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

In the crystal structure of the title compound, C₁₃H₁₁BrO₃S, the dihedral angle between the mean planes of the 4-tol­yl and 4-bromo­phen­yl rings is 67.3 (2)°. There are weak C—H...O hydrogen bonds which generate rings of graph-set motifs S(5), S(6), R₁²(4), R₂¹(6) and R₂²(8). The supramolecular aggregation is completed by the presence of C—H...π inter­actions. An R₂²(7) motif formed by the combination of a C—H...O and a C—H...π inter­action is a notable feature in the title compound.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.035
• wR factor = 0.094
• Data-to-parameter ratio = 7.6

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.543     0.738
            Tmin and Tmax expected:      0.435     0.723
            RR =      1.222
            Please check that your absorption correction is appropriate.
PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro .          ?
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.24
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       7.64
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O2      ..       2.85 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13    ..  O1      ..       2.88 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  O2      ..       2.94 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O2      ..       2.84 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7C    ..  O3      ..       2.84 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H7B    ..  O2      ..       2.90 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10    ..  CG2     ..       3.23 Ang.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C2     ..  O2      ..      95.00 Deg.
PLAT482_ALERT_4_C Small D-H..A Angle Rep for C13    ..  O1      ..      98.00 Deg.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.03
           From the CIF: _reflns_number_total               1253
           Count of symmetry unique reflns         1264
           Completeness (_total/calc)             99.13%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  15 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
  11 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius, 1997); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXL97.

4-bromophenyl 4-toluenesulfonate

Crystal data

C13H11BrO3S	Dx = 1.633 Mg m^−3
Mr = 327.19	Melting point = 366–367 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1207 reflections
a = 5.9422 (2) Å	θ = 2.5–25.0°
b = 28.3304 (10) Å	µ = 3.24 mm^−1
c = 7.9071 (3) Å	T = 120 K
V = 1331.12 (8) Å^3	Prism, colorless
Z = 4	0.27 × 0.22 × 0.10 mm
F(000) = 656

Data collection

KappaCCD diffractometer (with an Oxford Cryosystems Cryostream cooler)	1253 independent reflections
Radiation source: fine-focus sealed tube	1199 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans with κ offsets	θmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −7→7
Tmin = 0.543, Tmax = 0.738	k = −33→33
4173 measured reflections	l = −9→9

