Phenyl 4-toluene­sulfonate: supramolecular aggregation through weak C—H...O and C—H...π interactions

In the crystal structure of the title compound, C₁₃H₁₂O₃S, the dihedral angle between the mean planes of the 4-tolyl and phenyl rings is 52.6 (1)°. There are weak C—H...O hydrogen bonds, which generate rings of graph-set motifs R₁²(4) and R₂¹(9). The supramolecular aggregation is completed by the presence of van der Waals short contacts and C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.067
• wR factor = 0.177
• Data-to-parameter ratio = 20.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT480_ALERT_4_B Long H...A H-Bond Reported H2     ..  O2      ..       2.99 Ang.
PLAT480_ALERT_4_B Long H...A H-Bond Reported H7B    ..  O2      ..       2.98 Ang.
PLAT480_ALERT_4_B Long H...A H-Bond Reported H11    ..  CG1     ..       3.33 Ang.

Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -1.402
            Test value =     -1.200
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT098_ALERT_2_C Minimum (Negative) Residual Density ............      -1.40 e/A   3
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O2      ..       2.76 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9     ..  O1      ..       2.83 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O1      ..       2.83 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13    ..  O1      ..       2.76 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O3      ..       2.78 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O2      ..       2.76 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10    ..  O3      ..       2.89 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9     ..  CG2     ..       2.92 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12    ..  CG2     ..       3.08 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C2     ..  O2      ..       3.76 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C11    ..  CG1     ..       4.09 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C2     ..  O2      ..      99.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C9     ..  O1      ..      95.00 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           30.04
           From the CIF: _reflns_number_total               3277
           Count of symmetry unique reflns         1891
           Completeness (_total/calc)            173.29%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1386
           Fraction of Friedel pairs measured     0.733
           Are heavy atom types Z>Si present        yes

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

   1 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
   1 ALERT type 3 Indicator that the structure quality may be low
  17 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); 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.

Phenyl 4-toluenesulfonate

Crystal data

C13H12O3S	Dx = 1.390 Mg m^−3
Mr = 248.29	Melting point = 367–368 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 25.149 (4) Å	θ = 15–19°
b = 7.976 (5) Å	µ = 0.27 mm^−1
c = 5.916 (4) Å	T = 173 K
V = 1186.7 (10) Å^3	Plate, colorless
Z = 4	0.50 × 0.33 × 0.15 mm
F(000) = 520

Data collection

Rigaku AFC-5R diffractometer	2819 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 30.0°, θmin = 2.6°
ω scans	h = −35→35
Absorption correction: ψ scan (North et al., 1968)	k = −11→10
Tmin = 0.946, Tmax = 0.963	l = −8→8
3909 measured reflections	3 standard reflections every 150 reflections
3277 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.177	w = 1/[σ^2(Fo^2) + (0.1163P)^2 + 0.1087P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3277 reflections	Δρmax = 0.60 e Å^−3
157 parameters	Δρmin = −1.40 e Å^−3
1 restraint	Absolute structure: (Flack, 1983), 1386 Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (12)

