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

Selig, R.; Schollmeyer, D.; Albrecht, W.; Laufer, S.

doi:10.1107/S1600536809044559

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3018

doi:10.1107/S1600536809044559

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

Roland Selig,^a Dieter Schollmeyer,^b Wolfgang Albrecht ^c and Stefan Laufer ^a ^*

^aEberhard-Karls-University Tübingen, Auf der Morgenstelle 8, D-72076 Tübingen, Germany, ^bUniversity Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany, and ^cc-a-i-r biosciences GmbH, Paul-Ehrlich-Strasse 15, 72076 Tübingen, Germany
^*Correspondence e-mail: stefan.laufer@uni-tuebingen.de

(Received 23 October 2009; accepted 26 October 2009; online 7 November 2009)

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 ).

Experimental

Crystal data

C₁₄H₁₁ClN₂O₂S
M_r = 306.76
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.09
2580 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.49 e Å⁻³

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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%.

Computing details top

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

Figures top

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

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

Crystal data top

C₁₄H₁₁ClN₂O₂S	F(000) = 1264
M_r = 306.76	D_x = 1.493 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 21.7342 (12) Å	θ = 65–70°
b = 7.6313 (2) Å	µ = 3.94 mm⁻¹
c = 16.4649 (8) Å	T = 193 K
β = 91.531 (2)°	Block, colourless
V = 2729.9 (2) Å³	0.52 × 0.24 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	2435 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.000
Graphite monochromator	θ_max = 69.9°, θ_min = 4.1°
ω/2θ scans	h = 0→26
Absorption correction: numerical (PLATON; Spek, 2009)	k = 0→9
T_min = 0.319, T_max = 0.519	l = −20→20
2580 measured reflections	3 standard reflections every 60 min
2580 independent reflections	intensity decay: 2%

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0708P)² + 2.2448P] where P = (F_o² + 2F_c²)/3
2580 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₁₄H₁₁ClN₂O₂S	V = 2729.9 (2) Å³
M_r = 306.76	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 21.7342 (12) Å	µ = 3.94 mm⁻¹
b = 7.6313 (2) Å	T = 193 K
c = 16.4649 (8) Å	0.52 × 0.24 × 0.20 mm
β = 91.531 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2435 reflections with I > 2σ(I)
Absorption correction: numerical (PLATON; Spek, 2009)	R_int = 0.000
T_min = 0.319, T_max = 0.519	3 standard reflections every 60 min
2580 measured reflections	intensity decay: 2%
2580 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.09	Δρ_max = 0.26 e Å⁻³
2580 reflections	Δρ_min = −0.49 e Å⁻³
181 parameters

