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

Wan Saffiee, W.A.M.; Idris, A.; Aiyub, Z.; Abdullah, Z.; Ng, S.W.

doi:10.1107/S160053680803729X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2440

doi:10.1107/S160053680803729X

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

Wan Ainna Mardhiah Wan Saffiee,^a Azila Idris,^a Zaharah Aiyub,^a Zanariah Abdullah ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 19 October 2008; accepted 11 November 2008; online 26 November 2008)

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, C 2/c
a = 21.7179 (7) Å
b = 7.5323 (3) Å
c = 12.0073 (5) Å
β = 105.790 (3)°
V = 1890.1 (1) Å³
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[F² > 2σ(F²)] = 0.046
wR(F²) = 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

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) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680803729X/sg2277sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680803729X/sg2277Isup2.hkl

checkCIF report

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₁₁N₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₁₁H₁₁N₃	F(000) = 784
M_r = 185.23	D_x = 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 = 2.9–27.2°
b = 7.5323 (3) Å	µ = 0.08 mm⁻¹
c = 12.0073 (5) Å	T = 100 K
β = 105.790 (3)°	Prism, colorless
V = 1890.1 (1) Å³	0.30 × 0.20 × 0.05 mm
Z = 8

Data collection top

Bruker SMART APEX diffractometer	1437 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −28→28
6057 measured reflections	k = −9→9
2165 independent reflections	l = −15→15

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0652P)² + 0.9346P] where P = (F_o² + 2F_c²)/3
2165 reflections	(Δ/σ)_max = 0.001
132 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₁H₁₁N₃	V = 1890.1 (1) Å³
M_r = 185.23	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.7179 (7) Å	µ = 0.08 mm⁻¹
b = 7.5323 (3) Å	T = 100 K
c = 12.0073 (5) Å	0.30 × 0.20 × 0.05 mm
β = 105.790 (3)°

Data collection top

Bruker SMART APEX diffractometer	1437 reflections with I > 2σ(I)
6057 measured reflections	R_int = 0.041
2165 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.27 e Å⁻³
2165 reflections	Δρ_min = −0.26 e Å⁻³
132 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁N₃
M_r	185.23
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	21.7179 (7), 7.5323 (3), 12.0073 (5)
β (°)	105.790 (3)
V (Å³)	1890.1 (1)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6057, 2165, 1437
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.135, 1.03
No. of reflections	2165
No. of parameters	132
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

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) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

We thank the University of Malaya for supporting this study (grant No. FS 358/2008 A).

References

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