2-Meth­oxy-4-methyl­phenyl 4-toluene­sulfonate

Ramachandran, G.; Kanakam, C.C.; Gunasekaran, B.; Manivannan, V.

doi:10.1107/S1600536808025749

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1760

doi:10.1107/S1600536808025749

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2-Methoxy-4-methylphenyl 4-toluenesulfonate

G. Ramachandran,^a Charles Christopher Kanakam,^a B. Gunasekaran ^b and V. Manivannan ^c ^*

^aDepartment of Chemistry, Valliammai Engineering College, Chennai, India, ^bDepartment of Physics, AMET University, Kanathur, Chennai, India, and ^cDepartment of Physics, Presidency College, Chennai 600 005, India
^*Correspondence e-mail: manivan_1999@yahoo.com

(Received 6 August 2008; accepted 10 August 2008; online 16 August 2008)

In the title molecule, C₁₅H₁₆O₄S, the interplanar angle between the two aromatic rings is 45.07 (7)°. The crystal packing is stabilized by weak intermolecular C—H⋯O interactions.

Related literature

For related literature, see: Manivannan et al. (2005a ); Spungin et al. (1984 ); Yachi et al. (1989 ). Similar compounds have been reported by: Manivannan et al. (2005b ); Ramachandran et al.(2007 ).

Experimental

Crystal data

C₁₅H₁₆O₄S
M_r = 292.34
Triclinic, $[P \overline 1]$
a = 7.932 (2) Å
b = 8.736 (3) Å
c = 10.934 (3) Å
α = 93.785 (5)°
β = 98.453 (5)°
γ = 102.476 (4)°
V = 727.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 (2) K
0.48 × 0.46 × 0.14 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.902, T_max = 0.970
8439 measured reflections
3348 independent reflections
2220 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.140
S = 1.02
3348 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15C⋯O1ⁱ	0.96	2.60	3.327 (4)	133
Symmetry code: (i) x, y-1, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025749/bt2764sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808025749/bt2764Isup2.hkl

checkCIF report

Comment top

Several compounds containing the para-toluene sulfonate moiety are used in the fields of biology and industry. The merging of lipids can be monitored using a derivative of para-toluene sulfonate (Yachi et al., 1989). This method has been used in studying the membrane fusion during the acrosome reaction (Spungin et al., 1984).

The geometric parameters in the title compound agree with the reported values of similar structures (Manivannan et al., 2005a,b; Ramachandran et al., 2007). The aromatic rings make a dihedral angle of 45.07 (7)° with respect to each other. The crystal packing is stabilized by weak intermolecular C—H···O interactions.

The angle between the two oxygen atoms of the –SO2- group is much larger than the tetrahedral angle which leads to the decrease in the –O—S—Ar angle.

Related literature top

For related literature, see: Manivannan et al. (2005a); Spungin et al. (1984); Yachi et al. (1989). Similar compounds have been reported by: Manivannan et al. (2005b); Ramachandran et al.(2007).

Experimental top

A solution of vanillin in toluene was treated with amalgamated Zinc wool and concentrated HCl under reflux for thirty hours. The reaction mixture was cooled. The organic layer was separated and the aqueous layer was washed with ether. The combined ether and toluene solutions were washed with water, dried over anhydrous calcium chloride and the solvent removed under reduced pressure to get 2-methoxy-4-methyl phenol. A mixture of the above phenol and triethyl amine in acetone was treated with p-toluene sulfonyl chloride at room temperature for twelve hours. The residue was washed with triethyl amine solution and water and dried. Diffraction quality crystals were obtained from the solid by recrystallizing from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

2-Methoxy-4-methylphenyl 4-toluenesulfonate top

Crystal data top

C₁₅H₁₆O₄S	Z = 2
M_r = 292.34	F(000) = 308
Triclinic, P1	D_x = 1.334 Mg m⁻³
a = 7.932 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.736 (3) Å	Cell parameters from 2654 reflections
c = 10.934 (3) Å	θ = 1.9–24.7°
α = 93.785 (5)°	µ = 0.23 mm⁻¹
β = 98.453 (5)°	T = 293 K
γ = 102.476 (4)°	Block, colourless
V = 727.9 (4) Å³	0.48 × 0.46 × 0.14 mm

