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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3018.
Published online 2009 November 7. doi:  10.1107/S1600536809044559
PMCID: PMC2972132

4-Chloro-1-(4-methyl­phenyl­sulfon­yl)-1H-pyrrolo[2,3-b]pyridine

Abstract

The crystal structure of the title compound, C14H11ClN2O2S, features a three-dimensional network stabilized by π–π inter­actions between the rings of the 4-methyl­phenyl­sulfonyl protecting group [centroid–centroid distance = 3.623 (1) Å]. The 4-methyl­phenyl­sulfonyl ring makes a dihedral angle of 79.60 (6)° with the 4-chloro-1H-pyrrolo[2,3-b]pyridine unit.

Related literature

For the synthesis of the title compound, see: Desarbre et al. (1997 [triangle]).

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Object name is e-65-o3018-scheme1.jpg

Experimental

Crystal data

  • C14H11ClN2O2S
  • M r = 306.76
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3018-efi1.jpg
  • a = 21.7342 (12) Å
  • b = 7.6313 (2) Å
  • c = 16.4649 (8) Å
  • β = 91.531 (2)°
  • V = 2729.9 (2) Å3
  • Z = 8
  • Cu Kα radiation
  • μ = 3.94 mm−1
  • T = 193 K
  • 0.52 × 0.24 × 0.20 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: numerical (PLATON; Spek, 2009 [triangle]) T min = 0.319, T max = 0.519
  • 2580 measured reflections
  • 2580 independent reflections
  • 2435 reflections with I > 2σ(I)
  • 3 standard reflections frequency: 60 min intensity decay: 2%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.119
  • S = 1.09
  • 2580 reflections
  • 181 parameters
  • H-atom parameters constrained
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 [triangle]); program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809044559/bt5113sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044559/bt5113Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors would like to thank the Federal Ministry of Education and Research, Germany, Merckle GmbH, Ulm, Germany, and the Fonds der Chemischen Industrie, Germany, for their generous support of this work.

supplementary crystallographic information

Comment

In recent years, compounds with the 1H-pyrrolo[2,3-b]pyridine moiety have been shown to display significant biological activities. The N-protected 4-chloro-1H-pyrrolo[2,3-b]pyridine is an important precursor for NH sensitive reactions like coupling reactions or metalation experiments. The title compound forms a three dimensional network stabilized by π -π interactions between two phenyl moieties of the 4-methylphenylsulfonyl protecting group (distance between centroids 3.623 (1) Å). The 4-methylphenylsulfonyl ring makes a dihedral angle of 79.60 (6)° to the 4-chloro-1H-pyrrolo[2,3-b]pyridine.

Experimental

Finely powdered sodium hydroxide (1.9 g, 34 mmol) was added to a solution of dichloromethane containing benzyltriethylammonium chloride (67 mg, 0.30 mmol) and 4-chlor-1H-pyrrolo[2,3-b]pyridine (1.5 g, 9.8 mmol). p-Toluensulfonylchloride (2.2 g, 12 mmol) was slowly added at 273 K and the resulting suspension was stirred at this temperature for 2 h at room temperature. The suspension was filtered through celite, washed with dichloromethane and the filtrate was evaporated in vacuo. The residue was suspendet in methanol and filtered off. The filtrate was dried in vacuo to give the pure title compound in a good yield of 78%.

Refinement

Hydrogen atoms were placed at calculated positions with Caromatic—H = 0.95 Å or Cmethyl—H = 0.98Å and they were refined in the riding-model approximation with isotropic displacement parameters (set at 1.2–1.5 times of the Ueq of the parent atom).

Figures

Fig. 1.
View of compound I. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C14H11ClN2O2SF(000) = 1264
Mr = 306.76Dx = 1.493 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 21.7342 (12) Åθ = 65–70°
b = 7.6313 (2) ŵ = 3.94 mm1
c = 16.4649 (8) ÅT = 193 K
β = 91.531 (2)°Block, colourless
V = 2729.9 (2) Å30.52 × 0.24 × 0.20 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometer2435 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.0000
graphiteθmax = 69.9°, θmin = 4.1°
ω/2θ scansh = 0→26
Absorption correction: numerical (PLATON; Spek, 2009)k = 0→9
Tmin = 0.319, Tmax = 0.519l = −20→20
2580 measured reflections3 standard reflections every 60 min
2580 independent reflections intensity decay: 2%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0708P)2 + 2.2448P] where P = (Fo2 + 2Fc2)/3
2580 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = −0.48 e Å3

