Methyl 4-tosyl­oxy­benzoate: supramolecular aggregation through C—H...O, C—H...π and π–π interactions

In the title mol­ecule, C₁₅H₁₄O₅S, the dihedral angle between the mean planes of the 4-tolyl and the 4-benzoate rings is 58.63 (6)°. There are weak intermolecular C—H...O interactions, which generate rings of motifs S(5), S(6), R¹₂(5), R¹₂(6) and R²₁(4). The supramolecular aggregation is completed by C—H...π and π–π interactions.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.116
• Data-to-parameter ratio = 13.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

p-Toluene sulfonates are used in monitoring the merging of lipids (Yachi et al., 1989), studying membrane fusion during acrosome reaction (Spungin et al., 1992), development of immunoaffinity chromatography for the purification of human coagulation factor (Tharakan et al., 1992), chemical studies on viruses (Alford et al., 1991), development of technology for linking photosensitizer to model monoclonal antibody (Jiang et al., 1990) and chemical modification of sigma sub units of the E. coli RNA polymerase (Narayanan & Krakow, 1983). An X-ray study of the title compound, (I), was undertaken in order to determine its crystal and molecular structure owing to the biological importance of its analogues.

A search of version 5.23 (July 2002 updates) of the Cambridge Structural Database (Allen, 2002) revealed 16 structures (with the following refcodes: KAWDAN, FIXCAQ, NEDXUP, NEDYAW, NEDYIE, NUNCII, RASSOT, RELVUZ, SIMVUF, TCPTOS, TEBFOV, TMPDTS, TSMIPH, WOHCUR, ZZZBDA10 and MIWHIJ) that are closely related to the title compound. The S—C, S—O and S=O bond lengths (Table 1) are comparable to those found in these structures. Atoms C14, O4, O5 and C15 deviate from the mean plane through the phenyl ring (C8–C13) by 0.078 (2), −0.112 (1), 0.410 (1) and 0.591 (2) Å, respectively. The dihedral angle between the above plane and the plane formed by the 4-tolyl ring is 58.74 (8)°. This shows their non-coplanar orientation similar to that found between the 4-tolyl and 2-chlorophenyl rings in 2-chlorophenyl 4-toluenesulfonate (Vembu et al., 2003b) and the 4-tolyl and quinoline rings in 8-tosyloxyquinoline (Vembu et al., 2003c) and in contrast to the near coplanar orientation of the 4-tolyl and 2,4-dinitrophenyl rings in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu et al., 2003a) and 4-tolyl and 4-methoxyphenyl rings in 4-methoxyphenyl 4-toluenesulfonate (Vembu et al., 2003).

The crystal structure of (I) is stabilized by weak C—H···O interactions. The range for the H···O distances (Table 2) found in (I) agree with those found for weak C—H···O bonds (Desiraju & Steiner, 1999). The C9—H9···O1 (Fig. 1) interaction form a ring of graph set (Etter, 1990; Bernstein et al., 1995) motif S(6) and the C4—H4···O1 (Fig. 1) interaction form a ring of graph set S(5). The above two interactions together constitute a pair of bifurcated acceptor bonds and these two ring motifs are fused to each other. The C10—H10···O4 and C15—H15A···O4 interactions (Fig. 1) constitute a pair of bifurcated acceptor bonds each of them generating a S(5) ring motif which are fused to each other. Two other S(5) rings are formed by C12—H12···O5 and C6—H6···O2 interactions.

The C10—H10···O2ⁱⁱ and C9—H9···O2ⁱⁱ interactions constitute a pair of bifurcated acceptor bonds generating a ring of graph set R¹₂(5) (see Table 2 for symmetry codes). The C12—H12···O1ⁱⁱⁱ and C13—H13···O1ⁱⁱⁱ (Fig. 2) interactions form a pair of bifurcated acceptor bonds generating another R¹₂(5) motif. The C1—H1C···O4^iv and C7—H7···O4^iv interactions constitute a pair of bifurcated acceptor bonds generating a ring of graph-set R¹₂(6). The C15—H15A···O3^vi and C15—H15A···O2^vi interactions constitute a pair of bifurcated donor bonds generating a ring of graph set R²₁(4). The H15A···O2^vi and H15A···O3^vi distances differ only by 0.14 Å. The resulting configuration is best regarded as a three center symmetrical hydrogen bonded chelate (Desiraju, 1989) and is also observed in similar structures (Vembu et al., 2003, 2003b,c). There are several other weak C—H···O interactions (Fig. 2) and C—H···π interactions (Table 2) which contribute to the supramolecular aggregation. In Table 2, Cg1 and Cg2 denote the centroids of the phenyl rings comprising of atoms C2–C7 and C8–C13, respectively. In the crystal, the inversion related benzoate phenyl rings (symmetry code: 1 − x, −y, −z) are stacked with a centroid···centroid separation of 3.659 (1) Å, indicating weak π–π interactions.

