2-(1H-Pyrrolo­[2,3-b]pyridin-2-yl)pyridine

Huang, P.-H.; Wen, Y.-S.; Shen, J.-Y.

doi:10.1107/S1600536812023690

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1943

doi:10.1107/S1600536812023690

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2-(1H-Pyrrolo[2,3-b]pyridin-2-yl)pyridine

Ping-Hsin Huang,^a ^* Yuh-Sheng Wen ^b and Jiun-Yi Shen ^c

^aCardinal Tien College of Healthcare & Management, Taipei, Taiwan 231, Republic of China, ^bInstitute of Chemistry, Academia Sinica, Nankang, Taipei, Taiwan, Republic of China, and ^cDepartment of Chemistry, National Taiwan University, Taipei, Taiwan, Republic of China
^*Correspondence e-mail: pshuang@ctcn.edu.tw

(Received 1 May 2012; accepted 24 May 2012; online 31 May 2012)

In the title compound, C₁₂H₉N₃, the dihedral angle between the pyridine and azaindole rings is 6.20 (2)°. In the crystal, pairs of N—H⋯N hydrogen bonds link molecules into inversion dimers.

Related literature

For the production of luminescent organic/organometallic compounds, see: Liu et al. (2000 ). For related structures, see: Sakamoto et al. (1996 ); Huang et al. (2011 ).

Experimental

Crystal data

C₁₂H₉N₃
M_r = 195.22
Monoclinic, P 2₁ /c
a = 10.1416 (10) Å
b = 13.7428 (14) Å
c = 6.7395 (7) Å
β = 94.331 (2)°
V = 936.63 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.55 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.938, T_max = 0.996
7069 measured reflections
2154 independent reflections
1792 reflections with I > 2σa(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.145
S = 1.19
2154 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.88	2.10	2.944 (2)	162
Symmetry code: (i) -x+1, -y+2, -z.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812023690/rk2358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812023690/rk2358Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812023690/rk2358Isup3.cml

checkCIF report

Comment top

The title compound, has been shown to be an precursor for the production of luminescent organic/organometallic compound (Liu et al., 2000). A one pot synthesis of a 7-azaindole substituted in the 2-position has been achieved by Pd complex catalyzed Cross-coupling reaction of 2-bromopyridine (Sakamoto et al., 1996), in high yield (see Scheme). The molecular structure is shown in Fig. 1. The dihedral angle between the pyridine and azaindole rings is 6.20 (2)°, and that between the pyridine and pyrrole rings at 7-azaindole is 0.35 (2)° (Huang et al., 2011). Weak intermolecular N2—H2···N1ⁱ (see Table 1) interactions help to stabilize the crystal structure - formation of centrosymmetrical dimers. Symmetry code: (i) -x+1, -y+2, -z.

Related literature top

For the production of luminescent organic/organometallic compounds, see: Liu et al. (2000). For related structures, see: Sakamoto et al. (1996); Huang et al. (2011).

Experimental top

The compound was synthesized by the following procedure (Liu et al., 2000); (Sakamoto et al., 1996). A solution of 1-(benzenesulfonyl)-2-(2-pyridyl)-7-azaindole (2.00 g, 5.97 mmol), ethanol (340 ml), and 10% aqueous NaOH (34 ml) was heated at reflux overnight. The resulting mixture was concertrated, and the residue was dissolved in CH₂Cl₂. The organic solution was washed with water and aqueous Na₂CO₃, dried, and concertrated. The residue was purified by column chromatography using CH₂Cl₂/CH₃OH (20:1) as eluent, followed by recrystallization from CH₂Cl₂ and hexane to yield 0.82 g (70%) of title compound as a white solid. Crystals suitable for X-ray diffraction were grown from a CH₂Cl₂ solution layered with hexane at room temperature. ¹H NMR (CDCl₃): 10.90 (br s, 1H), 8.69 (ddd, 1H, J = 4.8, 1.6, 1.0 Hz), 8.46 (dd, 1H, J = 4.8, 1.6 Hz), 7.98 (dd, 1H, J = 7.8, 1.3 Hz), 7.85 (m, 1H), 7.76 (td, 1H, J = 7.8, 1.7 Hz), 7.24 (ddd, 1H, J = 7.8, 4.8, 1.2 Hz), 7.12 (dd, 1H, J = 4.8, 1.8 Hz), 6.99 (d, 1H, J = 1.8 Hz). Anal. Calcd for C₁₂H₉N₃: C, 73.83; H, 4.65; N, 21.52. Found: C, 73.26; H, 4.48; N, 21.58.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure of title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are shown as small spheres of the arbitrary radii.