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 1.694P] where P = (Fo^2 + 2Fc^2)/3
1253 reflections	(Δ/σ)max = 0.013
164 parameters	Δρmax = 0.39 e Å^−3
1 restraint	Δρmin = −0.51 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
Br1	0.63287 (11)	0.579171 (18)	0.01200 (13)	0.0466 (2)
S1	0.9586 (2)	0.33849 (5)	−0.02358 (15)	0.0257 (3)
O1	1.1598 (5)	0.36276 (12)	0.0210 (7)	0.0337 (8)
O2	0.9668 (8)	0.29766 (14)	−0.1271 (6)	0.0386 (10)
O3	0.8020 (6)	0.37387 (13)	−0.1287 (5)	0.0276 (8)
C1	0.8031 (9)	0.32696 (18)	0.1595 (7)	0.0225 (11)
C2	0.5995 (9)	0.3028 (2)	0.1475 (8)	0.0253 (11)
H2	0.5440	0.2932	0.0430	0.030*
C3	0.4815 (9)	0.29331 (19)	0.2952 (8)	0.0256 (11)
H3	0.3452	0.2773	0.2887	0.031*
C4	0.5619 (9)	0.30718 (19)	0.4525 (7)	0.0239 (11)
C5	0.7673 (9)	0.33101 (18)	0.4610 (7)	0.0266 (12)
H5	0.8237	0.3401	0.5658	0.032*
C6	0.8882 (9)	0.34137 (19)	0.3163 (7)	0.0244 (12)
H6	1.0238	0.3576	0.3230	0.029*
C7	0.4312 (11)	0.2969 (2)	0.6102 (8)	0.0353 (14)
H7A	0.4575	0.2649	0.6444	0.053*
H7B	0.2736	0.3014	0.5887	0.053*
H7C	0.4787	0.3180	0.6985	0.053*
C8	0.7749 (10)	0.42104 (17)	−0.0792 (7)	0.0260 (12)
C9	0.5850 (9)	0.43371 (19)	0.0085 (10)	0.0316 (12)
H9	0.4847	0.4109	0.0468	0.038*
C10	0.5458 (9)	0.4810 (2)	0.0386 (9)	0.0355 (13)
H10	0.4149	0.4904	0.0937	0.043*
C11	0.6999 (10)	0.51423 (18)	−0.0129 (8)	0.0308 (12)
C12	0.8953 (10)	0.5009 (2)	−0.0957 (9)	0.0373 (16)
H12	0.9999	0.5236	−0.1285	0.045*
C13	0.9334 (10)	0.4540 (2)	−0.1288 (9)	0.0343 (13)
H13	1.0641	0.4445	−0.1839	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0542 (4)	0.0291 (3)	0.0566 (4)	0.0073 (2)	0.0078 (4)	0.0054 (3)
S1	0.0259 (6)	0.0288 (6)	0.0222 (7)	0.0015 (5)	0.0050 (6)	0.0015 (5)
O1	0.0219 (16)	0.042 (2)	0.037 (2)	−0.0068 (14)	0.005 (2)	0.006 (2)
O2	0.054 (3)	0.036 (2)	0.026 (2)	0.0058 (19)	0.012 (2)	−0.0055 (19)
O3	0.035 (2)	0.0296 (19)	0.0183 (17)	0.0006 (17)	−0.0050 (17)	0.0005 (17)
C1	0.022 (2)	0.026 (3)	0.020 (3)	−0.002 (2)	0.003 (2)	−0.002 (2)
C2	0.024 (3)	0.028 (3)	0.025 (2)	−0.001 (2)	−0.002 (2)	0.004 (2)
C3	0.020 (3)	0.025 (3)	0.032 (3)	−0.004 (2)	−0.001 (2)	0.000 (2)
C4	0.025 (2)	0.026 (3)	0.021 (3)	0.003 (2)	0.003 (2)	0.005 (2)
C5	0.031 (3)	0.030 (3)	0.020 (3)	0.002 (2)	−0.005 (2)	−0.005 (2)
C6	0.021 (2)	0.027 (3)	0.026 (3)	−0.001 (2)	−0.001 (2)	−0.002 (2)
C7	0.035 (3)	0.040 (3)	0.031 (3)	0.003 (3)	0.013 (3)	0.005 (3)
C8	0.027 (3)	0.028 (3)	0.023 (3)	0.000 (2)	−0.002 (2)	0.009 (2)
C9	0.027 (3)	0.035 (3)	0.032 (3)	−0.007 (2)	0.004 (3)	0.006 (4)
C10	0.026 (3)	0.040 (3)	0.040 (4)	0.003 (2)	0.010 (3)	0.004 (3)
C11	0.034 (3)	0.030 (3)	0.028 (3)	0.000 (2)	0.003 (3)	0.002 (3)
C12	0.028 (3)	0.035 (3)	0.049 (4)	−0.008 (2)	0.008 (3)	0.014 (3)
C13	0.027 (3)	0.040 (3)	0.035 (3)	0.004 (3)	0.008 (3)	0.007 (3)

Geometric parameters (Å, º)

