organic compounds
5-Chloro-1-(4-methylphenylsulfonyl)-1H-indole
aDepartment of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa
*Correspondence e-mail: hassam@sun.ac.za
In the title compound, C15H12ClNO2S, the indole ring is essentially planar (r.m.s. deviation = 0.0107 Å) and makes a dihedral angle of 85.01 (6)° with the benzene ring. In the crystal, three C—H⋯O hydrogen bonds result in a hydrogen-bonded spiral running parallel to the c axis.
Related literature
For background to the use of indoles as scaffolds in the synthesis of HIV-agents, see: Hassam et al. (2012). For the of a closely related compound, see: Beddoes et al. (1986).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED.
Supporting information
10.1107/S1600536812046466/pv2597sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046466/pv2597Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812046466/pv2597Isup3.cml
Sodium hydride (0.325 g, 14.1 mmol) was added to a solution of 5-chloroindole (1.00 g, 6.59 mmol) in dry THF (50 ml) at 273.15 K (ice bath). The reaction mixture was stirred at the same temperature for 10 min, followed by addition of tosyl chloride (4-methyl-benzene-1-sulfonyl chloride, 1.88 g, 9.86 mmol). The reaction mixture was then stirred at 273.15 K for 2 h. Water (25 ml) was added to the flask and the mixture was extracted with diethyl ether (2 x 25 ml). The organic layer was washed with brine (25 ml) and dried over anhydrous sodium sulfate. Solvent was removed under vacuum and the resulting residue was recrystallized from hexane and dichloromethane (4:1) to obtain the title compound as a colourless crystalline material (1.61 g, 80%).
The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 and 0.98 Å, for aryl and methyl H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(methyl C) or 1.2Ueq(aryl C).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED (Barbour, 2001; Atwood & Barbour, 2003).C15H12ClNO2S | Dx = 1.423 Mg m−3 |
Mr = 305.77 | Melting point: 383 K |
Tetragonal, I41/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 4ad | Cell parameters from 3900 reflections |
a = 26.991 (7) Å | θ = 3.0–25.8° |
c = 7.8345 (19) Å | µ = 0.41 mm−1 |
V = 5708 (2) Å3 | T = 111 K |
Z = 16 | Plate, colourless |
F(000) = 2528 | 0.1 × 0.1 × 0.01 mm |
Bruker APEXII CCD diffractometer | 3565 independent reflections |
Radiation source: fine-focus sealed tube, Bruker SMART APEXII | 2760 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 28.9°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −36→26 |
Tmin = 0.950, Tmax = 0.968 | k = −36→30 |
17940 measured reflections | l = −10→9 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0395P)2 + 5.9559P] where P = (Fo2 + 2Fc2)/3 |
3565 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C15H12ClNO2S | Z = 16 |
Mr = 305.77 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.41 mm−1 |
a = 26.991 (7) Å | T = 111 K |
c = 7.8345 (19) Å | 0.1 × 0.1 × 0.01 mm |
V = 5708 (2) Å3 |
Bruker APEXII CCD diffractometer | 3565 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 2760 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.968 | Rint = 0.038 |
