4-Methyl­phenyl 4-toluene­sulfonate: supramolecular aggregation through weak C—H⋯O and C—H⋯π interactions

Manivannan, V.; Vembu, N.; Nallu, M.; Sivakumar, K.; Fronczek, F.R.

doi:10.1107/S1600536804033343

4-Methylphenyl 4-toluenesulfonate: supramolecular aggregation through weak C—HO and C—Hπ interactions

V. Manivannan, N. Vembu, M. Nallu, K. Sivakumar and F. R. Fronczek

In the crystal structure of the title compound, C₁₄H₁₄O₃S, the dihedral angle between the mean planes of the two rings is 51.97 (8)°. There are weak C—H

O hydrogen bonds which generate rings of graph-set motifs S(5), S(6), R₁²(4) and R₂¹(9). The supramolecular aggregation is completed by the presence of C—H

π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804033343/lh6339sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536804033343/lh6339Isup2.hkl Contains datablock I

CCDC reference: 263666

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.003 Å
R factor = 0.039
wR factor = 0.083
Data-to-parameter ratio = 20.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT480_ALERT_4_B Long H...A H-Bond Reported H7B    ..  O1      ..       3.00 Ang.
PLAT480_ALERT_4_B Long H...A H-Bond Reported H9     ..  CG2     ..       3.18 Ang.
PLAT480_ALERT_4_B Long H...A H-Bond Reported H10    ..  CG2     ..       3.36 Ang.

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.360
           From the CIF: _refine_ls_abs_structure_Flack_su    0.080
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.36
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         20 Ang.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     -   C8      ..       6.68 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  O1      ..       2.75 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9     ..  O2      ..       2.80 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O1      ..       2.70 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O3      ..       2.85 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6     ..  O2      ..       2.86 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  CG1     ..       2.84 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C3     ..  O3      ..       3.73 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C6     ..  O1      ..      99.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C9     ..  O2      ..      99.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C6     ..  O2      ..      99.00 Deg.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.03
           From the CIF: _reflns_number_total               3402
           Count of symmetry unique reflns         2093
           Completeness (_total/calc)            162.54%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1309
           Fraction of Friedel pairs measured     0.625
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  14 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
  16 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPAK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPAK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

4-methylphenyl 4-toluenesulfonate top

Crystal data top

C₁₄H₁₄O₃S	D_x = 1.328 Mg m⁻³
M_r = 262.31	Melting point = 341–342 K
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 11929 reflections
a = 27.6120 (2) Å	θ = 2.5–30.0°
b = 7.9470 (3) Å	µ = 0.24 mm⁻¹
c = 5.977 (1) Å	T = 150 K
V = 1311.5 (2) Å³	Plate, colorless
Z = 4	0.37 × 0.20 × 0.02 mm
F(000) = 552

Data collection top

KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	3402 independent reflections
Radiation source: fine-focus sealed tube	1991 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.000
ω scans with κ offsets	θ_max = 30.0°, θ_min = 2.6°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = 0→37
T_min = 0.926, T_max = 0.995	k = 0→11
19182 measured reflections	l = −8→8

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) = 0.083	w = 1/[σ²(F_o²) + (0.0392P)²] where P = (F_o² + 2F_c²)/3
S = 0.85	(Δ/σ)_max < 0.001
3402 reflections	Δρ_max = 0.17 e Å⁻³
167 parameters	Δρ_min = −0.29 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2093 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.36 (8)