S2. Experimental

Methyl 4-hydroxybenzoate (4.9 mmol) and triethylamine (4.9 mmol) were dissolved separately in acetone (10 ml) and mixed. To this solution, 4-toluenesulfonyl chloride (3.9 mmol) dissolved in acetone (10 ml) was added. The solution was left overnight and evaporated. The residue obtained was washed several times with 2% aqueous triethylamine solution to get the crude product. Diffraction quality crystals were obtained (2.5 mmol, 64% yield) by recrystallizing the crude product from ethanol.

S3. Refinement

All H atoms were located from a difference Fourier map and both positional and isotropic displacement paramaters were refined. The C—H bond lengths are in the range 0.90 (3)–0.98 (2) Å, the H—C—H angles for the methyl group are in the range 102 (3)–113 (2)° and the C—C—H angles for the aromatic rings are in the range 118 (1)–123 (1)°. The U_iso values range from 0.021 (5)–0.097 (12) Ų

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1998).

Figures

	Fig. 1. The structure of (I), showing 50% probablity displacement ellipsoids and intramolecular C—H···O interactions.
	Fig. 2. Part of the molecular network, showing intermolecular C—H···O interactions. Symmetry codes are as in Table 2.

Methyl 4-tosyloxybenzoate

Crystal data

C15H14O5S	F(000) = 640
Mr = 306.32	Dx = 1.427 Mg m^−3
Monoclinic, P21/c	Melting point: 363-364 K K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.2921 (10) Å	Cell parameters from 889 reflections
b = 12.2799 (16) Å	θ = 3.1–27.3°
c = 14.2746 (18) Å	µ = 0.25 mm^−1
β = 101.229 (3)°	T = 120 K
V = 1425.7 (3) Å^3	Block, colourless
Z = 4	0.28 × 0.24 × 0.15 mm

