2-(Bicyclo­[2.2.1]hept-5-en-2-yl)-1H-pyrrolo­[2,3-b]pyridine

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

doi:10.1107/S1600536810022087

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1800

doi:10.1107/S1600536810022087

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2-(Bicyclo[2.2.1]hept-5-en-2-yl)-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, 72076 Tübingen, Germany, ^bUniversity Mainz, Duesbergweg 10-14, 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 7 June 2010; accepted 9 June 2010; online 26 June 2010)

The crystal structure of the title compound, C₁₄H₁₄N₂, displays intermolecular N—H⋯N hydrogen bonds, forming dimers of enantiomeric molecules via a crystallographic centre of inversion.

Related literature

For the general synthetic procedure for 2-substituted 7-azaindoles, see Davis et al. (1992 ).

Experimental

Crystal data

C₁₄H₁₄N₂
M_r = 210.27
Monoclinic, P 2₁ /n
a = 7.7837 (12) Å
b = 8.9867 (14) Å
c = 15.973 (3) Å
β = 96.408 (8)°
V = 1110.3 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.58 mm⁻¹
T = 193 K
0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
2274 measured reflections
2113 independent reflections
1940 reflections with I > 2σ(I)
R_int = 0.050
3 standard reflections every 60 min intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.082
wR(F²) = 0.227
S = 1.09
2113 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N7ⁱ	0.90	2.05	2.932 (3)	166
Symmetry code: (i) -x+2, -y+1, -z+1.

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/S1600536810022087/im2211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810022087/im2211Isup2.hkl

checkCIF report

Comment top

The interest in 7- azaindoles as bioisoster of indole or purine has arisen in conjunction with recent pharmacological programs. Numerous publications on its derivatization reflect the increasing attention paid to this heterocyclic system. The crystal structure of 2-bicyclo[2.2.1]hept-5-en-2-yl-1H-pyrrolo[2,3-b]pyridine, C₁₄H₁₄N₂, is characterized by an intermolecular hydrogen bond N1—H1··· N7 (2.05 Å) forming dimers of enantiomeric molecules, which are related by a crystallographic centre of symmetry.

Related literature top

For the general synthetic procedure for 2-substituted 7-azaindoles, see Davis et al. (1992).

Experimental top

3-methylpyridine (4 g, 43 mmol) was added dropwise to a freshly prepared solution of LDA in THF (0.9M) (59 ml, 53 mmol) at 273 K. The resulting suspension was stirred at 273 K for 30 min. Racemic 5-norbornene-2-carbonitrile (5.12 g, 43 mmol) was added dropwise at such a rate that the temperature did not rise above 283 K. Stirring was continued for 60 min. at 273 K. Another portion of LDA solution (59 ml, 53 mmol) was added and stirring was continued overnight at 333 K. The final reaction mixture was allowed to cool and ice-water was added. The mixture was extracted with ethylacetate and the combined extracts were dried (Na₂SO₄) and the solvent was evaporated under reduced pressure. The residue was subjected to flash chromatography. The title compound was obtained in a yield of 31% (2.834 g, 13.48 mmol). Crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent from a methanolic solution.

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. Molecular structure of compound I. Displacement ellipsoids are drawn at the 50% probability level. H atoms are depicted as circles of arbitrary size.