Data collection top

Bruker KappaAPEX2 diffractometer	3348 independent reflections
Radiation source: fine-focus sealed tube	2220 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 28.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.902, T_max = 0.970	k = −11→11
8439 measured reflections	l = −13→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0612P)² + 0.2027P] where P = (F_o² + 2F_c²)/3
3348 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₅H₁₆O₄S	γ = 102.476 (4)°
M_r = 292.34	V = 727.9 (4) Å³
Triclinic, P1	Z = 2
a = 7.932 (2) Å	Mo Kα radiation
b = 8.736 (3) Å	µ = 0.23 mm⁻¹
c = 10.934 (3) Å	T = 293 K
α = 93.785 (5)°	0.48 × 0.46 × 0.14 mm
β = 98.453 (5)°

Data collection top

Bruker KappaAPEX2 diffractometer	3348 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2220 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.970	R_int = 0.028
8439 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.02	Δρ_max = 0.30 e Å⁻³
3348 reflections	Δρ_min = −0.20 e Å⁻³
184 parameters

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	0.14427 (8)	0.00747 (7)	0.26949 (6)	0.0589 (2)
O3	0.02375 (19)	−0.13695 (17)	0.32049 (15)	0.0545 (4)
C1	0.2907 (3)	−0.0764 (2)	0.1975 (2)	0.0494 (5)
O4	0.0552 (2)	−0.41635 (18)	0.23259 (14)	0.0597 (4)
C13	0.1215 (3)	−0.3741 (2)	0.3550 (2)	0.0460 (5)
C12	0.2000 (3)	−0.4645 (3)	0.4347 (2)	0.0538 (6)
H12	0.2116	−0.5631	0.4044	0.065*
O1	0.0236 (3)	0.0562 (2)	0.17935 (19)	0.0802 (6)
C8	0.1067 (3)	−0.2266 (2)	0.4028 (2)	0.0475 (5)
O2	0.2394 (2)	0.11439 (19)	0.37184 (19)	0.0777 (6)
C6	0.4487 (3)	−0.0852 (3)	0.2655 (2)	0.0572 (6)
H6	0.4773	−0.0476	0.3492	0.069*
C5	0.5639 (3)	−0.1506 (3)	0.2077 (2)	0.0616 (6)
H5	0.6705	−0.1567	0.2533	0.074*
C9	0.1631 (3)	−0.1736 (3)	0.5253 (2)	0.0626 (7)
H9	0.1489	−0.0762	0.5561	0.075*
C11	0.2616 (3)	−0.4110 (3)	0.5584 (2)	0.0629 (7)
C2	0.2475 (3)	−0.1326 (3)	0.0737 (2)	0.0637 (7)
H2	0.1408	−0.1269	0.0280	0.076*
C4	0.5240 (3)	−0.2066 (3)	0.0845 (3)	0.0608 (6)
C10	0.2412 (4)	−0.2652 (4)	0.6028 (2)	0.0706 (7)
H10	0.2808	−0.2287	0.6862	0.085*