Br1—C11	1.893 (5)	C5—H5	0.930
S1—O2	1.418 (4)	C6—H6	0.930
S1—O1	1.423 (4)	C7—H7A	0.960
S1—O3	1.600 (4)	C7—H7B	0.960
S1—C1	1.748 (5)	C7—H7C	0.960
O3—C8	1.402 (6)	C8—C9	1.372 (9)
C1—C2	1.394 (7)	C8—C13	1.383 (8)
C1—C6	1.400 (8)	C9—C10	1.380 (8)
C2—C3	1.388 (8)	C9—H9	0.930
C2—H2	0.930	C10—C11	1.375 (8)
C3—C4	1.389 (8)	C10—H10	0.930
C3—H3	0.930	C11—C12	1.385 (8)
C4—C5	1.396 (8)	C12—C13	1.374 (9)
C4—C7	1.497 (8)	C12—H12	0.930
C5—C6	1.382 (8)	C13—H13	0.930
O2—S1—O1	120.5 (3)	C4—C7—H7A	109.5
O2—S1—O3	103.4 (2)	C4—C7—H7B	109.5
O1—S1—O3	108.3 (2)	H7A—C7—H7B	109.5
O2—S1—C1	110.1 (3)	C4—C7—H7C	109.5
O1—S1—C1	109.2 (3)	H7A—C7—H7C	109.5
O3—S1—C1	103.9 (2)	H7B—C7—H7C	109.5
C8—O3—S1	121.3 (3)	C9—C8—C13	121.8 (5)
C2—C1—C6	121.1 (5)	C9—C8—O3	119.0 (5)
C2—C1—S1	119.6 (4)	C13—C8—O3	119.1 (5)
C6—C1—S1	119.2 (4)	C8—C9—C10	118.7 (5)
C3—C2—C1	118.4 (5)	C8—C9—H9	120.7
C3—C2—H2	120.8	C10—C9—H9	120.7
C1—C2—H2	120.8	C11—C10—C9	120.1 (5)
C2—C3—C4	121.7 (5)	C11—C10—H10	120.0
C2—C3—H3	119.2	C9—C10—H10	120.0
C4—C3—H3	119.2	C10—C11—C12	120.8 (5)
C3—C4—C5	118.7 (5)	C10—C11—Br1	119.7 (4)
C3—C4—C7	120.8 (5)	C12—C11—Br1	119.3 (4)
C5—C4—C7	120.5 (5)	C13—C12—C11	119.4 (5)
C6—C5—C4	121.1 (5)	C13—C12—H12	120.3
C6—C5—H5	119.4	C11—C12—H12	120.3
C4—C5—H5	119.4	C12—C13—C8	119.1 (6)
C5—C6—C1	118.9 (4)	C12—C13—H13	120.4
C5—C6—H6	120.5	C8—C13—H13	120.4
C1—C6—H6	120.5
O2—S1—O3—C8	−171.7 (4)	C4—C5—C6—C1	−0.9 (8)
O1—S1—O3—C8	−42.7 (5)	C2—C1—C6—C5	0.3 (8)
C1—S1—O3—C8	73.3 (4)	S1—C1—C6—C5	−178.3 (4)
O2—S1—C1—C2	−44.7 (5)	S1—O3—C8—C9	−99.9 (6)
O1—S1—C1—C2	−179.1 (4)	S1—O3—C8—C13	84.0 (6)
O3—S1—C1—C2	65.5 (5)	C13—C8—C9—C10	3.9 (10)
O2—S1—C1—C6	134.0 (5)	O3—C8—C9—C10	−172.1 (5)
O1—S1—C1—C6	−0.5 (5)	C8—C9—C10—C11	−2.6 (10)
O3—S1—C1—C6	−115.9 (5)	C9—C10—C11—C12	0.2 (10)
C6—C1—C2—C3	0.2 (8)	C9—C10—C11—Br1	174.7 (5)
S1—C1—C2—C3	178.8 (4)	C10—C11—C12—C13	1.0 (10)
C1—C2—C3—C4	−0.2 (8)	Br1—C11—C12—C13	−173.5 (5)
C2—C3—C4—C5	−0.3 (8)	C11—C12—C13—C8	0.2 (10)
C2—C3—C4—C7	179.6 (6)	C9—C8—C13—C12	−2.7 (10)
C3—C4—C5—C6	0.9 (8)	O3—C8—C13—C12	173.3 (6)
C7—C4—C5—C6	−179.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.85	3.082 (7)	95
C6—H6···O1	0.93	2.53	2.903 (8)	105
C13—H13···O1	0.93	2.88	3.145 (7)	98
C2—H2···O2^i	0.93	2.94	3.664 (7)	136
C5—H5···O2^ii	0.93	2.84	3.593 (7)	139
C7—H7C···O3^ii	0.96	2.84	3.724 (8)	154
C5—H5···O3^ii	0.93	2.60	3.470 (6)	156
C7—H7A···O2^iii	0.96	2.53	3.398 (8)	150
C7—H7B···O2^iv	0.96	2.90	3.454 (7)	118
C9—H9···O1^v	0.93	2.37	3.230 (6)	153
C3—H3···Cg1^i	0.93	2.84	3.595	139
C10—H10···Cg2^vi	0.93	3.23	3.980	139

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