Data collection

Bruker SMART CCD 6K area-detector diffractometer	3289 independent reflections
Radiation source: fine-focus sealed tube	2588 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 8 pixels mm^-1	θmax = 27.6°, θmin = 2.2°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −15→15
Tmin = 0.933, Tmax = 0.964	l = −18→18
15405 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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F^2) = 0.116	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0671P)^2 + 0.4296P] where P = (Fo^2 + 2Fc^2)/3
3289 reflections	(Δ/σ)max < 0.001
246 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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	0.52654 (5)	0.34668 (3)	0.18940 (3)	0.02394 (14)
O1	0.58226 (17)	0.27564 (11)	0.26789 (9)	0.0299 (3)
O2	0.38769 (16)	0.41488 (11)	0.18829 (10)	0.0333 (3)
O3	0.47160 (14)	0.27525 (9)	0.09497 (8)	0.0231 (3)
O4	0.86454 (17)	−0.16081 (10)	0.04397 (10)	0.0327 (3)
O5	0.83982 (17)	−0.07910 (10)	−0.09867 (9)	0.0306 (3)
C1	1.0938 (3)	0.61112 (17)	0.10540 (18)	0.0353 (4)
C2	0.9518 (2)	0.54593 (14)	0.12698 (13)	0.0273 (4)
C3	0.9799 (2)	0.45113 (15)	0.18124 (14)	0.0276 (4)
C4	0.8510 (2)	0.38974 (15)	0.20140 (13)	0.0263 (4)
C5	0.6911 (2)	0.42402 (14)	0.16630 (12)	0.0229 (3)
C6	0.6595 (2)	0.51848 (15)	0.11238 (14)	0.0296 (4)
C7	0.7900 (2)	0.57888 (15)	0.09304 (14)	0.0305 (4)
C8	0.5713 (2)	0.18780 (13)	0.07518 (11)	0.0208 (3)
C9	0.5910 (2)	0.09583 (14)	0.13215 (12)	0.0238 (4)
C10	0.6771 (2)	0.00886 (14)	0.10461 (12)	0.0237 (4)
C11	0.7394 (2)	0.01433 (13)	0.02111 (12)	0.0212 (3)
C12	0.7180 (2)	0.10779 (14)	−0.03469 (12)	0.0228 (4)
C13	0.6335 (2)	0.19602 (14)	−0.00723 (12)	0.0225 (4)
C14	0.8218 (2)	−0.08447 (14)	−0.00755 (13)	0.0241 (4)
C15	0.9092 (3)	−0.17449 (17)	−0.13494 (16)	0.0338 (4)
H1A	1.179 (4)	0.618 (3)	0.156 (2)	0.085 (11)*
H1B	1.141 (4)	0.582 (3)	0.056 (3)	0.097 (12)*
H1C	1.067 (4)	0.679 (3)	0.084 (2)	0.076 (9)*
H3	1.090 (3)	0.430 (2)	0.2058 (16)	0.042 (6)*
H4	0.872 (2)	0.3262 (18)	0.2383 (14)	0.027 (5)*
H6	0.547 (3)	0.540 (2)	0.0885 (18)	0.052 (7)*
H7	0.772 (3)	0.645 (2)	0.0572 (16)	0.038 (6)*
H9	0.543 (2)	0.0940 (16)	0.1884 (13)	0.021 (5)*
H10	0.690 (2)	−0.0573 (18)	0.1424 (15)	0.030 (5)*
H12	0.759 (2)	0.1109 (17)	−0.0948 (14)	0.026 (5)*
H13	0.615 (2)	0.2596 (17)	−0.0461 (14)	0.023 (5)*
H15A	0.852 (3)	−0.239 (2)	−0.1230 (19)	0.053 (7)*
H15B	1.019 (4)	−0.180 (2)	−0.1099 (19)	0.054 (8)*
H15C	0.887 (4)	−0.168 (2)	−0.202 (2)	0.061 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0254 (2)	0.0228 (2)	0.0246 (2)	−0.00066 (16)	0.00725 (16)	−0.00518 (16)
O1	0.0376 (7)	0.0307 (7)	0.0218 (6)	−0.0045 (6)	0.0066 (5)	−0.0031 (5)
O2	0.0287 (7)	0.0317 (7)	0.0416 (8)	0.0019 (6)	0.0125 (6)	−0.0091 (6)
O3	0.0220 (6)	0.0217 (6)	0.0248 (6)	0.0012 (5)	0.0030 (5)	−0.0048 (5)
O4	0.0403 (8)	0.0220 (6)	0.0368 (7)	0.0071 (5)	0.0095 (6)	0.0045 (5)
O5	0.0401 (8)	0.0242 (6)	0.0296 (7)	0.0063 (6)	0.0122 (6)	−0.0015 (5)
C1	0.0305 (11)	0.0264 (10)	0.0492 (13)	−0.0044 (8)	0.0080 (9)	−0.0016 (9)
C2	0.0284 (10)	0.0215 (8)	0.0317 (9)	−0.0011 (7)	0.0052 (7)	−0.0054 (7)
C3	0.0231 (9)	0.0242 (8)	0.0341 (10)	0.0039 (7)	0.0022 (7)	−0.0027 (7)
C4	0.0283 (10)	0.0217 (8)	0.0288 (9)	0.0039 (7)	0.0050 (7)	−0.0004 (7)
C5	0.0234 (9)	0.0205 (8)	0.0244 (8)	−0.0010 (6)	0.0040 (6)	−0.0052 (6)
C6	0.0247 (9)	0.0247 (9)	0.0373 (10)	0.0028 (7)	0.0008 (7)	−0.0006 (7)
C7	0.0291 (10)	0.0234 (9)	0.0375 (10)	0.0011 (7)	0.0025 (8)	0.0033 (8)
C8	0.0204 (8)	0.0187 (7)	0.0225 (8)	−0.0011 (6)	0.0024 (6)	−0.0044 (6)
C9	0.0261 (9)	0.0244 (8)	0.0216 (8)	−0.0027 (7)	0.0061 (7)	0.0003 (6)
C10	0.0265 (9)	0.0198 (8)	0.0239 (8)	−0.0014 (7)	0.0030 (7)	0.0023 (6)
C11	0.0215 (8)	0.0190 (8)	0.0227 (8)	−0.0017 (6)	0.0032 (6)	−0.0012 (6)
C12	0.0251 (9)	0.0224 (8)	0.0214 (8)	−0.0006 (7)	0.0053 (7)	0.0010 (6)
C13	0.0261 (9)	0.0196 (8)	0.0210 (8)	0.0000 (7)	0.0026 (6)	0.0017 (6)
C14	0.0205 (8)	0.0217 (8)	0.0296 (9)	−0.0020 (6)	0.0038 (7)	−0.0015 (7)
C15	0.0368 (12)	0.0288 (10)	0.0376 (11)	0.0034 (9)	0.0114 (9)	−0.0090 (8)