C3	0.3654 (4)	−0.1975 (3)	0.0186 (3)	0.0726 (8)
H3	0.3368	−0.2358	−0.0650	0.087*
C7	0.6524 (4)	−0.2766 (4)	0.0219 (3)	0.0907 (10)
H7A	0.6063	−0.3878	0.0013	0.136*
H7B	0.7620	−0.2589	0.0773	0.136*
H7C	0.6702	−0.2274	−0.0526	0.136*
C14	0.3479 (4)	−0.5125 (4)	0.6429 (3)	0.0940 (10)
H14A	0.4638	−0.4553	0.6794	0.141*
H14B	0.3544	−0.6069	0.5955	0.141*
H14C	0.2802	−0.5397	0.7075	0.141*
C15	0.0926 (5)	−0.5547 (4)	0.1778 (3)	0.0943 (10)
H15A	0.2171	−0.5422	0.1858	0.141*
H15B	0.0416	−0.5717	0.0913	0.141*
H15C	0.0444	−0.6435	0.2191	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0625 (4)	0.0381 (3)	0.0820 (5)	0.0201 (3)	0.0184 (3)	0.0062 (3)
O3	0.0500 (9)	0.0452 (8)	0.0746 (11)	0.0201 (7)	0.0160 (8)	0.0087 (7)
C1	0.0540 (13)	0.0374 (11)	0.0601 (14)	0.0134 (10)	0.0137 (11)	0.0086 (10)
O4	0.0777 (11)	0.0461 (9)	0.0574 (10)	0.0216 (8)	0.0090 (8)	0.0003 (7)
C13	0.0429 (11)	0.0438 (11)	0.0540 (13)	0.0108 (9)	0.0157 (10)	0.0054 (10)
C12	0.0507 (13)	0.0521 (13)	0.0676 (16)	0.0201 (11)	0.0225 (12)	0.0156 (11)
O1	0.0841 (13)	0.0644 (11)	0.1083 (15)	0.0442 (10)	0.0178 (11)	0.0297 (11)
C8	0.0453 (12)	0.0447 (11)	0.0562 (14)	0.0143 (9)	0.0138 (10)	0.0058 (10)
O2	0.0839 (13)	0.0459 (9)	0.1019 (14)	0.0120 (9)	0.0253 (11)	−0.0149 (9)
C6	0.0562 (14)	0.0547 (14)	0.0599 (15)	0.0118 (11)	0.0095 (12)	0.0019 (11)
C5	0.0524 (14)	0.0618 (15)	0.0749 (17)	0.0186 (12)	0.0144 (12)	0.0111 (13)
C9	0.0694 (16)	0.0578 (14)	0.0625 (16)	0.0150 (13)	0.0202 (13)	−0.0029 (12)
C11	0.0477 (13)	0.0779 (18)	0.0681 (17)	0.0152 (12)	0.0168 (12)	0.0248 (14)
C2	0.0634 (15)	0.0665 (16)	0.0623 (16)	0.0202 (13)	0.0043 (12)	0.0113 (13)
C4	0.0647 (16)	0.0496 (13)	0.0744 (17)	0.0145 (12)	0.0282 (13)	0.0106 (12)
C10	0.0700 (17)	0.0835 (19)	0.0542 (15)	0.0089 (15)	0.0104 (13)	0.0046 (14)
C3	0.090 (2)	0.0742 (18)	0.0568 (16)	0.0194 (16)	0.0220 (15)	0.0027 (13)
C7	0.093 (2)	0.080 (2)	0.114 (3)	0.0278 (18)	0.056 (2)	0.0064 (18)
C14	0.0724 (19)	0.129 (3)	0.092 (2)	0.036 (2)	0.0139 (17)	0.052 (2)
C15	0.144 (3)	0.0675 (18)	0.075 (2)	0.045 (2)	0.0110 (19)	−0.0157 (15)

