/S1600536811041420

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o2950

doi:10.1107/S1600536811041420

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1,2-Dimethoxy-4-methyl-3-[(S)-p-tolylsulfinyl]benzene

Virginia M. Mastranzo,^a José Luis Olivares,^a Rubén Sánchez-Obregón,^a Francisco Yuste ^a and Rubén A. Toscano ^a ^*

^aInstituto de Química, UNAM, Circuito Exterior, Ciudad Universitaria, Delegación Coyoacán, CP 04510, México, DF, Mexico
^*Correspondence e-mail: toscano@unam.mx

(Received 29 September 2011; accepted 7 October 2011; online 12 October 2011)

In the title compound, C₁₆H₁₈O₃S, the dihedral angle between the benzene rings is 75.48 (8)°. The absolute configuration at the stereogenic S-atom center was determined as S. The crystal structure is stabilized by intermolecular C—H⋯O contacts.

Related literature

For related sulfoxides, see: Brondel et al. (2010 ); Fuller et al. (2009 ). The title compound was prepared as a starting material for the synthesis of the tetrahydroprotoberberine alkaloids (S)-(−)-tetrahydropalmatine and (S)-(−)-canadine following a synthetic strategy similar to that used for the synthesis of (S)-(−)-xylopinine (Mastranzo et al., 2011 ).

Experimental

Crystal data

C₁₆H₁₈O₃S
M_r = 290.36
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.4170 (6) Å
b = 8.5406 (7) Å
c = 24.0980 (19) Å
V = 1526.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 298 K
0.38 × 0.37 × 0.31 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ) T_min = 0.922, T_max = 0.942
20418 measured reflections
3645 independent reflections
3380 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.099
S = 1.06
3645 reflections
185 parameters
H-atom parameters not refined
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack (1983 ), 1534 Friedel pairs
Flack parameter: 0.01 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O3ⁱ	0.96	2.58	3.366 (3)	139
C14—H14⋯O1ⁱⁱ	0.93	2.59	3.457 (2)	155
C15—H15⋯O2ⁱⁱ	0.93	2.55	3.3886 (18)	150
C12—H12⋯O3ⁱⁱⁱ	0.93	2.56	3.406 (2)	152
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 2006 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811041420/bt5660sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041420/bt5660Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811041420/bt5660Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811041420/bt5660Isup4.cml

checkCIF report

Comment top

The compound (S)-1,2-dimethoxy-4-methyl-3-(p-tolylsulfinyl)benzene was prepared as starting material for the synthesis of the tetrahydroprotoberberine alkaloids (S)-(-)-tetrahydropalmatine and (S)-(-)-canadine following a synthetic strategy similar to that used for the synthesis of (S)-(-)-xylopinine (Mastranzo et al., 2011). The absolute configuration of the levorotatory 1,2-dimethoxy-4-methyl-3- (p-tolylsulfinyl)benzene (I) was determined by X-ray structure analysis. Figure 1 clearly shows that has the (S) configuration at the stereogenic S1 center. The geometry at S1 conforms to that found for related p-tolyl sulfinyl derivatives, it adopts an asymmetric propeller-like conformation having the corresponding C_ortho—C_ipso—S—O dihedral angles equal to -53.11 (15) and -28.07 (16)°. The dihedral angle defined by the least-squares planes of the aromatic rings is 75.48 (8)°. In the structure there are some intermolecular C—H···O contacts.

Related literature top

For related sulfoxides, see: Brondel et al. (2010); Fuller et al. (2009). The title compound was prepared as a starting material for the synthesis of the tetrahydroprotoberberine alkaloids (S)-(-)-tetrahydropalmatine and (S)-(-)-canadine following a synthetic strategy similar to that used for the

synthesis of (S)-(-)-xylopinine (Mastranzo et al., 2011).