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 (Å2)

xyzUiso*/Ueq
S10.37591 (3)0.21601 (7)0.24460 (3)0.04415 (18)
Cl10.17076 (3)0.02839 (8)0.52042 (4)0.0552 (2)
O10.35059 (9)0.2966 (2)0.17315 (9)0.0568 (4)
O20.40887 (9)0.0548 (2)0.23960 (10)0.0574 (4)
N10.31423 (8)0.1778 (2)0.30138 (10)0.0419 (4)
C20.25596 (11)0.2537 (3)0.28739 (14)0.0471 (5)
H20.24480.32490.24200.057*
C30.21846 (10)0.2106 (3)0.34773 (14)0.0452 (5)
H30.17660.24400.35200.054*
C3A0.25318 (9)0.1048 (3)0.40466 (12)0.0393 (4)
C40.24293 (10)0.0231 (3)0.47865 (13)0.0428 (5)
C50.29115 (11)−0.0600 (3)0.51803 (13)0.0463 (5)
H50.2853−0.11650.56860.056*
C60.34872 (11)−0.0608 (3)0.48308 (13)0.0458 (5)
H60.3814−0.11780.51200.055*
N70.36143 (8)0.0130 (2)0.41150 (11)0.0427 (4)
C7A0.31332 (9)0.0897 (2)0.37609 (12)0.0374 (4)
C80.41925 (9)0.3694 (3)0.30021 (11)0.0381 (4)
C90.40403 (10)0.5448 (3)0.29162 (14)0.0466 (5)
H90.36960.57850.25850.056*
C100.43905 (10)0.6698 (3)0.33118 (14)0.0478 (5)
H100.42840.78990.32520.057*
C110.48956 (9)0.6237 (3)0.37969 (12)0.0434 (5)
C120.50321 (10)0.4468 (3)0.38851 (14)0.0484 (5)
H120.53730.41290.42230.058*
C130.46853 (10)0.3189 (3)0.34933 (13)0.0451 (5)
H130.47850.19850.35610.054*
C140.52904 (13)0.7648 (4)0.41851 (17)0.0615 (6)
H14A0.56280.71050.45020.092*
H14B0.50400.83620.45440.092*
H14C0.54610.83920.37610.092*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0603 (3)0.0409 (3)0.0313 (3)0.0037 (2)0.0033 (2)−0.00179 (18)
Cl10.0548 (3)0.0523 (3)0.0593 (4)−0.0143 (2)0.0148 (3)−0.0159 (2)
O10.0779 (11)0.0603 (11)0.0319 (7)−0.0021 (8)−0.0050 (7)0.0023 (7)
O20.0793 (12)0.0432 (9)0.0503 (9)0.0096 (8)0.0149 (8)−0.0083 (7)
N10.0500 (10)0.0398 (9)0.0359 (8)0.0004 (7)−0.0024 (7)0.0025 (7)
C20.0551 (12)0.0437 (11)0.0417 (11)0.0038 (10)−0.0146 (9)−0.0013 (9)
C30.0437 (11)0.0434 (12)0.0479 (11)−0.0010 (9)−0.0102 (9)−0.0115 (9)
C3A0.0450 (10)0.0315 (9)0.0411 (10)−0.0049 (8)−0.0031 (8)−0.0102 (8)
C40.0503 (11)0.0348 (10)0.0433 (11)−0.0095 (8)0.0045 (9)−0.0113 (8)
C50.0645 (13)0.0360 (10)0.0383 (10)−0.0070 (10)0.0012 (9)−0.0001 (8)
C60.0584 (12)0.0348 (10)0.0440 (11)0.0037 (9)−0.0036 (9)0.0026 (9)
N70.0509 (10)0.0355 (9)0.0416 (9)0.0038 (7)0.0007 (7)0.0006 (7)
C7A0.0473 (10)0.0285 (9)0.0362 (9)−0.0016 (8)−0.0013 (8)−0.0044 (7)
C80.0450 (10)0.0387 (10)0.0310 (9)0.0052 (8)0.0077 (7)0.0022 (7)
C90.0504 (12)0.0422 (11)0.0469 (11)0.0105 (9)−0.0042 (9)0.0061 (9)
C100.0551 (12)0.0367 (11)0.0519 (12)0.0071 (9)0.0051 (10)0.0053 (9)
C110.0431 (10)0.0476 (12)0.0401 (10)−0.0026 (9)0.0107 (8)0.0034 (9)
C120.0431 (11)0.0534 (13)0.0483 (12)0.0063 (10)−0.0025 (9)0.0077 (10)
C130.0505 (11)0.0402 (11)0.0447 (11)0.0120 (9)0.0038 (9)0.0061 (9)
C140.0609 (14)0.0572 (15)0.0665 (16)−0.0147 (12)0.0030 (12)0.0037 (12)

Geometric parameters (Å, °)