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	0.37591 (3)	0.21601 (7)	0.24460 (3)	0.04415 (18)
Cl1	0.17076 (3)	0.02839 (8)	0.52042 (4)	0.0552 (2)
O1	0.35059 (9)	0.2966 (2)	0.17315 (9)	0.0568 (4)
O2	0.40887 (9)	0.0548 (2)	0.23960 (10)	0.0574 (4)
N1	0.31423 (8)	0.1778 (2)	0.30138 (10)	0.0419 (4)
C2	0.25596 (11)	0.2537 (3)	0.28739 (14)	0.0471 (5)
H2	0.2448	0.3249	0.2420	0.057*
C3	0.21846 (10)	0.2106 (3)	0.34773 (14)	0.0452 (5)
H3	0.1766	0.2440	0.3520	0.054*
C3A	0.25318 (9)	0.1048 (3)	0.40466 (12)	0.0393 (4)
C4	0.24293 (10)	0.0231 (3)	0.47865 (13)	0.0428 (5)
C5	0.29115 (11)	−0.0600 (3)	0.51803 (13)	0.0463 (5)
H5	0.2853	−0.1165	0.5686	0.056*
C6	0.34872 (11)	−0.0608 (3)	0.48308 (13)	0.0458 (5)
H6	0.3814	−0.1178	0.5120	0.055*
N7	0.36143 (8)	0.0130 (2)	0.41150 (11)	0.0427 (4)
C7A	0.31332 (9)	0.0897 (2)	0.37609 (12)	0.0374 (4)
C8	0.41925 (9)	0.3694 (3)	0.30021 (11)	0.0381 (4)
C9	0.40403 (10)	0.5448 (3)	0.29162 (14)	0.0466 (5)
H9	0.3696	0.5785	0.2585	0.056*
C10	0.43905 (10)	0.6698 (3)	0.33118 (14)	0.0478 (5)
H10	0.4284	0.7899	0.3252	0.057*
C11	0.48956 (9)	0.6237 (3)	0.37969 (12)	0.0434 (5)
C12	0.50321 (10)	0.4468 (3)	0.38851 (14)	0.0484 (5)
H12	0.5373	0.4129	0.4223	0.058*
C13	0.46853 (10)	0.3189 (3)	0.34933 (13)	0.0451 (5)
H13	0.4785	0.1985	0.3561	0.054*
C14	0.52904 (13)	0.7648 (4)	0.41851 (17)	0.0615 (6)
H14A	0.5628	0.7105	0.4502	0.092*
H14B	0.5040	0.8362	0.4544	0.092*
H14C	0.5461	0.8392	0.3761	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0603 (3)	0.0409 (3)	0.0313 (3)	0.0037 (2)	0.0033 (2)	−0.00179 (18)
Cl1	0.0548 (3)	0.0523 (3)	0.0593 (4)	−0.0143 (2)	0.0148 (3)	−0.0159 (2)
O1	0.0779 (11)	0.0603 (11)	0.0319 (7)	−0.0021 (8)	−0.0050 (7)	0.0023 (7)
O2	0.0793 (12)	0.0432 (9)	0.0503 (9)	0.0096 (8)	0.0149 (8)	−0.0083 (7)
N1	0.0500 (10)	0.0398 (9)	0.0359 (8)	0.0004 (7)	−0.0024 (7)	0.0025 (7)
C2	0.0551 (12)	0.0437 (11)	0.0417 (11)	0.0038 (10)	−0.0146 (9)	−0.0013 (9)
C3	0.0437 (11)	0.0434 (12)	0.0479 (11)	−0.0010 (9)	−0.0102 (9)	−0.0115 (9)
C3A	0.0450 (10)	0.0315 (9)	0.0411 (10)	−0.0049 (8)	−0.0031 (8)	−0.0102 (8)
C4	0.0503 (11)	0.0348 (10)	0.0433 (11)	−0.0095 (8)	0.0045 (9)	−0.0113 (8)
C5	0.0645 (13)	0.0360 (10)	0.0383 (10)	−0.0070 (10)	0.0012 (9)	−0.0001 (8)
C6	0.0584 (12)	0.0348 (10)	0.0440 (11)	0.0037 (9)	−0.0036 (9)	0.0026 (9)
N7	0.0509 (10)	0.0355 (9)	0.0416 (9)	0.0038 (7)	0.0007 (7)	0.0006 (7)
C7A	0.0473 (10)	0.0285 (9)	0.0362 (9)	−0.0016 (8)	−0.0013 (8)	−0.0044 (7)
C8	0.0450 (10)	0.0387 (10)	0.0310 (9)	0.0052 (8)	0.0077 (7)	0.0022 (7)
C9	0.0504 (12)	0.0422 (11)	0.0469 (11)	0.0105 (9)	−0.0042 (9)	0.0061 (9)
C10	0.0551 (12)	0.0367 (11)	0.0519 (12)	0.0071 (9)	0.0051 (10)	0.0053 (9)
C11	0.0431 (10)	0.0476 (12)	0.0401 (10)	−0.0026 (9)	0.0107 (8)	0.0034 (9)
C12	0.0431 (11)	0.0534 (13)	0.0483 (12)	0.0063 (10)	−0.0025 (9)	0.0077 (10)
C13	0.0505 (11)	0.0402 (11)	0.0447 (11)	0.0120 (9)	0.0038 (9)	0.0061 (9)
C14	0.0609 (14)	0.0572 (15)	0.0665 (16)	−0.0147 (12)	0.0030 (12)	0.0037 (12)

Geometric parameters (Å, º) top

S1—O1	1.4250 (16)	C6—H6	0.9500
S1—O2	1.4269 (17)	N7—C7A	1.320 (3)
S1—N1	1.6803 (18)	C8—C13	1.380 (3)
S1—C8	1.746 (2)	C8—C9	1.385 (3)
Cl1—C4	1.730 (2)	C9—C10	1.374 (3)
N1—C7A	1.402 (3)	C9—H9	0.9500
N1—C2	1.406 (3)	C10—C11	1.386 (3)
C2—C3	1.343 (3)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.389 (3)
C3—C3A	1.436 (3)	C11—C14	1.508 (3)
C3—H3	0.9500	C12—C13	1.382 (3)
C3A—C4	1.392 (3)	C12—H12	0.9500
C3A—C7A	1.406 (3)	C13—H13	0.9500
C4—C5	1.373 (3)	C14—H14A	0.9800
C5—C6	1.391 (3)	C14—H14B	0.9800
C5—H5	0.9500	C14—H14C	0.9800
C6—N7	1.342 (3)