Experimental top

1-(3,4-Dimethoxyphenyl)-N,N-dimethylmethanamine

To a stirred solution of dimethylamine hydrochloride (6.4 g, 78.48 mmol) in MeOH (100 ml) KOH (1.2 g, 21.38 mmol) was added. When the pellets were completely dissolved, 3,4-dimethoxybenzaldehyde (10.0 g, 60.17 mmol) was added in one portion. The resulting suspension was stirred at room temperature for 15 min. Then, a solution of NaBH₃CN (1.5 g, 23.87 mmol) in MeOH (15 ml) was added dropwise over 30 min. After the addition was complete, the suspension was stirred for 5 h. Potassium hydroxide (15 g) was then added, and stirring was continued until the pellets were completely dissolved. The reaction mixture was filtered with suction, and the filtrate was reduced to approximately 50 ml with a rotary evaporator while the bath temperature was kept below 40°C. To this concentrate EtOAc (100 mL) and brine (25 ml) were added and the layers were separated. The aqueous layer was extracted with EtOAc (2x50 ml). The combined organic layers were washed with brine (10 ml), dried over anhydrous potassium carbonate and concentrated. The residue was purified by flash chromatography (98:2 EtOAc/Et₃N) to obtain a pale yellow liquid (8.21 g, 70% yield).

(S)-1-[3,4-Dimethoxy-2-(p-tolylsulfinyl)phenyl]-N,N-dimethylmethanamine

To a stirred solution of 1-(3,4-dimethoxyphenyl)-N,N-dimethylmethanamine (1.6 g, 8.20 mmol) in THF (30 ml) cooled at 0–5°C a 2.3 M solution in hexanes of n-BuLi (4.1 ml, 9.02 mmol) was added dropwise. After 2 h, a solution of (S)-menthyl p-toluenesulfinate (2.9 g, 9.84 mmol) in THF (10 ml) was added via cannula. The resulting mixture was stirred at room temperature for 4 h. Then, the reaction mixture was quenched with of saturated NH₄Cl (10 ml) and extracted with EtOAc (3 x 20 ml). The combined organic layers were dried over Na₂SO₄ and evaporated. The residue was purified by flash chromatography (99:1 EtOAc/Et₃N) to give a pale yellow oil (2.4 g, 88% yield), [α]_D -16.5 (c 1, CHCl₃).

(S)-1-(Chloromethyl)-3,4-dimethoxy-2-(p-tolylsulfinyl)benzene

To a slurry of (S)-1-[3,4-dimethoxy-2-(p-tolylsulfinyl)phenyl]-N,N- dimethyl methanamine (4.02 g, 11.98 mmol, 1 equiv) and K₂CO₃ (2.64 g, 19.17 mmol, 1.6 equiv) in THF (10 ml) cooled at -78°C ethyl chloroformate (2.08 g, 19.17 mmol, 1.6 equiv) was added. The reaction was stirred at room temperature for 12 h. The resulting mixture was quenched with water (10 ml) and extracted with EtOAc (3x15 ml). The combined organic layers were dried over Na₂SO₄ and evaporated. The residue was purified by flash chromatography (70:30 hexane/EtOAc) to give a pale yellow solid (2.66 g, 68% yield), mp 77–78°C, [α]_D -132.4 (c 1, CHCl₃).

(S)-1,2-Dimethoxy-4-methyl-3-(p-tolylsulfinyl)benzene (I)

A mixture of (S)-1-(chloromethyl)-3,4-dimethoxy-2-(p-tolylsulfinyl) benzene (1.72 g, 5.29 mmol) and NaBH₄ (1.2 g, 31.77 mmol) in THF (30 ml) was heated at reflux for 18 h. The reaction mixture was quenched with Na₂SO₄.10H₂O and filtered through Celite. The filtrate was evaporated under vacuum and the residue purified by flash chromatography (80:20 hexane/EtOAc) to obtain a white solid (1.03 g, 67%), mp 127–128°C, [α]_D -198.2 (c 1, CHCl₃).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 2006); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound, viewed down the b axis, showing one layer of molecules connected by C—H···O—C and C—H···O—-S hydrogen bonds (dashed lines).