Geometric parameters (Å, º)

O4—C14	1.202 (2)	C5—S1	1.7461 (18)
C3—C4	1.384 (3)	C10—H10	0.97 (2)
C3—C2	1.393 (3)	C6—C7	1.383 (3)
C3—H3	0.94 (2)	C6—H6	0.97 (3)
C11—C12	1.388 (2)	C1—C2	1.505 (3)
C11—C10	1.390 (2)	C1—H1A	0.91 (4)
C11—C14	1.489 (2)	C1—H1B	0.94 (4)
C9—C8	1.383 (2)	C1—H1C	0.90 (3)
C9—C10	1.384 (2)	C2—C7	1.394 (3)
C9—H9	0.964 (18)	C7—H7	0.95 (2)
C8—C13	1.377 (2)	C4—H4	0.94 (2)
C8—O3	1.4171 (19)	S1—O2	1.4213 (14)
C12—C13	1.388 (2)	S1—O1	1.4242 (13)
C12—H12	0.98 (2)	S1—O3	1.5983 (12)
C13—H13	0.95 (2)	O5—C15	1.445 (2)
C14—O5	1.339 (2)	C15—H15A	0.96 (3)
C5—C4	1.388 (2)	C15—H15B	0.91 (3)
C5—C6	1.389 (2)	C15—H15C	0.95 (3)
C4—C3—C2	121.24 (17)	C2—C1—H1A	114 (2)
C4—C3—H3	120.2 (14)	C2—C1—H1B	114 (2)
C2—C3—H3	118.6 (15)	H1A—C1—H1B	105 (3)
C12—C11—C10	120.33 (15)	C2—C1—H1C	114 (2)
C12—C11—C14	122.00 (15)	H1A—C1—H1C	106 (3)
C10—C11—C14	117.61 (15)	H1B—C1—H1C	102 (3)
C8—C9—C10	118.12 (15)	C3—C2—C7	118.79 (17)
C8—C9—H9	119.2 (12)	C3—C2—C1	120.36 (17)
C10—C9—H9	122.7 (12)	C7—C2—C1	120.85 (18)
C13—C8—C9	122.80 (15)	C6—C7—C2	120.80 (18)
C13—C8—O3	116.42 (14)	C6—C7—H7	121.2 (14)
C9—C8—O3	120.53 (14)	C2—C7—H7	118.0 (14)
C13—C12—C11	119.88 (15)	C3—C4—C5	118.82 (17)
C13—C12—H12	119.8 (12)	C3—C4—H4	120.1 (12)
C11—C12—H12	120.3 (12)	C5—C4—H4	121.1 (13)
C8—C13—C12	118.53 (15)	O2—S1—O1	120.51 (8)
C8—C13—H13	120.8 (12)	O2—S1—O3	102.52 (7)
C12—C13—H13	120.6 (12)	O1—S1—O3	108.83 (7)
O4—C14—O5	123.88 (16)	O2—S1—C5	109.80 (8)
O4—C14—C11	124.34 (16)	O1—S1—C5	109.63 (8)
O5—C14—C11	111.77 (14)	O3—S1—C5	104.13 (7)
C4—C5—C6	121.15 (17)	C8—O3—S1	120.17 (10)
C4—C5—S1	119.58 (14)	C14—O5—C15	115.82 (15)
C6—C5—S1	119.27 (14)	O5—C15—H15A	111.3 (16)
C9—C10—C11	120.32 (15)	O5—C15—H15B	110.8 (17)
C9—C10—H10	119.8 (12)	H15A—C15—H15B	111 (2)
C11—C10—H10	119.8 (12)	O5—C15—H15C	106.5 (18)
C7—C6—C5	119.21 (17)	H15A—C15—H15C	104 (2)
C7—C6—H6	121.4 (15)	H15B—C15—H15C	113 (2)
C5—C6—H6	119.4 (16)
C10—C9—C8—C13	0.1 (3)	C3—C2—C7—C6	−0.3 (3)
C10—C9—C8—O3	174.15 (15)	C1—C2—C7—C6	179.56 (18)
C10—C11—C12—C13	−0.3 (2)	C2—C3—C4—C5	0.1 (3)