O1—S1—O2	120.52 (10)	N7—C7A—N1	124.77 (19)
O1—S1—N1	103.77 (10)	N7—C7A—C3A	128.40 (19)
O2—S1—N1	106.95 (10)	N1—C7A—C3A	106.81 (17)
O1—S1—C8	109.55 (10)	C13—C8—C9	120.6 (2)
O2—S1—C8	110.09 (10)	C13—C8—S1	121.32 (17)
N1—S1—C8	104.58 (9)	C9—C8—S1	118.05 (16)
C7A—N1—C2	107.91 (18)	C10—C9—C8	119.7 (2)
C7A—N1—S1	126.97 (15)	C10—C9—H9	120.2
C2—N1—S1	124.46 (16)	C8—C9—H9	120.2
C3—C2—N1	109.85 (19)	C9—C10—C11	121.2 (2)
C3—C2—H2	125.1	C9—C10—H10	119.4
N1—C2—H2	125.1	C11—C10—H10	119.4
C2—C3—C3A	107.59 (19)	C10—C11—C12	118.1 (2)
C2—C3—H3	126.2	C10—C11—C14	119.7 (2)
C3A—C3—H3	126.2	C12—C11—C14	122.1 (2)
C4—C3A—C7A	115.35 (19)	C13—C12—C11	121.7 (2)
C4—C3A—C3	136.9 (2)	C13—C12—H12	119.2
C7A—C3A—C3	107.75 (19)	C11—C12—H12	119.2
C5—C4—C3A	118.8 (2)	C8—C13—C12	118.8 (2)
C5—C4—Cl1	120.78 (17)	C8—C13—H13	120.6
C3A—C4—Cl1	120.37 (17)	C12—C13—H13	120.6
C4—C5—C6	119.4 (2)	C11—C14—H14A	109.5
C4—C5—H5	120.3	C11—C14—H14B	109.5
C6—C5—H5	120.3	H14A—C14—H14B	109.5
N7—C6—C5	124.8 (2)	C11—C14—H14C	109.5
N7—C6—H6	117.6	H14A—C14—H14C	109.5
C5—C6—H6	117.6	H14B—C14—H14C	109.5
C7A—N7—C6	113.26 (19)

O1—S1—N1—C7A	175.64 (17)	C2—N1—C7A—C3A	3.3 (2)
O2—S1—N1—C7A	47.22 (19)	S1—N1—C7A—C3A	174.17 (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—N7	175.68 (19)
O2—S1—N1—C2	−143.28 (18)	C4—C3A—C7A—N1	179.38 (16)
C8—S1—N1—C2	99.95 (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—C3A	1.0 (2)	N1—S1—C8—C13	97.86 (17)
C2—C3—C3A—C4	178.3 (2)	O1—S1—C8—C9	26.4 (2)
C2—C3—C3A—C7A	1.0 (2)	O2—S1—C8—C9	161.17 (17)
C7A—C3A—C4—C5	1.5 (3)	N1—S1—C8—C9	−84.25 (18)
C3—C3A—C4—C5	−175.7 (2)	C13—C8—C9—C10	1.2 (3)
C7A—C3A—C4—Cl1	−179.07 (14)	S1—C8—C9—C10	−176.68 (17)
C3—C3A—C4—Cl1	3.8 (3)	C8—C9—C10—C11	0.0 (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—C14	176.6 (2)
C4—C5—C6—N7	−0.9 (3)	C10—C11—C12—C13	1.1 (3)
C5—C6—N7—C7A	0.3 (3)	C14—C11—C12—C13	−176.7 (2)
C6—N7—C7A—N1	179.39 (18)	C9—C8—C13—C12	−1.3 (3)
C6—N7—C7A—C3A	1.4 (3)	S1—C8—C13—C12	176.54 (17)
C2—N1—C7A—N7	−175.14 (19)	C11—C12—C13—C8	0.1 (3)
S1—N1—C7A—N7	−4.2 (3)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClN₂O₂S
M_r	306.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	193
a, b, c (Å)	21.7342 (12), 7.6313 (2), 16.4649 (8)
β (°)	91.531 (2)
V (Å³)	2729.9 (2)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	3.94
Crystal size (mm)	0.52 × 0.24 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	Numerical (PLATON; Spek, 2009)
T_min, T_max	0.319, 0.519
No. of measured, independent and observed [I > 2σ(I)] reflections	2580, 2580, 2435
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.119, 1.09
No. of reflections	2580
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.49

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Dräger & Gattow, 1971), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

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.

References

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