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	0.34695 (2)	0.69543 (8)	0.44852 (13)	0.02728 (19)
O1	0.36778 (11)	0.7369 (3)	0.2305 (4)	0.0381 (5)
O2	0.30335 (9)	0.5822 (3)	0.4718 (5)	0.0418 (6)
O3	0.39332 (8)	0.6063 (2)	0.5929 (4)	0.0287 (4)
C1	0.33453 (10)	0.8811 (4)	0.5984 (5)	0.0237 (5)
C2	0.30789 (11)	0.8722 (4)	0.8058 (5)	0.0268 (5)
H2	0.2964	0.7699	0.8632	0.055 (4)*
C3	0.29905 (11)	1.0202 (4)	0.9237 (5)	0.0293 (6)
H3	0.2813	1.0159	1.0614	0.055 (4)*
C4	0.31605 (12)	1.1749 (4)	0.8415 (5)	0.0285 (6)
C5	0.34174 (12)	1.1797 (4)	0.6319 (6)	0.0308 (6)
H5	0.3526	1.2821	0.5725	0.055 (4)*
C6	0.35127 (12)	1.0336 (4)	0.5115 (5)	0.0290 (6)
H6	0.3688	1.0379	0.3732	0.055 (4)*
C7	0.30695 (14)	1.3344 (5)	0.9751 (7)	0.0412 (8)
H7A	0.3371	1.4071	0.9581	0.083 (11)*
H7B	0.3023	1.3072	1.1319	0.083 (11)*
H7C	0.2757	1.3898	0.9199	0.083 (11)*
C8	0.44463 (11)	0.6773 (4)	0.5835 (5)	0.0268 (5)
C9	0.47793 (12)	0.6383 (4)	0.4047 (5)	0.0318 (6)
H9	0.4662	0.5698	0.2876	0.055 (4)*
C10	0.52921 (13)	0.7034 (4)	0.4036 (5)	0.0371 (7)
H10	0.5521	0.6782	0.2850	0.055 (4)*
C11	0.54647 (13)	0.8061 (5)	0.5794 (7)	0.0400 (8)
H11	0.5807	0.8503	0.5770	0.055 (4)*
C12	0.51273 (13)	0.8425 (5)	0.7578 (6)	0.0394 (7)
H12	0.5244	0.9110	0.8749	0.055 (4)*
C13	0.46117 (13)	0.7769 (4)	0.7629 (5)	0.0335 (7)
H13	0.4385	0.7994	0.8833	0.055 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0307 (3)	0.0287 (3)	0.0224 (3)	0.0025 (2)	−0.0044 (3)	−0.0034 (3)
O1	0.0505 (13)	0.0461 (13)	0.0177 (8)	0.0077 (11)	−0.0009 (9)	−0.0034 (10)
O2	0.0379 (10)	0.0380 (12)	0.0494 (15)	−0.0036 (9)	−0.0088 (11)	−0.0114 (12)
O3	0.0305 (9)	0.0282 (10)	0.0272 (9)	0.0022 (7)	−0.0014 (8)	0.0034 (8)
C1	0.0238 (10)	0.0289 (13)	0.0183 (10)	0.0032 (9)	−0.0010 (9)	0.0002 (10)
C2	0.0309 (12)	0.0304 (14)	0.0190 (11)	0.0002 (10)	−0.0005 (10)	0.0065 (11)
C3	0.0307 (11)	0.0389 (15)	0.0183 (11)	0.0019 (10)	0.0012 (10)	0.0019 (12)
C4	0.0289 (12)	0.0326 (14)	0.0240 (12)	0.0031 (11)	−0.0027 (10)	−0.0017 (11)
C5	0.0362 (14)	0.0294 (14)	0.0267 (15)	−0.0051 (11)	0.0024 (11)	0.0013 (12)
C6	0.0332 (12)	0.0319 (15)	0.0219 (11)	−0.0022 (11)	0.0031 (9)	−0.0004 (10)
C7	0.0463 (16)	0.0402 (17)	0.0372 (18)	0.0077 (13)	−0.0025 (15)	−0.0108 (16)
C8	0.0294 (12)	0.0282 (13)	0.0227 (11)	0.0014 (9)	−0.0016 (10)	0.0019 (11)
C9	0.0350 (14)	0.0367 (15)	0.0238 (13)	0.0034 (12)	−0.0020 (11)	−0.0077 (12)
C10	0.0353 (14)	0.0484 (18)	0.0276 (16)	0.0036 (12)	0.0051 (12)	−0.0081 (14)
C11	0.0321 (14)	0.055 (2)	0.0330 (15)	−0.0025 (13)	−0.0011 (14)	−0.0089 (15)
C12	0.0363 (15)	0.052 (2)	0.0298 (15)	−0.0009 (14)	−0.0044 (13)	−0.0141 (15)
C13	0.0364 (14)	0.0451 (18)	0.0189 (12)	0.0045 (13)	−0.0014 (10)	−0.0048 (12)

Geometric parameters (Å, º)

