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

Abstract

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,

• a = 10.1416 (10) Å

• b = 13.7428 (14) Å

• c = 6.7395 (7) Å

• β = 94.331 (2)°

• V = 936.63 (16) ų

• 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[F ² > 2σ(F ²)] = 0.064

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812023690/rk2358Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were located geometrically and treated as riding atoms, with C—H = 0.93Å, and with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C12H9N3	F(000) = 408
Mr = 195.22	Dx = 1.384 Mg m−3Dm = 1.384 Mg m−3Dm 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

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

Refinement

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(Fo2) + (0.0366P)2 + 0.2976P] where P = (Fo2 + 2Fc2)/3
2154 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.