2-(Bicyclo[2.2.1]hept-5-en-2-yl)-1H-pyrrolo[2,3-b]pyridine top

Crystal data top

C₁₄H₁₄N₂	F(000) = 448
M_r = 210.27	D_x = 1.258 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.7837 (12) Å	θ = 65–69°
b = 8.9867 (14) Å	µ = 0.58 mm⁻¹
c = 15.973 (3) Å	T = 193 K
β = 96.408 (8)°	Block, colourless
V = 1110.3 (3) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.050
Radiation source: rotating anode	θ_max = 70.0°, θ_min = 5.6°
Graphite monochromator	h = −9→0
ω/2θ scans	k = −10→0
2274 measured reflections	l = −19→19
2113 independent reflections	3 standard reflections every 60 min
1940 reflections with I > 2σ(I)	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)] = 0.082	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.227	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.1178P)² + 1.2641P] where P = (F_o² + 2F_c²)/3
2113 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₄H₁₄N₂	V = 1110.3 (3) Å³
M_r = 210.27	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.7837 (12) Å	µ = 0.58 mm⁻¹
b = 8.9867 (14) Å	T = 193 K
c = 15.973 (3) Å	0.40 × 0.30 × 0.20 mm
β = 96.408 (8)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.050
2274 measured reflections	3 standard reflections every 60 min
2113 independent reflections	intensity decay: 2%
1940 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.082	0 restraints
wR(F²) = 0.227	H-atom parameters constrained
S = 1.09	Δρ_max = 0.47 e Å⁻³
2113 reflections	Δρ_min = −0.36 e Å⁻³
145 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
N1	0.8046 (3)	0.5132 (3)	0.41997 (15)	0.0360 (6)
H1	0.8691	0.5799	0.4519	0.043*
C2	0.6512 (3)	0.5373 (3)	0.36871 (17)	0.0362 (6)
C3	0.5981 (3)	0.4080 (3)	0.32996 (18)	0.0399 (7)
H3	0.4964	0.3943	0.2920	0.048*
C3A	0.7228 (3)	0.2965 (3)	0.35653 (16)	0.0345 (6)
C4	0.7490 (4)	0.1469 (3)	0.33978 (17)	0.0391 (7)
H4	0.6692	0.0929	0.3020	0.047*
C5	0.8949 (4)	0.0794 (3)	0.37998 (18)	0.0411 (7)
H5	0.9164	−0.0228	0.3700	0.049*
C6	1.0105 (3)	0.1604 (3)	0.43497 (18)	0.0387 (7)