S1—O2	1.427 (2)	C6—H6	0.9300
S1—O1	1.431 (3)	C7—H7A	0.9600
S1—O3	1.611 (2)	C7—H7B	0.9600
S1—C1	1.754 (3)	C7—H7C	0.9600
O3—C8	1.410 (3)	C8—C9	1.384 (4)
C1—C6	1.386 (4)	C8—C13	1.390 (4)
C1—C2	1.400 (4)	C9—C10	1.390 (4)
C2—C3	1.388 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.394 (5)
C3—C4	1.394 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.385 (5)
C4—C5	1.399 (4)	C11—H11	0.9300
C4—C7	1.515 (4)	C12—C13	1.398 (5)
C5—C6	1.387 (4)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
O2—S1—O1	120.98 (17)	C4—C7—H7A	109.5
O2—S1—O3	103.05 (13)	C4—C7—H7B	109.5
O1—S1—O3	108.36 (14)	H7A—C7—H7B	109.5
O2—S1—C1	110.40 (14)	C4—C7—H7C	109.5
O1—S1—C1	108.99 (14)	H7A—C7—H7C	109.5
O3—S1—C1	103.50 (13)	H7B—C7—H7C	109.5
C8—O3—S1	117.68 (18)	C9—C8—C13	122.1 (3)
C6—C1—C2	121.0 (3)	C9—C8—O3	119.6 (3)
C6—C1—S1	120.0 (2)	C13—C8—O3	118.2 (3)
C2—C1—S1	119.1 (2)	C8—C9—C10	118.7 (3)
C3—C2—C1	118.3 (3)	C8—C9—H9	120.6
C3—C2—H2	120.9	C10—C9—H9	120.6
C1—C2—H2	120.9	C9—C10—C11	120.3 (3)
C2—C3—C4	121.9 (3)	C9—C10—H10	119.8
C2—C3—H3	119.1	C11—C10—H10	119.8
C4—C3—H3	119.1	C12—C11—C10	120.1 (3)
C3—C4—C5	118.3 (3)	C12—C11—H11	120.0
C3—C4—C7	121.0 (3)	C10—C11—H11	120.0
C5—C4—C7	120.6 (3)	C11—C12—C13	120.4 (3)
C6—C5—C4	120.8 (3)	C11—C12—H12	119.8
C6—C5—H5	119.6	C13—C12—H12	119.8
C4—C5—H5	119.6	C8—C13—C12	118.4 (3)
C1—C6—C5	119.6 (3)	C8—C13—H13	120.8
C1—C6—H6	120.2	C12—C13—H13	120.8
C5—C6—H6	120.2
O2—S1—O3—C8	172.8 (2)	C7—C4—C5—C6	178.5 (3)
O1—S1—O3—C8	43.5 (3)	C2—C1—C6—C5	0.3 (4)
C1—S1—O3—C8	−72.1 (2)	S1—C1—C6—C5	−179.4 (2)
O2—S1—C1—C6	−143.2 (2)	C4—C5—C6—C1	0.9 (4)
O1—S1—C1—C6	−8.1 (3)	S1—O3—C8—C9	−82.7 (3)
O3—S1—C1—C6	107.1 (2)	S1—O3—C8—C13	101.1 (3)
O2—S1—C1—C2	37.1 (3)	C13—C8—C9—C10	−1.1 (5)
O1—S1—C1—C2	172.2 (2)	O3—C8—C9—C10	−177.1 (3)
O3—S1—C1—C2	−72.6 (2)	C8—C9—C10—C11	−0.1 (5)
C6—C1—C2—C3	−0.6 (4)	C9—C10—C11—C12	0.7 (6)
S1—C1—C2—C3	179.1 (2)	C10—C11—C12—C13	−0.1 (6)
C1—C2—C3—C4	−0.2 (4)	C9—C8—C13—C12	1.6 (5)
C2—C3—C4—C5	1.3 (4)	O3—C8—C13—C12	177.7 (3)
C2—C3—C4—C7	−178.8 (3)	C11—C12—C13—C8	−1.0 (5)
C3—C4—C5—C6	−1.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.76	3.044 (4)	99
C6—H6···O1	0.93	2.54	2.921 (4)	105
C9—H9···O1	0.93	2.83	3.058 (4)	95
C2—H2···O1^i	0.93	2.83	3.122 (4)	100
C13—H13···O1^i	0.93	2.76	3.643 (4)	158
C2—H2···O2^ii	0.93	2.99	3.761 (4)	141
C5—H5···O3^iii	0.93	2.78	3.649 (4)	155
C5—H5···O2^iii	0.93	2.76	3.484 (4)	135
C7—H7B···O2^iv	0.96	2.98	3.543 (5)	119
C7—H7C···O2^v	0.96	2.53	3.406 (4)	152
C10—H10···O3^vi	0.93	2.89	3.644 (4)	140
C3—H3···Cg1^ii	0.93	2.83	3.577	138
C9—H9···Cg2^vii	0.93	2.92	3.638	135
C11—H11···Cg1^viii	0.93	3.33	4.094	141
C12—H12···Cg2^ix	0.93	3.08	3.843	141

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