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	0.161632 (18)	0.37628 (6)	0.47787 (11)	0.03394 (14)
O1	0.19964 (5)	0.49418 (16)	0.4521 (3)	0.0451 (4)
O2	0.14396 (6)	0.33311 (19)	0.6935 (2)	0.0422 (4)
O3	0.11816 (5)	0.45990 (15)	0.3394 (3)	0.0352 (4)
C1	0.17432 (7)	0.1919 (2)	0.3292 (4)	0.0281 (5)
C2	0.15944 (7)	0.0378 (2)	0.4142 (3)	0.0331 (5)
H2	0.1442	0.0311	0.5527	0.038 (2)*
C3	0.16773 (8)	−0.1056 (2)	0.2891 (4)	0.0356 (5)
H3	0.1579	−0.2090	0.3457	0.038 (2)*
C4	0.19014 (7)	−0.1002 (2)	0.0830 (4)	0.0317 (5)
C5	0.20511 (7)	0.0568 (2)	0.0035 (4)	0.0341 (5)
H5	0.2206	0.0632	−0.1344	0.038 (2)*
C6	0.19752 (7)	0.2026 (2)	0.1240 (4)	0.0325 (5)
H6	0.2078	0.3060	0.0686	0.038 (2)*
C7	0.19888 (8)	−0.2574 (2)	−0.0509 (5)	0.0452 (6)
H7A	0.2288	−0.3082	−0.0045	0.097 (4)*
H7B	0.2007	−0.2294	−0.2070	0.097 (4)*
H7C	0.1727	−0.3350	−0.0269	0.097 (4)*
C8	0.07377 (8)	0.3713 (2)	0.3284 (4)	0.0316 (5)
C9	0.04095 (8)	0.3844 (2)	0.5030 (5)	0.0394 (6)
H9	0.0487	0.4449	0.6313	0.038 (2)*
C10	−0.00348 (8)	0.3061 (3)	0.4834 (5)	0.0450 (6)
H10	−0.0255	0.3137	0.6008	0.038 (2)*
C11	−0.01612 (8)	0.2166 (3)	0.2934 (5)	0.0428 (6)
C12	0.01776 (9)	0.2061 (3)	0.1230 (4)	0.0443 (6)
H12	0.0102	0.1454	−0.0054	0.038 (2)*
C13	0.06256 (8)	0.2835 (2)	0.1388 (4)	0.0374 (5)
H13	0.0847	0.2759	0.0220	0.038 (2)*
C14	−0.06533 (9)	0.1370 (3)	0.2657 (6)	0.0699 (9)
H14A	−0.0800	0.1223	0.4100	0.097 (4)*
H14B	−0.0619	0.0296	0.1941	0.097 (4)*
H14C	−0.0854	0.2086	0.1755	0.097 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0408 (3)	0.0269 (2)	0.0342 (3)	0.0000 (2)	−0.0053 (3)	−0.0015 (3)
O1	0.0483 (8)	0.0320 (6)	0.0550 (11)	−0.0088 (6)	−0.0072 (9)	−0.0038 (8)
O2	0.0531 (10)	0.0430 (8)	0.0305 (9)	0.0048 (7)	−0.0030 (8)	−0.0033 (7)
O3	0.0370 (8)	0.0235 (7)	0.0451 (9)	0.0000 (6)	−0.0026 (7)	0.0029 (7)
C1	0.0271 (11)	0.0270 (9)	0.0302 (12)	−0.0006 (8)	−0.0058 (9)	−0.0001 (10)
C2	0.0365 (11)	0.0331 (11)	0.0297 (13)	−0.0029 (9)	0.0062 (10)	0.0043 (9)
C3	0.0419 (13)	0.0248 (10)	0.0400 (14)	0.0003 (9)	0.0022 (11)	0.0069 (11)
C4	0.0299 (12)	0.0337 (11)	0.0315 (12)	0.0050 (9)	−0.0022 (10)	−0.0011 (9)
C5	0.0293 (10)	0.0455 (10)	0.0275 (13)	0.0005 (9)	0.0032 (11)	0.0051 (12)
C6	0.0355 (12)	0.0319 (11)	0.0301 (14)	−0.0037 (10)	−0.0032 (10)	0.0048 (10)
C7	0.0491 (13)	0.0411 (11)	0.0454 (16)	0.0057 (10)	0.0014 (14)	−0.0099 (13)
C8	0.0396 (13)	0.0252 (9)	0.0302 (12)	0.0083 (9)	−0.0028 (11)	0.0001 (11)
C9	0.0480 (14)	0.0373 (10)	0.0329 (15)	0.0123 (10)	−0.0004 (12)	−0.0065 (11)
C10	0.0426 (13)	0.0515 (12)	0.0410 (14)	0.0141 (10)	0.0081 (14)	0.0075 (16)
C11	0.0341 (14)	0.0396 (12)	0.0548 (18)	0.0055 (11)	−0.0036 (13)	0.0086 (13)
C12	0.0507 (15)	0.0400 (13)	0.0421 (16)	0.0044 (12)	−0.0146 (13)	−0.0064 (11)
C13	0.0388 (13)	0.0427 (12)	0.0308 (14)	0.0071 (11)	−0.0002 (10)	−0.0040 (11)
C14	0.0441 (16)	0.0709 (17)	0.095 (3)	0.0010 (14)	−0.0122 (16)	0.0101 (18)

Geometric parameters (Å, º) top

S1—O1	1.4153 (14)	C7—H7B	0.9600
S1—O2	1.4199 (16)	C7—H7C	0.9600
S1—O3	1.6023 (15)	C8—C13	1.366 (3)
S1—C1	1.749 (2)	C8—C9	1.386 (3)
O3—C8	1.415 (2)	C9—C10	1.381 (3)
C1—C6	1.386 (3)	C9—H9	0.9300
C1—C2	1.389 (3)	C10—C11	1.385 (4)
C2—C3	1.382 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.385 (4)
C3—C4	1.379 (3)	C11—C14	1.508 (3)
C3—H3	0.9300	C12—C13	1.385 (3)
C4—C5	1.398 (3)	C12—H12	0.9300
C4—C7	1.503 (3)	C13—H13	0.9300
C5—C6	1.381 (3)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—H7A	0.9600