H6	1.1092	0.1100	0.4615	0.046*
N7	0.9921 (3)	0.3044 (3)	0.45291 (14)	0.0355 (6)
C7A	0.8499 (3)	0.3677 (3)	0.41290 (16)	0.0317 (6)
C8	0.3998 (4)	0.7013 (4)	0.3032 (2)	0.0472 (8)
H8	0.3817	0.6311	0.2544	0.057*
C9	0.5793 (3)	0.6919 (3)	0.35899 (18)	0.0383 (7)
H9	0.6638	0.7548	0.3321	0.046*
C10	0.5422 (5)	0.7683 (4)	0.4420 (2)	0.0528 (9)
H10A	0.6201	0.8542	0.4552	0.063*
H10B	0.5561	0.6974	0.4897	0.063*
C11	0.3507 (4)	0.8199 (4)	0.4233 (2)	0.0545 (9)
H11	0.2909	0.8473	0.4734	0.065*
C12	0.3445 (4)	0.9316 (4)	0.3555 (2)	0.0485 (8)
H12	0.3232	1.0350	0.3612	0.058*
C13	0.3743 (4)	0.8614 (4)	0.2839 (2)	0.0532 (9)
H13	0.3782	0.9068	0.2304	0.064*
C14	0.2793 (4)	0.6819 (4)	0.3730 (2)	0.0573 (9)
H14A	0.3002	0.5879	0.4049	0.069*
H14B	0.1554	0.6913	0.3518	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0236 (10)	0.0376 (12)	0.0445 (12)	0.0054 (9)	−0.0063 (9)	−0.0044 (10)
C2	0.0249 (12)	0.0446 (15)	0.0376 (13)	0.0056 (11)	−0.0034 (10)	0.0010 (11)
C3	0.0298 (13)	0.0458 (16)	0.0417 (14)	0.0002 (11)	−0.0058 (11)	−0.0010 (12)
C3A	0.0302 (13)	0.0406 (14)	0.0325 (12)	−0.0005 (11)	0.0024 (10)	−0.0005 (11)
C4	0.0386 (14)	0.0425 (15)	0.0365 (14)	−0.0024 (12)	0.0052 (11)	−0.0048 (12)
C5	0.0428 (15)	0.0378 (15)	0.0440 (15)	0.0057 (12)	0.0109 (12)	−0.0055 (12)
C6	0.0319 (13)	0.0412 (15)	0.0436 (15)	0.0109 (11)	0.0070 (11)	−0.0003 (12)
N7	0.0236 (10)	0.0402 (12)	0.0422 (12)	0.0070 (9)	0.0013 (9)	−0.0024 (10)
C7A	0.0246 (12)	0.0362 (13)	0.0342 (13)	0.0042 (10)	0.0028 (10)	0.0004 (10)
C8	0.0381 (15)	0.0533 (18)	0.0484 (17)	0.0099 (13)	−0.0028 (13)	−0.0038 (14)
C9	0.0264 (13)	0.0452 (16)	0.0424 (14)	0.0059 (11)	0.0006 (11)	0.0011 (12)
C10	0.0521 (19)	0.059 (2)	0.0451 (16)	0.0176 (15)	−0.0032 (14)	−0.0003 (15)
C11	0.0504 (19)	0.064 (2)	0.0525 (18)	0.0156 (16)	0.0187 (15)	0.0002 (16)
C12	0.0328 (14)	0.0534 (18)	0.0593 (19)	0.0152 (13)	0.0044 (13)	−0.0024 (14)
C13	0.0432 (17)	0.065 (2)	0.0508 (17)	0.0135 (15)	0.0010 (14)	0.0083 (16)
C14	0.0337 (16)	0.068 (2)	0.072 (2)	−0.0002 (15)	0.0140 (15)	−0.0068 (18)