17940 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.31 e Å−3 |
3565 reflections | Δρmin = −0.36 e Å−3 |
182 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.309589 (17) | 0.612848 (17) | 0.38622 (6) | 0.02904 (13) | |
Cl1 | 0.494357 (19) | 0.67701 (2) | 0.99440 (8) | 0.04639 (17) | |
C9 | 0.27756 (6) | 0.66717 (7) | 0.4379 (2) | 0.0244 (4) | |
N1 | 0.33623 (5) | 0.59487 (5) | 0.56768 (19) | 0.0257 (3) | |
O2 | 0.27557 (6) | 0.57429 (5) | 0.34641 (19) | 0.0423 (4) | |
C1 | 0.31014 (7) | 0.56870 (7) | 0.6945 (3) | 0.0306 (4) | |
H1 | 0.2805 | 0.5505 | 0.6762 | 0.037* | |
C5 | 0.44798 (7) | 0.65358 (7) | 0.8611 (3) | 0.0304 (4) | |
O1 | 0.34919 (5) | 0.62485 (6) | 0.27270 (16) | 0.0384 (3) | |
C4 | 0.41247 (7) | 0.62301 (7) | 0.9286 (2) | 0.0299 (4) | |
H4 | 0.4129 | 0.6143 | 1.0461 | 0.036* | |
C8 | 0.37656 (6) | 0.61872 (6) | 0.6465 (2) | 0.0223 (3) | |
C6 | 0.44862 (7) | 0.66693 (7) | 0.6895 (3) | 0.0321 (4) | |
H6 | 0.4741 | 0.6879 | 0.6477 | 0.039* | |
C7 | 0.41247 (7) | 0.64987 (7) | 0.5795 (2) | 0.0282 (4) | |
H7 | 0.4122 | 0.6591 | 0.4625 | 0.034* | |
C3 | 0.37571 (6) | 0.60502 (6) | 0.8196 (2) | 0.0245 (4) | |
C11 | 0.27459 (7) | 0.75507 (7) | 0.4642 (3) | 0.0324 (4) | |
H11 | 0.2898 | 0.7865 | 0.4496 | 0.039* | |
C10 | 0.30006 (7) | 0.71282 (7) | 0.4162 (2) | 0.0290 (4) | |
H10 | 0.3324 | 0.7151 | 0.3692 | 0.035* | |
C2 | 0.33347 (7) | 0.57340 (7) | 0.8452 (2) | 0.0306 (4) | |
H2 | 0.3238 | 0.5585 | 0.9499 | 0.037* | |
C12 | 0.22732 (7) | 0.75243 (7) | 0.5330 (2) | 0.0298 (4) | |
C14 | 0.23055 (7) | 0.66336 (7) | 0.5066 (3) | 0.0325 (4) | |
H14 | 0.2155 | 0.6319 | 0.5215 | 0.039* | |
C13 | 0.20586 (7) | 0.70613 (8) | 0.5533 (3) | 0.0343 (4) | |
H13 | 0.1735 | 0.7038 | 0.6002 | 0.041* | |
C15 | 0.19970 (8) | 0.79851 (8) | 0.5824 (3) | 0.0417 (5) | |
H15A | 0.1849 | 0.7940 | 0.6956 | 0.063* | |
H16B | 0.1735 | 0.8050 | 0.4987 | 0.063* | |
H17C | 0.2227 | 0.8266 | 0.5851 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0320 (3) | 0.0321 (3) | 0.0230 (2) | 0.00953 (18) | −0.00349 (18) | −0.00451 (18) |
Cl1 | 0.0310 (3) | 0.0522 (3) | 0.0560 (3) | 0.0064 (2) | −0.0073 (2) | −0.0294 (3) |
C9 | 0.0226 (8) | 0.0297 (9) | 0.0209 (8) | 0.0049 (7) | −0.0012 (7) | −0.0012 (7) |
N1 | 0.0264 (8) | 0.0276 (8) | 0.0231 (7) | 0.0022 (6) | −0.0005 (6) | 0.0019 (6) |
O2 | 0.0480 (9) | 0.0340 (8) | 0.0448 (9) | 0.0065 (6) | −0.0175 (7) | −0.0127 (7) |
C1 | 0.0291 (10) | 0.0247 (9) | 0.0382 (10) | −0.0007 (7) | 0.0041 (8) | 0.0034 (8) |
C5 | 0.0243 (9) | 0.0296 (9) | 0.0375 (10) | 0.0075 (7) | −0.0022 (8) | −0.0120 (8) |
O1 | 0.0414 (8) | 0.0520 (9) | 0.0218 (6) | 0.0217 (7) | 0.0058 (6) | 0.0028 (6) |
C4 | 0.0309 (10) | 0.0356 (10) | 0.0230 (9) | 0.0116 (8) | 0.0002 (7) | −0.0038 (8) |
C8 | 0.0226 (8) | 0.0221 (8) | 0.0224 (8) | 0.0063 (6) | 0.0019 (7) | 0.0009 (6) |
C6 | 0.0243 (9) | 0.0261 (9) | 0.0460 (11) | 0.0023 (7) | 0.0051 (8) | −0.0002 (8) |
C7 | 0.0268 (9) | 0.0296 (9) | 0.0283 (9) | 0.0054 (7) | 0.0062 (7) | 0.0056 (7) |
C3 | 0.0262 (9) | 0.0243 (8) | 0.0230 (8) | 0.0079 (7) | 0.0039 (7) | 0.0019 (7) |
C11 | 0.0338 (10) | 0.0267 (9) | 0.0368 (11) | 0.0006 (8) | 0.0011 (8) | 0.0051 (8) |