2-(1H-Pyrrolo[2,3-b]pyridin-2-yl)pyridine top

Crystal data top

C₁₂H₉N₃	F(000) = 408
M_r = 195.22	D_x = 1.384 Mg m⁻³ D_m = 1.384 Mg m⁻³ D_m measured by not measured
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1871 reflections
a = 10.1416 (10) Å	θ = 2.5–26.3°
b = 13.7428 (14) Å	µ = 0.09 mm⁻¹
c = 6.7395 (7) Å	T = 200 K
β = 94.331 (2)°	Needle, colourless
V = 936.63 (16) Å³	0.55 × 0.15 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2154 independent reflections
Radiation source: fine-focus sealed tube	1792 reflections with I > 2σa(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
T_min = 0.938, T_max = 0.996	k = −17→17
7069 measured reflections	l = −8→8

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0366P)² + 0.2976P] where P = (F_o² + 2F_c²)/3
2154 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₉N₃	V = 936.63 (16) Å³
M_r = 195.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1416 (10) Å	µ = 0.09 mm⁻¹
b = 13.7428 (14) Å	T = 200 K
c = 6.7395 (7) Å	0.55 × 0.15 × 0.05 mm
β = 94.331 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2154 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1792 reflections with I > 2σa(I)
T_min = 0.938, T_max = 0.996	R_int = 0.056
7069 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.19	Δρ_max = 0.25 e Å⁻³
2154 reflections	Δρ_min = −0.20 e Å⁻³
136 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.66995 (16)	0.94501 (12)	0.0034 (2)	0.0382 (4)
N2	0.50593 (15)	0.92225 (11)	0.2357 (2)	0.0324 (4)
H2	0.4394	0.9513	0.1684	0.039*
N3	0.27130 (16)	0.91454 (12)	0.4136 (2)	0.0371 (4)
C1	0.7961 (2)	0.92562 (16)	−0.0253 (3)	0.0418 (5)
H1	0.8296	0.9475	−0.1454	0.050*
C2	0.8818 (2)	0.87517 (16)	0.1101 (3)	0.0412 (5)
H2A	0.9707	0.8639	0.0808	0.049*
C3	0.8377 (2)	0.84179 (14)	0.2859 (3)	0.0391 (5)
H3	0.8948	0.8070	0.3790	0.047*
C4	0.70684 (19)	0.86035 (13)	0.3238 (3)	0.0333 (4)
C5	0.62979 (18)	0.91210 (13)	0.1741 (3)	0.0316 (4)
C6	0.62305 (19)	0.84091 (13)	0.4777 (3)	0.0351 (5)
H6	0.6466	0.8073	0.5984	0.042*
C7	0.50115 (19)	0.87982 (13)	0.4198 (3)	0.0323 (4)
C8	0.37880 (18)	0.87873 (13)	0.5192 (3)	0.0327 (4)
C9	0.3725 (2)	0.84151 (14)	0.7108 (3)	0.0411 (5)
H9	0.4501	0.8179	0.7828	0.049*
C10	0.2536 (2)	0.83931 (15)	0.7945 (3)	0.0465 (6)
H10	0.2474	0.8138	0.9244	0.056*
C11	0.1429 (2)	0.87497 (16)	0.6860 (3)	0.0460 (5)
H11	0.0586	0.8738	0.7388	0.055*
C12	0.1579 (2)	0.91213 (16)	0.5003 (3)	0.0440 (5)
H12	0.0817	0.9380	0.4283	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0389 (9)	0.0415 (9)	0.0336 (9)	0.0069 (7)	−0.0001 (7)	0.0021 (7)
N2	0.0326 (8)	0.0329 (8)	0.0306 (8)	0.0031 (6)	−0.0059 (6)	0.0030 (7)
N3	0.0347 (9)	0.0376 (9)	0.0382 (9)	−0.0009 (7)	−0.0026 (7)	0.0040 (7)
C1	0.0422 (11)	0.0459 (12)	0.0373 (11)	0.0069 (9)	0.0026 (9)	0.0005 (9)
C2	0.0352 (11)	0.0435 (12)	0.0444 (12)	0.0067 (9)	−0.0013 (9)	−0.0031 (10)
C3	0.0366 (11)	0.0361 (11)	0.0426 (12)	0.0037 (8)	−0.0104 (9)	0.0006 (9)
C4	0.0379 (10)	0.0259 (9)	0.0341 (10)	−0.0004 (8)	−0.0101 (8)	−0.0009 (8)
C5	0.0336 (10)	0.0281 (9)	0.0319 (10)	0.0027 (8)	−0.0050 (8)	−0.0030 (8)
C6	0.0390 (11)	0.0298 (10)	0.0344 (10)	−0.0013 (8)	−0.0106 (8)	0.0053 (8)
C7	0.0382 (10)	0.0253 (9)	0.0321 (10)	−0.0037 (8)	−0.0065 (8)	0.0015 (8)
C8	0.0357 (10)	0.0253 (9)	0.0358 (10)	−0.0038 (7)	−0.0054 (8)	−0.0002 (8)
C9	0.0453 (12)	0.0367 (11)	0.0401 (11)	−0.0023 (9)	−0.0050 (9)	0.0062 (9)
C10	0.0566 (14)	0.0433 (12)	0.0397 (12)	−0.0035 (10)	0.0054 (10)	0.0083 (10)
C11	0.0410 (12)	0.0458 (12)	0.0521 (13)	−0.0032 (10)	0.0094 (10)	0.0023 (10)
C12	0.0393 (11)	0.0444 (12)	0.0473 (12)	0.0000 (9)	−0.0027 (9)	0.0011 (10)