1,2-Dimethoxy-4-methyl-3-[(S)-p-tolylsulfinyl]benzene top

Crystal data top

C₁₆H₁₈O₃S	D_x = 1.263 Mg m⁻³
M_r = 290.36	Melting point: 400 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9922 reflections
a = 7.4170 (6) Å	θ = 2.5–27.6°
b = 8.5406 (7) Å	µ = 0.22 mm⁻¹
c = 24.0980 (19) Å	T = 298 K
V = 1526.5 (2) Å³	Prism, colourless
Z = 4	0.38 × 0.37 × 0.31 mm
F(000) = 616

Data collection top

Bruker SMART APEX CCD diffractometer	3645 independent reflections
Radiation source: fine-focus sealed tube	3380 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 0.661 pixels mm^-1	θ_max = 27.9°, θ_min = 1.7°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −11→11
T_min = 0.922, T_max = 0.942	l = −31→31
20418 measured reflections

Refinement top

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)] = 0.039	H-atom parameters not refined
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0693P)² + 0.0141P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3645 reflections	Δρ_max = 0.25 e Å⁻³
185 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1534 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (6)

Crystal data top

C₁₆H₁₈O₃S	V = 1526.5 (2) Å³
M_r = 290.36	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.4170 (6) Å	µ = 0.22 mm⁻¹
b = 8.5406 (7) Å	T = 298 K
c = 24.0980 (19) Å	0.38 × 0.37 × 0.31 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3645 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	3380 reflections with I > 2σ(I)
T_min = 0.922, T_max = 0.942	R_int = 0.028
20418 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters not refined
wR(F²) = 0.099	Δρ_max = 0.25 e Å⁻³
S = 1.06	Δρ_min = −0.13 e Å⁻³
3645 reflections	Absolute structure: Flack (1983), 1534 Friedel pairs
185 parameters	Absolute structure parameter: 0.01 (6)
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	0.57970 (5)	0.27901 (5)	0.149352 (15)	0.04842 (12)
O1	0.77239 (19)	0.07949 (18)	0.33551 (5)	0.0664 (4)
O2	0.57075 (15)	0.25318 (11)	0.26763 (4)	0.0500 (3)
O3	0.6876 (2)	0.39213 (16)	0.11616 (5)	0.0671 (4)
C1	0.8129 (2)	0.0711 (2)	0.28050 (7)	0.0527 (4)
C2	0.7012 (2)	0.15921 (17)	0.24538 (6)	0.0447 (3)
C3	0.73064 (19)	0.15714 (18)	0.18847 (6)	0.0451 (3)
C4	0.8742 (2)	0.0726 (2)	0.16503 (7)	0.0544 (4)
C5	0.9821 (2)	−0.0114 (2)	0.20084 (9)	0.0621 (4)
H5	1.0779	−0.0684	0.1863	0.074*
C6	0.9531 (2)	−0.0143 (2)	0.25777 (8)	0.0621 (4)
H6	1.0278	−0.0736	0.2806	0.074*
C7	0.9144 (3)	0.0710 (3)	0.10365 (8)	0.0695 (5)
H7A	1.0391	0.0458	0.0979	0.104*