C14—C11—C12—C13	176.94 (15)	C6—C5—C4—C3	−0.4 (3)
C9—C8—C13—C12	0.6 (3)	S1—C5—C4—C3	179.06 (13)
O3—C8—C13—C12	−173.65 (14)	C4—C5—S1—O2	153.15 (14)
C11—C12—C13—C8	−0.5 (2)	C6—C5—S1—O2	−27.34 (17)
C12—C11—C14—O4	168.62 (17)	C4—C5—S1—O1	18.62 (16)
C10—C11—C14—O4	−14.1 (3)	C6—C5—S1—O1	−161.87 (14)
C12—C11—C14—O5	−12.6 (2)	C4—C5—S1—O3	−97.69 (14)
C10—C11—C14—O5	164.68 (15)	C6—C5—S1—O3	81.82 (15)
C8—C9—C10—C11	−0.9 (3)	C13—C8—O3—S1	−118.05 (14)
C12—C11—C10—C9	1.1 (3)	C9—C8—O3—S1	67.53 (18)
C14—C11—C10—C9	−176.30 (15)	O2—S1—O3—C8	−173.36 (12)
C4—C5—C6—C7	0.4 (3)	O1—S1—O3—C8	−44.66 (13)
S1—C5—C6—C7	−179.13 (14)	C5—S1—O3—C8	72.20 (13)
C4—C3—C2—C7	0.2 (3)	O4—C14—O5—C15	2.6 (3)
C4—C3—C2—C1	−179.63 (18)	C11—C14—O5—C15	−176.18 (15)
C5—C6—C7—C2	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1	0.964 (18)	2.495 (19)	2.948 (2)	108.6 (14)
C12—H12···O5	0.98 (2)	2.43 (2)	2.735 (2)	97.3 (13)
C10—H10···O4	0.97 (2)	2.54 (2)	2.834 (2)	97.3 (13)
C6—H6···O2	0.97 (3)	2.62 (3)	2.971 (2)	101.6 (18)
C4—H4···O1	0.94 (2)	2.60 (2)	2.942 (2)	102.2 (14)
C15—H15A···O4	0.96 (3)	2.55 (3)	2.656 (3)	85.5 (17)
C3—H3···O2^i	0.94 (2)	2.54 (2)	3.392 (2)	150.3 (19)
C10—H10···O2^ii	0.97 (2)	2.64 (2)	3.314 (2)	126.6 (16)
C9—H9···O2^ii	0.964 (18)	2.807 (19)	3.371 (2)	118.2 (14)
C13—H13···O1^iii	0.95 (2)	2.652 (19)	3.174 (2)	115.0 (14)
C12—H12···O1^iii	0.98 (2)	2.61 (2)	3.166 (2)	115.7 (14)
C1—H1C···O4^iv	0.90 (3)	2.58 (4)	3.403 (3)	153 (3)
C7—H7···O4^iv	0.95 (2)	2.52 (2)	3.355 (2)	145.7 (18)
C7—H7···O3^v	0.95 (2)	2.84 (2)	3.585 (2)	135.6 (18)
C15—H15A···O3^vi	0.96 (3)	2.82 (3)	3.540 (3)	132 (2)
C15—H15A···O2^vi	0.96 (3)	2.96 (3)	3.824 (3)	151 (2)
C1—H1A···O1^vii	0.91 (4)	2.83 (4)	3.560 (3)	139 (3)
C1—H1B···Cg1^viii	0.94 (4)	3.09 (4)	3.982 (3)	160 (3)
C15—H15B···Cg2^ix	0.91 (3)	2.84 (3)	3.693 (3)	156 (2)
C15—H15C···Cg1^iii	0.95 (3)	3.09 (3)	3.844 (2)	138 (2)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) x, y+1, z; (v) −x+1, −y+1, −z; (vi) −x+1, −y, −z; (vii) −x+2, y+1/2, −z+1/2; (viii) −x+2, −y+1, −z; (ix) −x+2, −y, −z.