1,2-Dimeth-oxy-4-methyl-3-[(S)-p-tolyl-sulfin-yl]benzene.

In the title compound, C(16)H(18)O(3)S, 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 inter-molecular 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 = 290.36

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.099

S = 1.06

3645 reflections

185 parameters

H-atom parameters not refined

Δρmax = 0.25 e Å−3

Δρmin = −0.13 e Å−3

Absolute structure: Flack (1983 ▶), 1534 Friedel pairs

Flack parameter: 0.01 (6)

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041420/bt5660sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811041420/bt5660Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536811041420/bt5660Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H18O3S	Dx = 1.263 Mg m−3
Mr = 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

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

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(Fo2) + (0.0693P)2 + 0.0141P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3645 reflections	Δρmax = 0.25 e Å−3
185 parameters	Δρmin = −0.13 e Å−3
0 restraints	Absolute structure: Flack (1983), 1534 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (6)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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.

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) ; (ii) ; (iii) .