Geometric parameters (Å, º) top

N1—C5	1.328 (2)	C4—C6	1.415 (3)
N1—C1	1.335 (3)	C4—C5	1.420 (3)
N2—C5	1.360 (2)	C6—C7	1.376 (3)
N2—C7	1.376 (2)	C6—H6	0.9500
N2—H2	0.8800	C7—C8	1.454 (3)
N3—C12	1.329 (3)	C8—C9	1.395 (3)
N3—C8	1.349 (2)	C9—C10	1.369 (3)
C1—C2	1.396 (3)	C9—H9	0.9500
C1—H1	0.9500	C10—C11	1.383 (3)
C2—C3	1.377 (3)	C10—H10	0.9500
C2—H2A	0.9500	C11—C12	1.371 (3)
C3—C4	1.393 (3)	C11—H11	0.9500
C3—H3	0.9500	C12—H12	0.9500

C5—N1—C1	114.66 (18)	C7—C6—H6	126.4
C5—N2—C7	109.17 (15)	C4—C6—H6	126.4
C5—N2—H2	125.4	N2—C7—C6	109.17 (17)
C7—N2—H2	125.4	N2—C7—C8	120.62 (16)
C12—N3—C8	116.82 (17)	C6—C7—C8	130.19 (18)
N1—C1—C2	124.1 (2)	N3—C8—C9	122.01 (18)
N1—C1—H1	117.9	N3—C8—C7	115.95 (17)
C2—C1—H1	117.9	C9—C8—C7	122.04 (18)
C3—C2—C1	120.04 (19)	C10—C9—C8	119.5 (2)
C3—C2—H2A	120.0	C10—C9—H9	120.2
C1—C2—H2A	120.0	C8—C9—H9	120.2
C2—C3—C4	118.22 (19)	C9—C10—C11	118.7 (2)
C2—C3—H3	120.9	C9—C10—H10	120.7
C4—C3—H3	120.9	C11—C10—H10	120.7
C3—C4—C6	137.09 (19)	C12—C11—C10	118.2 (2)
C3—C4—C5	116.24 (18)	C12—C11—H11	120.9
C6—C4—C5	106.67 (17)	C10—C11—H11	120.9
N1—C5—N2	125.47 (17)	N3—C12—C11	124.7 (2)
N1—C5—C4	126.71 (18)	N3—C12—H12	117.6
N2—C5—C4	107.81 (17)	C11—C12—H12	117.6
C7—C6—C4	107.17 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.88	2.10	2.944 (2)	162

Symmetry code: (i) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₉N₃
M_r	195.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	10.1416 (10), 13.7428 (14), 6.7395 (7)
β (°)	94.331 (2)
V (Å³)	936.63 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.55 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.938, 0.996
No. of measured, independent and observed [I > 2σa(I)] reflections	7069, 2154, 1792
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.145, 1.19
No. of reflections	2154
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.20

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.88	2.100	2.944 (2)	162

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

This work was partially supported by the Instrumentation Center, National Taiwan University, and Cardinal Tien College of Healthcare & Management.

References

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