O1—S1—O2	120.89 (12)	C4—C7—H7C	109.5
O1—S1—O3	102.99 (9)	H7A—C7—H7C	109.5
O2—S1—O3	108.15 (9)	H7B—C7—H7C	109.5
O1—S1—C1	110.54 (10)	C13—C8—C9	121.0 (2)
O2—S1—C1	109.12 (10)	C13—C8—O3	119.26 (19)
O3—S1—C1	103.59 (9)	C9—C8—O3	119.59 (19)
C8—O3—S1	117.81 (12)	C10—C9—C8	118.9 (2)
C6—C1—C2	120.99 (19)	C10—C9—H9	120.6
C6—C1—S1	119.38 (15)	C8—C9—H9	120.6
C2—C1—S1	119.59 (17)	C9—C10—C11	121.7 (3)
C3—C2—C1	118.68 (19)	C9—C10—H10	119.2
C3—C2—H2	120.7	C11—C10—H10	119.2
C1—C2—H2	120.7	C10—C11—C12	117.6 (2)
C4—C3—C2	122.19 (19)	C10—C11—C14	122.2 (3)
C4—C3—H3	118.9	C12—C11—C14	120.2 (3)
C2—C3—H3	118.9	C13—C12—C11	121.8 (2)
C3—C4—C5	117.64 (19)	C13—C12—H12	119.1
C3—C4—C7	121.49 (19)	C11—C12—H12	119.1
C5—C4—C7	120.9 (2)	C8—C13—C12	119.1 (2)
C6—C5—C4	121.8 (2)	C8—C13—H13	120.5
C6—C5—H5	119.1	C12—C13—H13	120.5
C4—C5—H5	119.1	C11—C14—H14A	109.5
C5—C6—C1	118.69 (19)	C11—C14—H14B	109.5
C5—C6—H6	120.7	H14A—C14—H14B	109.5
C1—C6—H6	120.7	C11—C14—H14C	109.5
C4—C7—H7A	109.5	H14A—C14—H14C	109.5
C4—C7—H7B	109.5	H14B—C14—H14C	109.5
H7A—C7—H7B	109.5

O1—S1—O3—C8	179.25 (15)	C4—C5—C6—C1	−0.1 (3)
O2—S1—O3—C8	−51.70 (16)	C2—C1—C6—C5	0.8 (3)
C1—S1—O3—C8	64.02 (17)	S1—C1—C6—C5	−176.80 (14)
O1—S1—C1—C6	−37.0 (2)	S1—O3—C8—C13	−101.8 (2)
O2—S1—C1—C6	−172.25 (16)	S1—O3—C8—C9	82.6 (2)
O3—S1—C1—C6	72.73 (18)	C13—C8—C9—C10	0.4 (3)
O1—S1—C1—C2	145.37 (16)	O3—C8—C9—C10	175.83 (18)
O2—S1—C1—C2	10.1 (2)	C8—C9—C10—C11	−0.6 (3)
O3—S1—C1—C2	−104.91 (17)	C9—C10—C11—C12	0.8 (3)
C6—C1—C2—C3	−0.7 (3)	C9—C10—C11—C14	−177.2 (2)
S1—C1—C2—C3	176.90 (16)	C10—C11—C12—C13	−0.8 (3)
C1—C2—C3—C4	−0.1 (3)	C14—C11—C12—C13	177.3 (2)
C2—C3—C4—C5	0.8 (3)	C9—C8—C13—C12	−0.4 (3)
C2—C3—C4—C7	179.99 (19)	O3—C8—C13—C12	−175.85 (17)
C3—C4—C5—C6	−0.7 (3)	C11—C12—C13—C8	0.6 (3)
C7—C4—C5—C6	−179.88 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.54	2.912 (2)	104
C6—H6···O1	0.93	2.75	3.036 (3)	99
C9—H9···O2	0.93	2.80	3.091 (3)	99
C3—H3···O1ⁱ	0.93	2.70	3.442 (2)	137
C3—H3···O3ⁱ	0.93	2.85	3.727 (2)	158
C6—H6···O2ⁱⁱ	0.93	2.86	3.144 (3)	99
C13—H13···O2ⁱⁱ	0.93	2.60	3.506 (3)	166
C7—H7A···O1ⁱⁱⁱ	0.96	2.54	3.428 (2)	154
C7—H7B···O1^iv	0.96	3.00	3.566 (3)	119
C5—H5···Cg1ⁱⁱⁱ	0.93	2.84	3.58	137
C9—H9···Cg2^v	0.93	3.18	3.70	117
C10—H10···Cg2^v	0.93	3.36	3.80	111

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

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4-Methyl­phenyl 4-toluene­sulfonate: supramolecular aggregation through weak C—HO and C—Hπ interactions

Supporting information

Key indicators

checkCIF/PLATON results

4-Methylphenyl 4-toluenesulfonate: supramolecular aggregation through weak C—HO and C—Hπ interactions