H7B	0.8892	0.1723	0.0882	0.104*
H7C	0.8403	−0.0062	0.0858	0.104*
C8	0.8723 (4)	−0.0178 (4)	0.37212 (9)	0.0968 (8)
H8A	0.8235	−0.0095	0.4089	0.145*
H8B	0.9962	0.0149	0.3724	0.145*
H8C	0.8649	−0.1245	0.3598	0.145*
C9	0.4070 (3)	0.1761 (2)	0.28212 (10)	0.0709 (5)
H9A	0.3163	0.2528	0.2903	0.106*
H9B	0.4267	0.1114	0.3141	0.106*
H9C	0.3679	0.1122	0.2517	0.106*
C10	0.49336 (19)	0.13539 (18)	0.10183 (6)	0.0454 (3)
C11	0.4650 (3)	0.1815 (2)	0.04729 (7)	0.0563 (4)
H11	0.4975	0.2815	0.0358	0.068*
C12	0.3884 (3)	0.0780 (2)	0.01049 (7)	0.0613 (4)
H12	0.3698	0.1089	−0.0261	0.074*
C13	0.3386 (2)	−0.0713 (2)	0.02686 (7)	0.0588 (4)
C14	0.3663 (2)	−0.1131 (2)	0.08149 (8)	0.0580 (4)
H14	0.3330	−0.2128	0.0931	0.070*
C15	0.4417 (2)	−0.01158 (18)	0.11920 (6)	0.0511 (3)
H15	0.4577	−0.0418	0.1560	0.061*
C16	0.2546 (4)	−0.1816 (3)	−0.01457 (11)	0.0911 (8)
H16A	0.3326	−0.1919	−0.0462	0.137*
H16B	0.1401	−0.1410	−0.0263	0.137*
H16C	0.2378	−0.2824	0.0023	0.137*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0537 (2)	0.04504 (19)	0.04650 (18)	0.00360 (16)	0.00099 (15)	−0.00251 (14)
O1	0.0699 (8)	0.0764 (9)	0.0528 (6)	0.0157 (7)	−0.0092 (5)	0.0025 (6)
O2	0.0525 (6)	0.0466 (6)	0.0509 (5)	0.0076 (5)	0.0038 (5)	−0.0048 (4)
O3	0.0840 (9)	0.0527 (7)	0.0645 (7)	−0.0127 (6)	0.0057 (7)	0.0006 (6)
C1	0.0492 (8)	0.0512 (9)	0.0576 (9)	−0.0011 (7)	−0.0075 (7)	−0.0026 (7)
C2	0.0422 (7)	0.0406 (7)	0.0513 (8)	−0.0022 (6)	−0.0032 (6)	−0.0052 (6)
C3	0.0405 (7)	0.0431 (7)	0.0518 (8)	−0.0004 (6)	−0.0019 (6)	−0.0059 (6)
C4	0.0432 (7)	0.0558 (9)	0.0642 (9)	−0.0004 (7)	0.0034 (6)	−0.0108 (8)
C5	0.0406 (7)	0.0647 (10)	0.0808 (12)	0.0102 (7)	0.0022 (8)	−0.0110 (9)
C6	0.0455 (9)	0.0640 (10)	0.0766 (11)	0.0082 (8)	−0.0098 (8)	−0.0002 (9)
C7	0.0604 (10)	0.0814 (13)	0.0667 (10)	0.0081 (10)	0.0142 (9)	−0.0172 (9)
C8	0.1024 (18)	0.120 (2)	0.0680 (12)	0.0358 (17)	−0.0160 (12)	0.0157 (14)
C9	0.0540 (9)	0.0672 (11)	0.0915 (14)	0.0034 (8)	0.0160 (9)	−0.0008 (10)
C10	0.0431 (7)	0.0479 (8)	0.0452 (7)	0.0019 (6)	0.0009 (6)	−0.0012 (6)
C11	0.0641 (10)	0.0556 (9)	0.0493 (8)	−0.0001 (8)	−0.0012 (7)	0.0050 (7)
C12	0.0646 (11)	0.0735 (11)	0.0457 (7)	0.0000 (9)	−0.0038 (7)	−0.0004 (8)
C13	0.0483 (8)	0.0698 (11)	0.0583 (9)	−0.0012 (8)	−0.0009 (7)	−0.0117 (8)
C14	0.0550 (9)	0.0525 (9)	0.0665 (9)	−0.0093 (7)	0.0023 (7)	0.0003 (7)
C15	0.0505 (8)	0.0536 (8)	0.0490 (7)	−0.0021 (7)	0.0000 (6)	0.0049 (6)
C16	0.0964 (17)	0.0960 (17)	0.0808 (14)	−0.0243 (15)	−0.0147 (13)	−0.0228 (13)