C10 | 0.0234 (9) | 0.0347 (10) | 0.0287 (9) | 0.0025 (7) | 0.0048 (7) | 0.0051 (8) |
C2 | 0.0327 (10) | 0.0302 (10) | 0.0288 (10) | 0.0028 (7) | 0.0048 (8) | 0.0083 (8) |
C12 | 0.0312 (10) | 0.0360 (10) | 0.0221 (9) | 0.0096 (8) | −0.0027 (7) | −0.0014 (8) |
C14 | 0.0240 (9) | 0.0331 (10) | 0.0405 (11) | −0.0029 (7) | 0.0030 (8) | −0.0014 (8) |
C13 | 0.0219 (9) | 0.0430 (11) | 0.0379 (11) | 0.0040 (8) | 0.0075 (8) | −0.0015 (9) |
C15 | 0.0483 (13) | 0.0416 (12) | 0.0352 (11) | 0.0223 (10) | −0.0008 (9) | −0.0042 (9) |
S1—O2 | 1.4224 (15) | C6—C7 | 1.381 (3) |
S1—O1 | 1.4278 (15) | C6—H6 | 0.9500 |
S1—N1 | 1.6654 (15) | C7—H7 | 0.9500 |
S1—C9 | 1.7496 (18) | C3—C2 | 1.438 (3) |
Cl1—C5 | 1.7487 (19) | C11—C10 | 1.383 (3) |
C9—C14 | 1.382 (2) | C11—C12 | 1.387 (3) |
C9—C10 | 1.384 (3) | C11—H11 | 0.9500 |
N1—C8 | 1.407 (2) | C10—H10 | 0.9500 |
N1—C1 | 1.408 (2) | C2—H2 | 0.9500 |
C1—C2 | 1.345 (3) | C12—C13 | 1.387 (3) |
C1—H1 | 0.9500 | C12—C15 | 1.501 (3) |
C5—C4 | 1.371 (3) | C14—C13 | 1.382 (3) |
C5—C6 | 1.392 (3) | C14—H14 | 0.9500 |
C4—C3 | 1.396 (3) | C13—H13 | 0.9500 |
C4—H4 | 0.9500 | C15—H15A | 0.9800 |
C8—C7 | 1.386 (2) | C15—H16B | 0.9800 |
C8—C3 | 1.406 (2) | C15—H17C | 0.9800 |
O2—S1—O1 | 120.84 (9) | C8—C7—H7 | 121.3 |
O2—S1—N1 | 104.64 (8) | C4—C3—C8 | 119.13 (17) |
O1—S1—N1 | 105.94 (8) | C4—C3—C2 | 133.19 (17) |
O2—S1—C9 | 110.18 (9) | C8—C3—C2 | 107.68 (16) |
O1—S1—C9 | 108.90 (9) | C10—C11—C12 | 121.37 (18) |
N1—S1—C9 | 105.07 (8) | C10—C11—H11 | 119.3 |
C14—C9—C10 | 121.13 (17) | C12—C11—H11 | 119.3 |
C14—C9—S1 | 118.77 (14) | C11—C10—C9 | 118.83 (17) |
C10—C9—S1 | 120.05 (13) | C11—C10—H10 | 120.6 |
C8—N1—C1 | 107.88 (14) | C9—C10—H10 | 120.6 |
C8—N1—S1 | 125.11 (12) | C1—C2—C3 | 107.74 (16) |
C1—N1—S1 | 122.18 (13) | C1—C2—H2 | 126.1 |
C2—C1—N1 | 109.77 (17) | C3—C2—H2 | 126.1 |
C2—C1—H1 | 125.1 | C13—C12—C11 | 118.36 (17) |
N1—C1—H1 | 125.1 | C13—C12—C15 | 120.65 (18) |
C4—C5—C6 | 122.48 (18) | C11—C12—C15 | 120.98 (19) |
C4—C5—Cl1 | 119.19 (15) | C9—C14—C13 | 118.91 (18) |
C6—C5—Cl1 | 118.33 (15) | C9—C14—H14 | 120.5 |
C5—C4—C3 | 118.06 (17) | C13—C14—H14 | 120.5 |
C5—C4—H4 | 121.0 | C14—C13—C12 | 121.40 (17) |
C3—C4—H4 | 121.0 | C14—C13—H13 | 119.3 |
C7—C8—C3 | 122.42 (17) | C12—C13—H13 | 119.3 |
C7—C8—N1 | 130.71 (16) | C12—C15—H15A | 109.5 |
C3—C8—N1 | 106.86 (15) | C12—C15—H16B | 109.5 |
C7—C6—C5 | 120.51 (18) | H15A—C15—H16B | 109.5 |
C7—C6—H6 | 119.7 | C12—C15—H17C | 109.5 |
C5—C6—H6 | 119.7 | H15A—C15—H17C | 109.5 |
C6—C7—C8 | 117.39 (17) | H16B—C15—H17C | 109.5 |
C6—C7—H7 | 121.3 | ||
O2—S1—C9—C14 | 27.82 (18) | C5—C6—C7—C8 | −1.0 (3) |
O1—S1—C9—C14 | 162.50 (15) | C3—C8—C7—C6 | 0.9 (3) |
N1—S1—C9—C14 | −84.38 (16) | N1—C8—C7—C6 | −178.52 (16) |
O2—S1—C9—C10 | −154.75 (15) | C5—C4—C3—C8 | 0.1 (2) |
O1—S1—C9—C10 | −20.06 (17) | C5—C4—C3—C2 | −179.33 (18) |
N1—S1—C9—C10 | 93.06 (16) | C7—C8—C3—C4 | −0.5 (3) |
O2—S1—N1—C8 | 172.54 (14) | N1—C8—C3—C4 | 179.06 (15) |
O1—S1—N1—C8 | 43.81 (16) | C7—C8—C3—C2 | 179.10 (16) |
C9—S1—N1—C8 | −71.38 (15) | N1—C8—C3—C2 | −1.36 (18) |
O2—S1—N1—C1 | −35.12 (16) | C12—C11—C10—C9 | 0.0 (3) |
O1—S1—N1—C1 | −163.85 (14) | C14—C9—C10—C11 | −0.2 (3) |
C9—S1—N1—C1 | 80.95 (15) | S1—C9—C10—C11 | −177.58 (14) |