Geometric parameters (Å, º) top

N1—C7A	1.362 (3)	C8—C14	1.546 (5)
N1—C2	1.388 (3)	C8—C9	1.573 (4)
N1—H1	0.9027	C8—H8	1.0000
C2—C3	1.359 (4)	C9—C10	1.548 (4)
C2—C9	1.500 (4)	C9—H9	1.0000
C3—C3A	1.426 (4)	C10—C11	1.558 (5)
C3—H3	0.9500	C10—H10A	0.9900
C3A—C4	1.391 (4)	C10—H10B	0.9900
C3A—C7A	1.414 (4)	C11—C12	1.473 (5)
C4—C5	1.381 (4)	C11—C14	1.547 (5)
C4—H4	0.9500	C11—H11	1.0000
C5—C6	1.391 (4)	C12—C13	1.349 (5)
C5—H5	0.9500	C12—H12	0.9500
C6—N7	1.336 (4)	C13—H13	0.9500
C6—H6	0.9500	C14—H14A	0.9900
N7—C7A	1.342 (3)	C14—H14B	0.9900
C8—C13	1.480 (5)

C7A—N1—C2	108.4 (2)	C2—C9—C10	115.2 (2)
C7A—N1—H1	123.5	C2—C9—C8	114.0 (2)
C2—N1—H1	128.1	C10—C9—C8	102.9 (2)
C3—C2—N1	109.4 (2)	C2—C9—H9	108.2
C3—C2—C9	130.9 (2)	C10—C9—H9	108.2
N1—C2—C9	119.5 (2)	C8—C9—H9	108.2
C2—C3—C3A	107.6 (2)	C9—C10—C11	103.5 (2)
C2—C3—H3	126.2	C9—C10—H10A	111.1
C3A—C3—H3	126.2	C11—C10—H10A	111.1
C4—C3A—C7A	116.9 (2)	C9—C10—H10B	111.1
C4—C3A—C3	137.0 (3)	C11—C10—H10B	111.1
C7A—C3A—C3	106.0 (2)	H10A—C10—H10B	109.0
C5—C4—C3A	117.8 (3)	C12—C11—C14	100.6 (3)
C5—C4—H4	121.1	C12—C11—C10	107.2 (3)
C3A—C4—H4	121.1	C14—C11—C10	98.1 (3)
C4—C5—C6	120.3 (3)	C12—C11—H11	116.1
C4—C5—H5	119.9	C14—C11—H11	116.1
C6—C5—H5	119.9	C10—C11—H11	116.1
N7—C6—C5	124.4 (3)	C13—C12—C11	108.0 (3)
N7—C6—H6	117.8	C13—C12—H12	126.0
C5—C6—H6	117.8	C11—C12—H12	126.0
C6—N7—C7A	114.3 (2)	C12—C13—C8	108.1 (3)
N7—C7A—N1	125.1 (2)	C12—C13—H13	126.0
N7—C7A—C3A	126.3 (2)	C8—C13—H13	126.0
N1—C7A—C3A	108.6 (2)	C8—C14—C11	94.1 (3)
C13—C8—C14	100.5 (3)	C8—C14—H14A	112.9
C13—C8—C9	105.1 (3)	C11—C14—H14A	112.9
C14—C8—C9	99.0 (2)	C8—C14—H14B	112.9
C13—C8—H8	116.5	C11—C14—H14B	112.9
C14—C8—H8	116.5	H14A—C14—H14B	110.3
C9—C8—H8	116.5

C7A—N1—C2—C3	0.6 (3)	N1—C2—C9—C10	−58.2 (4)
C7A—N1—C2—C9	−175.0 (2)	C3—C2—C9—C8	8.7 (4)
N1—C2—C3—C3A	−0.6 (3)	N1—C2—C9—C8	−176.8 (2)
C9—C2—C3—C3A	174.4 (3)	C13—C8—C9—C2	−166.1 (3)
C2—C3—C3A—C4	−177.8 (3)	C14—C8—C9—C2	90.4 (3)
C2—C3—C3A—C7A	0.3 (3)	C13—C8—C9—C10	68.6 (3)
C7A—C3A—C4—C5	0.8 (4)	C14—C8—C9—C10	−35.0 (3)
C3—C3A—C4—C5	178.8 (3)	C2—C9—C10—C11	−127.4 (3)
C3A—C4—C5—C6	−0.2 (4)	C8—C9—C10—C11	−2.8 (3)
C4—C5—C6—N7	−0.2 (4)	C9—C10—C11—C12	−64.3 (3)
C5—C6—N7—C7A	−0.1 (4)	C9—C10—C11—C14	39.5 (3)
C6—N7—C7A—N1	−179.0 (2)	C14—C11—C12—C13	−32.7 (3)
C6—N7—C7A—C3A	0.8 (4)	C10—C11—C12—C13	69.4 (4)
C2—N1—C7A—N7	179.4 (2)	C11—C12—C13—C8	0.3 (4)
C2—N1—C7A—C3A	−0.4 (3)	C14—C8—C13—C12	32.2 (3)
C4—C3A—C7A—N7	−1.1 (4)	C9—C8—C13—C12	−70.2 (3)
C3—C3A—C7A—N7	−179.7 (3)	C13—C8—C14—C11	−48.3 (3)
C4—C3A—C7A—N1	178.6 (2)	C9—C8—C14—C11	59.0 (3)
C3—C3A—C7A—N1	0.1 (3)	C12—C11—C14—C8	48.6 (3)
C3—C2—C9—C10	127.3 (3)	C10—C11—C14—C8	−60.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N7ⁱ	0.90	2.05	2.932 (3)	166

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₂
M_r	210.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	193
a, b, c (Å)	7.7837 (12), 8.9867 (14), 15.973 (3)
β (°)	96.408 (8)
V (Å³)	1110.3 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2274, 2113, 1940
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.082, 0.227, 1.09
No. of reflections	2113
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.36

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N7ⁱ	0.90	2.05	2.932 (3)	166

Symmetry code: (i) −x+2, −y+1, −z+1.

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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