N-(Pyrazin-2-yl)-4-toluidine

Abstract

The two aromatic systems in the title compound, C₁₁H₁₁N₃, are inclined by 19.1 (1)°, whilst the angle at the central amino N atom is 130.3 (2)°. The amino group forms a hydrogen bond to the pyrazine N-4 atom of an adjacent mol­ecule, forming a chain motif.

Related literature

For the structure of amino­pyrazine, see: Chao et al. (1976 ▶) and for that of N-(pyrazin-2-yl)-2-nitro­aniline; see: Parsons et al. (2006 ▶). For two monoclinic modifications of N-(pyrazin-2-yl)aniline, see: Abdullah & Ng (2008 ▶); Wan Saffiee et al. (2008 ▶).

Experimental

Crystal data

• C₁₁H₁₁N₃

• M _r = 185.23

• Monoclinic,

• a = 21.7179 (7) Å

• b = 7.5323 (3) Å

• c = 12.0073 (5) Å

• β = 105.790 (3)°

• V = 1890.1 (1) ų

• Z = 8

• Mo Kα radiation

• μ = 0.08 mm⁻¹

• T = 100 (2) K

• 0.30 × 0.20 × 0.05 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: none

• 6057 measured reflections

• 2165 independent reflections

• 1437 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.135

• S = 1.03

• 2165 reflections

• 132 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

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
N1—H1⋯N3i	0.89 (2)	2.10 (2)	2.963 (2)	163 (2)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Chloropyrazine (1 ml, 1.1 mmol) and 4-toluidine (1.2 g, 1.1 mmol) were heated at 423–433 K for 3 h. The solid was dissolved in water. The compound was extracted with ether. The ether extract was dried over sodium sulfate; evaporation of the solvent gave colorless crystals among some unidentified dark brown materials.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with U(H) fixed at 1.2–1.5U(C). The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.88±0.01 Å.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C11H11N3 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C11H11N3	F000 = 784
Mr = 185.23	Dx = 1.302 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1368 reflections
a = 21.7179 (7) Å	θ = 2.9–27.2º
b = 7.5323 (3) Å	µ = 0.08 mm−1
c = 12.0073 (5) Å	T = 100 (2) K
β = 105.790 (3)º	Prism, colorless
V = 1890.1 (1) Å3	0.30 × 0.20 × 0.05 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer	1437 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Monochromator: graphite	θmax = 27.5º
T = 100(2) K	θmin = 2.0º
ω scans	h = −28→28
Absorption correction: None	k = −9→9
6057 measured reflections	l = −15→15
2165 independent reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.135	w = 1/[σ2(Fo2) + (0.0652P)2 + 0.9346P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2165 reflections	Δρmax = 0.27 e Å−3
132 parameters	Δρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.31486 (7)	0.7286 (2)	0.14663 (14)	0.0223 (4)
H1	0.2746 (10)	0.754 (3)	0.1433 (17)	0.025 (5)*
N2	0.39338 (7)	0.5068 (2)	0.20972 (13)	0.0215 (4)
N3	0.30867 (7)	0.3328 (2)	0.31234 (14)	0.0240 (4)
C1	0.34916 (8)	0.8610 (2)	0.10751 (15)	0.0209 (4)
C2	0.31332 (8)	0.9994 (2)	0.04370 (15)	0.0225 (4)
H2	0.2680	0.9977	0.0274	0.027*
C3	0.34299 (9)	1.1385 (2)	0.00420 (15)	0.0243 (4)
H3	0.3176	1.2305	−0.0396	0.029*
C4	0.40936 (9)	1.1472 (2)	0.02707 (15)	0.0231 (4)
C5	0.44431 (8)	1.0095 (2)	0.09091 (15)	0.0226 (4)
H5	0.4897	1.0127	0.1081	0.027*
C6	0.41565 (8)	0.8672 (2)	0.13069 (15)	0.0222 (4)
H6	0.4412	0.7745	0.1734	0.027*
C7	0.44137 (10)	1.3010 (3)	−0.01539 (18)	0.0302 (5)
H7A	0.4876	1.2958	0.0203	0.045*
H7B	0.4244	1.4129	0.0056	0.045*
H7C	0.4328	1.2941	−0.0997	0.045*
C8	0.33543 (8)	0.5719 (2)	0.20318 (15)	0.0201 (4)
C9	0.29286 (8)	0.4818 (2)	0.25360 (16)	0.0231 (4)
H9	0.2514	0.5298	0.2450	0.028*
C10	0.36764 (8)	0.2678 (2)	0.32060 (16)	0.0231 (4)
H10	0.3813	0.1616	0.3628	0.028*
C11	0.40806 (9)	0.3538 (2)	0.26845 (16)	0.0235 (4)
H11	0.4487	0.3022	0.2742	0.028*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0217 (8)	0.0194 (8)	0.0284 (9)	0.0007 (6)	0.0110 (7)	0.0031 (7)
N2	0.0249 (8)	0.0191 (8)	0.0223 (8)	0.0013 (6)	0.0095 (6)	−0.0011 (6)
N3	0.0254 (8)	0.0213 (8)	0.0262 (9)	−0.0016 (6)	0.0087 (7)	0.0019 (7)
C1	0.0275 (9)	0.0177 (9)	0.0191 (9)	−0.0009 (7)	0.0089 (7)	−0.0013 (7)
C2	0.0240 (9)	0.0224 (10)	0.0214 (10)	0.0019 (8)	0.0067 (7)	−0.0018 (8)
C3	0.0344 (10)	0.0191 (9)	0.0194 (10)	0.0024 (8)	0.0072 (8)	0.0004 (7)
C4	0.0316 (10)	0.0193 (9)	0.0200 (9)	−0.0032 (8)	0.0096 (8)	−0.0008 (7)
C5	0.0252 (9)	0.0222 (10)	0.0221 (10)	−0.0018 (8)	0.0093 (8)	−0.0018 (8)
C6	0.0261 (9)	0.0207 (9)	0.0204 (9)	0.0004 (7)	0.0071 (7)	0.0004 (7)
C7	0.0390 (11)	0.0250 (11)	0.0287 (11)	−0.0033 (9)	0.0128 (9)	0.0045 (8)
C8	0.0237 (9)	0.0196 (9)	0.0177 (9)	−0.0013 (7)	0.0065 (7)	−0.0023 (7)
C9	0.0222 (9)	0.0211 (9)	0.0267 (10)	0.0003 (7)	0.0079 (8)	0.0002 (8)
C10	0.0275 (9)	0.0187 (9)	0.0237 (10)	0.0022 (7)	0.0077 (8)	0.0003 (8)
C11	0.0264 (9)	0.0211 (10)	0.0238 (10)	0.0020 (8)	0.0080 (8)	−0.0020 (8)