Geometric parameters (Å, º) top

S1—O3	1.4877 (13)	C8—H8A	0.9600
S1—C3	1.7959 (15)	C8—H8B	0.9600
S1—C10	1.7961 (15)	C8—H8C	0.9600
S1—O2	2.8595 (11)	C9—H9A	0.9600
O1—C1	1.361 (2)	C9—H9B	0.9600
O1—C8	1.421 (2)	C9—H9C	0.9600
O2—C2	1.3665 (18)	C10—C15	1.377 (2)
O2—C9	1.425 (2)	C10—C11	1.388 (2)
C1—C6	1.384 (2)	C11—C12	1.375 (2)
C1—C2	1.403 (2)	C11—H11	0.9300
C2—C3	1.389 (2)	C12—C13	1.385 (3)
C3—C4	1.405 (2)	C12—H12	0.9300
C4—C5	1.378 (3)	C13—C14	1.380 (3)
C4—C7	1.509 (3)	C13—C16	1.508 (3)
C5—C6	1.389 (3)	C14—C15	1.375 (2)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—H15	0.9300
C7—H7A	0.9600	C16—H16A	0.9600
C7—H7B	0.9600	C16—H16B	0.9600
C7—H7C	0.9600	C16—H16C	0.9600

O3—S1—C3	108.86 (8)	O1—C8—H8B	109.5
O3—S1—C10	107.00 (7)	H8A—C8—H8B	109.5
C3—S1—C10	99.27 (7)	O1—C8—H8C	109.5
O3—S1—O2	126.76 (6)	H8A—C8—H8C	109.5
C3—S1—O2	56.39 (5)	H8B—C8—H8C	109.5
C10—S1—O2	125.07 (5)	O2—C9—H9A	109.5
C1—O1—C8	117.33 (16)	O2—C9—H9B	109.5
C2—O2—C9	115.36 (12)	H9A—C9—H9B	109.5
C2—O2—S1	68.76 (8)	O2—C9—H9C	109.5
C9—O2—S1	107.45 (11)	H9A—C9—H9C	109.5
O1—C1—C6	125.38 (15)	H9B—C9—H9C	109.5
O1—C1—C2	115.42 (15)	C15—C10—C11	120.28 (15)
C6—C1—C2	119.19 (16)	C15—C10—S1	121.85 (11)
O2—C2—C3	120.42 (13)	C11—C10—S1	117.64 (13)
O2—C2—C1	119.74 (14)	C12—C11—C10	119.40 (16)
C3—C2—C1	119.74 (14)	C12—C11—H11	120.3
C2—C3—C4	121.52 (14)	C10—C11—H11	120.3
C2—C3—S1	114.39 (11)	C11—C12—C13	121.22 (15)
C4—C3—S1	123.99 (12)	C11—C12—H12	119.4
C5—C4—C3	117.11 (16)	C13—C12—H12	119.4
C5—C4—C7	119.62 (16)	C14—C13—C12	118.07 (16)
C3—C4—C7	123.27 (16)	C14—C13—C16	122.10 (19)
C4—C5—C6	122.54 (15)	C12—C13—C16	119.83 (18)
C4—C5—H5	118.7	C15—C14—C13	121.86 (16)
C6—C5—H5	118.7	C15—C14—H14	119.1
C1—C6—C5	119.86 (16)	C13—C14—H14	119.1
C1—C6—H6	120.1	C14—C15—C10	119.14 (14)
C5—C6—H6	120.1	C14—C15—H15	120.4
C4—C7—H7A	109.5	C10—C15—H15	120.4
C4—C7—H7B	109.5	C13—C16—H16A	109.5
H7A—C7—H7B	109.5	C13—C16—H16B	109.5
C4—C7—H7C	109.5	H16A—C16—H16B	109.5
H7A—C7—H7C	109.5	C13—C16—H16C	109.5
H7B—C7—H7C	109.5	H16A—C16—H16C	109.5
O1—C8—H8A	109.5	H16B—C16—H16C	109.5