C8—N1—C1—C2 | −2.7 (2) | N1—C1—C2—C3 | 1.8 (2) |
S1—N1—C1—C2 | −159.19 (13) | C4—C3—C2—C1 | 179.22 (19) |
C6—C5—C4—C3 | −0.2 (3) | C8—C3—C2—C1 | −0.3 (2) |
Cl1—C5—C4—C3 | 179.67 (13) | C10—C11—C12—C13 | 0.1 (3) |
C1—N1—C8—C7 | −178.07 (17) | C10—C11—C12—C15 | −179.14 (18) |
S1—N1—C8—C7 | −22.5 (3) | C10—C9—C14—C13 | 0.3 (3) |
C1—N1—C8—C3 | 2.45 (18) | S1—C9—C14—C13 | 177.70 (15) |
S1—N1—C8—C3 | 158.06 (12) | C9—C14—C13—C12 | −0.2 (3) |
C4—C5—C6—C7 | 0.7 (3) | C11—C12—C13—C14 | 0.0 (3) |
Cl1—C5—C6—C7 | −179.22 (14) | C15—C12—C13—C14 | 179.24 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.95 | 2.54 | 3.327 (2) | 140 |
C4—H4···O1ii | 0.95 | 2.49 | 3.192 (2) | 131 |
C14—H14···O1iii | 0.95 | 2.59 | 3.333 (2) | 135 |
C7—H7···O1 | 0.95 | 2.44 | 3.025 (2) | 120 |
C10—H10···O1 | 0.95 | 2.59 | 2.943 (2) | 102 |
Symmetry codes: (i) y−1/4, −x+3/4, z+3/4; (ii) x, y, z+1; (iii) −y+3/4, x+1/4, z+1/4. |
Experimental details
Crystal data | |
Chemical formula | C15H12ClNO2S |
Mr | 305.77 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 111 |
a, c (Å) | 26.991 (7), 7.8345 (19) |
V (Å3) | 5708 (2) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.1 × 0.1 × 0.01 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.950, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17940, 3565, 2760 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.680 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.101, 1.06 |
No. of reflections | 3565 |
No. of parameters | 182 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.36 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O2i | 0.95 | 2.54 | 3.327 (2) | 140.0 |
C4—H4···O1ii | 0.95 | 2.49 | 3.192 (2) | 131.0 |
C14—H14···O1iii | 0.95 | 2.59 | 3.333 (2) | 135.1 |
Symmetry codes: (i) y−1/4, −x+3/4, z+3/4; (ii) x, y, z+1; (iii) −y+3/4, x+1/4, z+1/4. |
Acknowledgements
MH thanks Professor Willem A. L. van Otterlo and Dr S. C. Pelly for their valuable input and research oversight. Stellenbosch University's Science Faculty is also acknowledged for providing laboratory space and financial research support (Subcommittee B). The South African National Research Foundation (NRF), Pretoria, is also acknowledged for providing some research funds.
References
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5-Chloroindole is frequently employed as a building block in the synthesis of various biologically active molecules (Hassam et al., 2012). For this communication, tosylation of 5-chloroindole was performed by deprotonation of the indole with sodium hydride, followed by the addition of tosyl chloride.
In the title molecule (Fig. 1), the indole ring is essentially planar (rmsd = 0.0107 Å) with Cl1 lying in its plane (deviation 0.008 (2) Å). The dihedral angle between the mean planes of the indole and benzene rings is 85.01 (6)°. The bond distances and angles in the title compound agree very well with the corresponding bond distances and angles reported for 1-phenylsulfonyl-indole (Beddoes et al., 1986). There are three C—H···O hydrogen bonds which connect four symmetry related molecules into a hydrogen bonded spiral that runs parallel to the c-axis (Table 1 and Fig. 2).