Geometric parameters (Å, °)

N1—C8	1.374 (2)	C4—C5	1.386 (3)
N1—C1	1.401 (2)	C4—C7	1.509 (3)
N1—H1	0.89 (2)	C5—C6	1.388 (2)
N2—C8	1.333 (2)	C5—H5	0.9500
N2—C11	1.344 (2)	C6—H6	0.9500
N3—C9	1.320 (2)	C7—H7A	0.9800
N3—C10	1.349 (2)	C7—H7B	0.9800
C1—C6	1.395 (2)	C7—H7C	0.9800
C1—C2	1.398 (2)	C8—C9	1.410 (2)
C2—C3	1.380 (3)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.372 (3)
C3—C4	1.393 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—H11	0.9500
C8—N1—C1	130.28 (15)	C5—C6—H6	120.2
C8—N1—H1	113.3 (13)	C1—C6—H6	120.2
C1—N1—H1	115.9 (14)	C4—C7—H7A	109.5
C8—N2—C11	115.60 (15)	C4—C7—H7B	109.5
C9—N3—C10	116.84 (15)	H7A—C7—H7B	109.5
C6—C1—C2	118.44 (16)	C4—C7—H7C	109.5
C6—C1—N1	124.95 (16)	H7A—C7—H7C	109.5
C2—C1—N1	116.58 (15)	H7B—C7—H7C	109.5
C3—C2—C1	120.81 (16)	N2—C8—N1	121.33 (16)
C3—C2—H2	119.6	N2—C8—C9	121.10 (16)
C1—C2—H2	119.6	N1—C8—C9	117.57 (15)
C2—C3—C4	121.50 (17)	N3—C9—C8	122.23 (16)
C2—C3—H3	119.3	N3—C9—H9	118.9
C4—C3—H3	119.3	C8—C9—H9	118.9
C5—C4—C3	117.08 (16)	N3—C10—C11	120.51 (17)
C5—C4—C7	121.84 (16)	N3—C10—H10	119.7
C3—C4—C7	121.08 (17)	C11—C10—H10	119.7
C4—C5—C6	122.59 (16)	N2—C11—C10	123.68 (17)
C4—C5—H5	118.7	N2—C11—H11	118.2
C6—C5—H5	118.7	C10—C11—H11	118.2
C5—C6—C1	119.58 (17)
C8—N1—C1—C6	−7.4 (3)	N1—C1—C6—C5	−177.39 (17)
C8—N1—C1—C2	174.81 (17)	C11—N2—C8—N1	179.29 (16)
C6—C1—C2—C3	0.2 (3)	C11—N2—C8—C9	−1.1 (2)
N1—C1—C2—C3	178.22 (16)	C1—N1—C8—N2	−13.4 (3)
C1—C2—C3—C4	−0.6 (3)	C1—N1—C8—C9	166.96 (17)
C2—C3—C4—C5	0.2 (3)	C10—N3—C9—C8	−1.1 (3)
C2—C3—C4—C7	−179.30 (17)	N2—C8—C9—N3	2.1 (3)
C3—C4—C5—C6	0.4 (3)	N1—C8—C9—N3	−178.20 (16)
C7—C4—C5—C6	179.96 (17)	C9—N3—C10—C11	−0.8 (3)
C4—C5—C6—C1	−0.7 (3)	C8—N2—C11—C10	−0.8 (3)
C2—C1—C6—C5	0.4 (3)	N3—C10—C11—N2	1.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3i	0.89 (2)	2.10 (2)	2.963 (2)	163 (2)

Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2.