Geometric parameters (Å, º) top

S1—O2	1.4154 (19)	C9—H9	0.9300
S1—O1	1.4219 (19)	C11—C10	1.383 (4)
S1—O3	1.5954 (17)	C11—C14	1.514 (4)
S1—C1	1.751 (2)	C2—C3	1.382 (4)
O3—C8	1.414 (3)	C2—H2	0.9300
C1—C2	1.376 (3)	C4—C3	1.376 (4)
C1—C6	1.380 (3)	C4—C7	1.516 (3)
O4—C13	1.360 (3)	C10—H10	0.9300
O4—C15	1.421 (3)	C3—H3	0.9300
C13—C12	1.383 (3)	C7—H7A	0.9600
C13—C8	1.393 (3)	C7—H7B	0.9600
C12—C11	1.382 (3)	C7—H7C	0.9600
C12—H12	0.9300	C14—H14A	0.9600
C8—C9	1.364 (3)	C14—H14B	0.9600
C6—C5	1.381 (3)	C14—H14C	0.9600
C6—H6	0.9300	C15—H15A	0.9600
C5—C4	1.369 (4)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C9—C10	1.376 (4)

O2—S1—O1	120.05 (12)	C10—C11—C14	121.2 (3)
O2—S1—O3	108.67 (11)	C1—C2—C3	118.8 (2)
O1—S1—O3	102.79 (10)	C1—C2—H2	120.6
O2—S1—C1	108.96 (11)	C3—C2—H2	120.6
O1—S1—C1	110.55 (12)	C5—C4—C3	118.6 (2)
O3—S1—C1	104.58 (9)	C5—C4—C7	120.7 (3)
C8—O3—S1	117.90 (13)	C3—C4—C7	120.7 (3)
C2—C1—C6	120.6 (2)	C9—C10—C11	120.9 (2)
C2—C1—S1	119.77 (18)	C9—C10—H10	119.6
C6—C1—S1	119.66 (18)	C11—C10—H10	119.6
C13—O4—C15	116.8 (2)	C4—C3—C2	121.5 (2)
O4—C13—C12	125.8 (2)	C4—C3—H3	119.2
O4—C13—C8	116.1 (2)	C2—C3—H3	119.2
C12—C13—C8	118.1 (2)	C4—C7—H7A	109.5
C11—C12—C13	121.2 (2)	C4—C7—H7B	109.5
C11—C12—H12	119.4	H7A—C7—H7B	109.5
C13—C12—H12	119.4	C4—C7—H7C	109.5
C9—C8—C13	121.4 (2)	H7A—C7—H7C	109.5
C9—C8—O3	121.2 (2)	H7B—C7—H7C	109.5
C13—C8—O3	117.30 (19)	C11—C14—H14A	109.5
C1—C6—C5	119.3 (2)	C11—C14—H14B	109.5
C1—C6—H6	120.4	H14A—C14—H14B	109.5
C5—C6—H6	120.4	C11—C14—H14C	109.5
C4—C5—C6	121.2 (2)	H14A—C14—H14C	109.5
C4—C5—H5	119.4	H14B—C14—H14C	109.5
C6—C5—H5	119.4	O4—C15—H15A	109.5
C8—C9—C10	119.5 (2)	O4—C15—H15B	109.5
C8—C9—H9	120.3	H15A—C15—H15B	109.5
C10—C9—H9	120.3	O4—C15—H15C	109.5
C12—C11—C10	118.9 (2)	H15A—C15—H15C	109.5
C12—C11—C14	119.9 (3)	H15B—C15—H15C	109.5

O2—S1—O3—C8	−59.07 (17)	S1—O3—C8—C13	−104.3 (2)
O1—S1—O3—C8	172.70 (15)	C2—C1—C6—C5	0.3 (4)
C1—S1—O3—C8	57.18 (17)	S1—C1—C6—C5	−179.55 (18)
O2—S1—C1—C2	−154.40 (19)	C1—C6—C5—C4	0.0 (4)
O1—S1—C1—C2	−20.4 (2)	C13—C8—C9—C10	2.0 (4)
O3—S1—C1—C2	89.5 (2)	O3—C8—C9—C10	179.2 (2)
O2—S1—C1—C6	25.4 (2)	C13—C12—C11—C10	1.0 (4)
O1—S1—C1—C6	159.38 (18)	C13—C12—C11—C14	−179.6 (2)
O3—S1—C1—C6	−90.64 (19)	C6—C1—C2—C3	−0.2 (4)
C15—O4—C13—C12	−9.7 (3)	S1—C1—C2—C3	179.6 (2)
C15—O4—C13—C8	170.7 (2)	C6—C5—C4—C3	−0.4 (4)
O4—C13—C12—C11	−179.3 (2)	C6—C5—C4—C7	179.4 (2)
C8—C13—C12—C11	0.3 (3)	C8—C9—C10—C11	−0.7 (4)
O4—C13—C8—C9	177.8 (2)	C12—C11—C10—C9	−0.8 (4)
C12—C13—C8—C9	−1.8 (3)	C14—C11—C10—C9	179.8 (2)
O4—C13—C8—O3	0.6 (3)	C5—C4—C3—C2	0.4 (4)
C12—C13—C8—O3	−179.08 (18)	C7—C4—C3—C2	−179.3 (3)
S1—O3—C8—C9	78.4 (2)	C1—C2—C3—C4	−0.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15C···O1ⁱ	0.96	2.60	3.327 (4)	133

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₆O₄S
M_r	292.34
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.932 (2), 8.736 (3), 10.934 (3)
α, β, γ (°)	93.785 (5), 98.453 (5), 102.476 (4)
V (Å³)	727.9 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.48 × 0.46 × 0.14

Data collection
Diffractometer	Bruker KappaAPEX2 diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.902, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	8439, 3348, 2220
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.140, 1.02
No. of reflections	3348
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.20

Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15C···O1ⁱ	0.96	2.60	3.327 (4)	133

Symmetry code: (i) x, y−1, z.

References

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Volume 64| Part 9| September 2008| Page o1760

doi:10.1107/S1600536808025749

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