O3—S1—O2—C2	−90.50 (11)	C2—C3—C4—C5	1.6 (2)
C3—S1—O2—C2	−1.18 (9)	S1—C3—C4—C5	177.80 (13)
C10—S1—O2—C2	75.52 (10)	C2—C3—C4—C7	−178.16 (17)
O3—S1—O2—C9	158.43 (11)	S1—C3—C4—C7	−2.0 (2)
C3—S1—O2—C9	−112.24 (11)	C3—C4—C5—C6	−0.1 (3)
C10—S1—O2—C9	−35.55 (12)	C7—C4—C5—C6	179.69 (19)
C8—O1—C1—C6	−5.7 (3)	O1—C1—C6—C5	−179.05 (18)
C8—O1—C1—C2	174.92 (19)	C2—C1—C6—C5	0.3 (3)
C9—O2—C2—C3	101.36 (18)	C4—C5—C6—C1	−0.9 (3)
S1—O2—C2—C3	1.47 (11)	O3—S1—C10—C15	157.47 (13)
C9—O2—C2—C1	−82.32 (19)	C3—S1—C10—C15	44.36 (14)
S1—O2—C2—C1	177.79 (15)	O2—S1—C10—C15	−10.85 (15)
O1—C1—C2—O2	4.2 (2)	O3—S1—C10—C11	−28.07 (16)
C6—C1—C2—O2	−175.16 (14)	C3—S1—C10—C11	−141.18 (14)
O1—C1—C2—C3	−179.42 (15)	O2—S1—C10—C11	163.61 (12)
C6—C1—C2—C3	1.2 (2)	C15—C10—C11—C12	−1.4 (3)
O2—C2—C3—C4	174.15 (14)	S1—C10—C11—C12	−175.92 (14)
C1—C2—C3—C4	−2.2 (2)	C10—C11—C12—C13	0.2 (3)
O2—C2—C3—S1	−2.40 (19)	C11—C12—C13—C14	0.6 (3)
C1—C2—C3—S1	−178.71 (12)	C11—C12—C13—C16	179.9 (2)
O3—S1—C3—C2	123.34 (12)	C12—C13—C14—C15	−0.3 (3)
C10—S1—C3—C2	−125.01 (12)	C16—C13—C14—C15	−179.6 (2)
O2—S1—C3—C2	1.19 (9)	C13—C14—C15—C10	−0.9 (3)
O3—S1—C3—C4	−53.11 (15)	C11—C10—C15—C14	1.7 (2)
C10—S1—C3—C4	58.54 (14)	S1—C10—C15—C14	176.01 (13)
O2—S1—C3—C4	−175.27 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O3ⁱ	0.96	2.58	3.366 (3)	139
C14—H14···O1ⁱⁱ	0.93	2.59	3.457 (2)	155
C15—H15···O2ⁱⁱ	0.93	2.55	3.3886 (18)	150
C12—H12···O3ⁱⁱⁱ	0.93	2.56	3.406 (2)	152

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈O₃S
M_r	290.36
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.4170 (6), 8.5406 (7), 24.0980 (19)
V (Å³)	1526.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.38 × 0.37 × 0.31

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.922, 0.942
No. of measured, independent and observed [I > 2σ(I)] reflections	20418, 3645, 3380
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.099, 1.06
No. of reflections	3645
No. of parameters	185
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.13
Absolute structure	Flack (1983), 1534 Friedel pairs
Absolute structure parameter	0.01 (6)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O3ⁱ	0.96	2.58	3.366 (3)	138.7
C14—H14···O1ⁱⁱ	0.93	2.59	3.457 (2)	155.1
C15—H15···O2ⁱⁱ	0.93	2.55	3.3886 (18)	150.2
C12—H12···O3ⁱⁱⁱ	0.93	2.56	3.406 (2)	151.9

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

References

Brondel, N., Moyniham, E. J. A., Lehane, K. N., Eccles, K. S., Elcoate, C. J., Coles, S. J., Lawrence, S. E. & Maguire, A. R. (2010). CrystEngComm, 12, 2910–2927. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1999). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2006). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fuller, A. L., Aitken, R. A., Ryan, B. M., Slawin, A. M. Z. & Woollins, J. D. (2009). J. Chem. Crystallogr. 39, 407–415. Web of Science CSD CrossRef CAS Google Scholar
Mastranzo, V. M., Yuste, F., Ortiz, B., Sánchez-Obregón, R., Toscano, R. A. & García Ruano, J. L. (2011). J. Org. Chem. 76, 5036–5041. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 67| Part 11| November 2011| Page o2950

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