S1—O11.4250 (16)C6—H60.9500
S1—O21.4269 (17)N7—C7A1.320 (3)
S1—N11.6803 (18)C8—C131.380 (3)
S1—C81.746 (2)C8—C91.385 (3)
Cl1—C41.730 (2)C9—C101.374 (3)
N1—C7A1.402 (3)C9—H90.9500
N1—C21.406 (3)C10—C111.386 (3)
C2—C31.343 (3)C10—H100.9500
C2—H20.9500C11—C121.389 (3)
C3—C3A1.436 (3)C11—C141.508 (3)
C3—H30.9500C12—C131.382 (3)
C3A—C41.392 (3)C12—H120.9500
C3A—C7A1.406 (3)C13—H130.9500
C4—C51.373 (3)C14—H14A0.9800
C5—C61.391 (3)C14—H14B0.9800
C5—H50.9500C14—H14C0.9800
C6—N71.342 (3)
O1—S1—O2120.52 (10)N7—C7A—N1124.77 (19)
O1—S1—N1103.77 (10)N7—C7A—C3A128.40 (19)
O2—S1—N1106.95 (10)N1—C7A—C3A106.81 (17)
O1—S1—C8109.55 (10)C13—C8—C9120.6 (2)
O2—S1—C8110.09 (10)C13—C8—S1121.32 (17)
N1—S1—C8104.58 (9)C9—C8—S1118.05 (16)
C7A—N1—C2107.91 (18)C10—C9—C8119.7 (2)
C7A—N1—S1126.97 (15)C10—C9—H9120.2
C2—N1—S1124.46 (16)C8—C9—H9120.2
C3—C2—N1109.85 (19)C9—C10—C11121.2 (2)
C3—C2—H2125.1C9—C10—H10119.4
N1—C2—H2125.1C11—C10—H10119.4
C2—C3—C3A107.59 (19)C10—C11—C12118.1 (2)
C2—C3—H3126.2C10—C11—C14119.7 (2)
C3A—C3—H3126.2C12—C11—C14122.1 (2)
C4—C3A—C7A115.35 (19)C13—C12—C11121.7 (2)
C4—C3A—C3136.9 (2)C13—C12—H12119.2
C7A—C3A—C3107.75 (19)C11—C12—H12119.2
C5—C4—C3A118.8 (2)C8—C13—C12118.8 (2)
C5—C4—Cl1120.78 (17)C8—C13—H13120.6
C3A—C4—Cl1120.37 (17)C12—C13—H13120.6
C4—C5—C6119.4 (2)C11—C14—H14A109.5
C4—C5—H5120.3C11—C14—H14B109.5
C6—C5—H5120.3H14A—C14—H14B109.5
N7—C6—C5124.8 (2)C11—C14—H14C109.5
N7—C6—H6117.6H14A—C14—H14C109.5
C5—C6—H6117.6H14B—C14—H14C109.5
C7A—N7—C6113.26 (19)
O1—S1—N1—C7A175.64 (17)C2—N1—C7A—C3A3.3 (2)
O2—S1—N1—C7A47.22 (19)S1—N1—C7A—C3A174.17 (14)
C8—S1—N1—C7A−69.55 (19)C4—C3A—C7A—N7−2.3 (3)
O1—S1—N1—C2−14.9 (2)C3—C3A—C7A—N7175.68 (19)
O2—S1—N1—C2−143.28 (18)C4—C3A—C7A—N1179.38 (16)
C8—S1—N1—C299.95 (18)C3—C3A—C7A—N1−2.6 (2)
C7A—N1—C2—C3−2.7 (2)O1—S1—C8—C13−151.45 (17)
S1—N1—C2—C3−173.92 (15)O2—S1—C8—C13−16.72 (19)
N1—C2—C3—C3A1.0 (2)N1—S1—C8—C1397.86 (17)
C2—C3—C3A—C4178.3 (2)O1—S1—C8—C926.4 (2)
C2—C3—C3A—C7A1.0 (2)O2—S1—C8—C9161.17 (17)
C7A—C3A—C4—C51.5 (3)N1—S1—C8—C9−84.25 (18)
C3—C3A—C4—C5−175.7 (2)C13—C8—C9—C101.2 (3)
C7A—C3A—C4—Cl1−179.07 (14)S1—C8—C9—C10−176.68 (17)
C3—C3A—C4—Cl13.8 (3)C8—C9—C10—C110.0 (3)
C3A—C4—C5—C6−0.1 (3)C9—C10—C11—C12−1.2 (3)
Cl1—C4—C5—C6−179.55 (16)C9—C10—C11—C14176.6 (2)
C4—C5—C6—N7−0.9 (3)C10—C11—C12—C131.1 (3)
C5—C6—N7—C7A0.3 (3)C14—C11—C12—C13−176.7 (2)
C6—N7—C7A—N1179.39 (18)C9—C8—C13—C12−1.3 (3)
C6—N7—C7A—C3A1.4 (3)S1—C8—C13—C12176.54 (17)
C2—N1—C7A—N7−175.14 (19)C11—C12—C13—C80.1 (3)
S1—N1—C7A—N7−4.2 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT5113).

References

  • Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119.
  • Desarbre, E., Coudret, S., Meheust, C. & Merour, J.-Y. (1997). Tetrahedron, 53, 3637–3648.
  • Dräger, M. & Gattow, G. (1971). Acta Chem. Scand. 25, 761–762.
  • Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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