A second monoclinic polymorph of N-(pyrazin-2-yl)aniline

Abdullah, Z.; Ng, S.W.

doi:10.1107/S1600536808031954

organic compounds

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Volume 64| Part 11| November 2008| Page o2106

doi:10.1107/S1600536808031954

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A second monoclinic polymorph of N-(pyrazin-2-yl)aniline

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 23 September 2008; accepted 4 October 2008; online 11 October 2008)

The two aromatic rings in the title compound, C₁₀H₉N₃, are aligned at 23.4 (1)° and the bridging C—N—C angle is 128.9 (1)°. In the crystal structure, intermolecular N—H⋯N hydrogen bonds result in a chain motif, the repeat distance of which is half the b axial length of 8.8851 (3) Å.

Related literature

In the P2₁/c modification, the aromatic rings are aligned at 15.2 (1)°, and the repeat distance of the helical chain is half the b-axial length of 7.8423 (3) Å; see: Wan Saffiee et al. (2008 ).

Experimental

Crystal data

C₁₀H₉N₃
M_r = 171.20
Monoclinic, P 2₁ /n
a = 8.2194 (3) Å
b = 8.8851 (3) Å
c = 11.8395 (4) Å
β = 104.643 (2)°
V = 836.56 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 (2) K
0.25 × 0.05 × 0.03 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
7621 measured reflections
1922 independent reflections
1389 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.113
S = 1.03
1922 reflections
122 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N3ⁱ	0.90 (2)	2.17 (2)	3.062 (2)	175 (2)
Symmetry code: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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/S1600536808031954/pk2124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031954/pk2124Isup2.hkl

checkCIF report

Comment top

The cell dimensions of the reported monoclinic P2₁/c modification are: a = 10.0644 (3), b = 7.8423 (3), c = 10.8907 (3) Å; β = 116.439 (2)° (Wan Saffiee et al., 2008). The cell dimensions of the present modification (Scheme I, Fig. 1), after transformation to the standard P2₁/c setting, are: a = 8.2194 (3), b = 8.8851 (3), c = 12.5909 (4) Å, β = 114.525 (2)°.

Related literature top

In the P2₁/c modification, the aromatic rings are aligned at 15.2 (1)°, and the repeat distance of the helical chain is half the b-axial length of 7.8423 (3) Å; see: Wan Saffiee et al. (2008).

Experimental top

The P2₁/c modification of 2-pyrazinyl-N-aniline (0.10 g, 0.4 mmol), zinc acetate (0.09 g, 0.4 mmol) and water (18 ml) were heated in a 23-ml Teflon-lined Parr bomb at 403 K for 2 days. The bomb was cooled to room temperature at 5 K min^-1. Several faint yellow prisms were picked out manually from the cool solution.

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 C₁₀H₉N₃ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

N-(pyrazin-2-yl)aniline top

Crystal data top

C₁₀H₉N₃	F(000) = 360
M_r = 171.20	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1282 reflections
a = 8.2194 (3) Å	θ = 2.7–26.1°
b = 8.8851 (3) Å	µ = 0.09 mm⁻¹
c = 11.8395 (4) Å	T = 100 K
β = 104.643 (2)°	Prism, pale yellow
V = 836.56 (5) Å³	0.25 × 0.05 × 0.03 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1389 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 27.5°, θ_min = 2.7°
ω scans	h = −10→10
7621 measured reflections	k = −11→11
1922 independent reflections	l = −15→14

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0547P)² + 0.1331P] where P = (F_o² + 2F_c²)/3
1922 reflections	(Δ/σ)_max = 0.001
122 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₀H₉N₃	V = 836.56 (5) Å³
M_r = 171.20	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.2194 (3) Å	µ = 0.09 mm⁻¹
b = 8.8851 (3) Å	T = 100 K
c = 11.8395 (4) Å	0.25 × 0.05 × 0.03 mm
β = 104.643 (2)°

Data collection top

Bruker SMART APEX diffractometer	1389 reflections with I > 2σ(I)
7621 measured reflections	R_int = 0.045
1922 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.20 e Å⁻³
1922 reflections	Δρ_min = −0.23 e Å⁻³
122 parameters

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

	x	y	z	U_iso*/U_eq
N1	1.00115 (16)	0.42084 (14)	0.63143 (11)	0.0216 (3)
H1	1.103 (2)	0.377 (2)	0.6527 (15)	0.035 (5)*
N2	0.84988 (15)	0.63197 (14)	0.66840 (11)	0.0230 (3)
N3	1.15770 (16)	0.76478 (14)	0.78284 (11)	0.0228 (3)
C1	0.86787 (18)	0.33136 (16)	0.56827 (12)	0.0193 (3)
C2	0.89595 (19)	0.17682 (17)	0.56499 (13)	0.0254 (4)
H2	1.0021	0.1367	0.6049	0.030*
C3	0.7717 (2)	0.08147 (17)	0.50462 (14)	0.0264 (4)
H3	0.7933	−0.0235	0.5030	0.032*
C4	0.61582 (19)	0.13750 (17)	0.44633 (13)	0.0232 (3)
H4	0.5296	0.0717	0.4058	0.028*
C5	0.58777 (19)	0.29106 (17)	0.44814 (13)	0.0222 (3)
H5	0.4815	0.3305	0.4079	0.027*
C6	0.71238 (18)	0.38836 (16)	0.50783 (13)	0.0211 (3)
H6	0.6916	0.4936	0.5074	0.025*
C7	0.99583 (18)	0.56191 (16)	0.67668 (13)	0.0192 (3)
C8	1.14967 (18)	0.63040 (16)	0.73478 (13)	0.0213 (3)
H8	1.2514	0.5772	0.7393	0.026*
C9	1.00948 (18)	0.83515 (18)	0.77382 (13)	0.0248 (4)
H9	1.0085	0.9325	0.8069	0.030*
C10	0.8604 (2)	0.76892 (17)	0.71788 (14)	0.0254 (4)
H10	0.7592	0.8226	0.7139	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0144 (7)	0.0200 (7)	0.0276 (7)	0.0019 (5)	0.0003 (5)	−0.0014 (5)
N2	0.0173 (6)	0.0230 (7)	0.0272 (7)	0.0004 (5)	0.0027 (5)	−0.0036 (5)
N3	0.0195 (7)	0.0228 (7)	0.0251 (7)	−0.0033 (5)	0.0037 (5)	−0.0011 (5)
C1	0.0180 (7)	0.0205 (7)	0.0193 (7)	−0.0010 (6)	0.0048 (6)	−0.0009 (6)
C2	0.0217 (8)	0.0227 (8)	0.0289 (8)	0.0040 (6)	0.0012 (6)	0.0000 (6)
C3	0.0293 (9)	0.0176 (8)	0.0307 (9)	0.0005 (6)	0.0043 (7)	−0.0019 (6)
C4	0.0217 (8)	0.0233 (8)	0.0244 (8)	−0.0059 (6)	0.0053 (6)	−0.0035 (6)
C5	0.0173 (7)	0.0251 (8)	0.0229 (8)	0.0005 (6)	0.0026 (6)	−0.0006 (6)
C6	0.0195 (8)	0.0190 (7)	0.0237 (8)	0.0005 (6)	0.0031 (6)	−0.0011 (6)
C7	0.0175 (7)	0.0198 (7)	0.0194 (7)	0.0004 (6)	0.0030 (6)	0.0020 (6)
C8	0.0177 (7)	0.0224 (8)	0.0233 (8)	−0.0001 (6)	0.0041 (6)	0.0015 (6)
C9	0.0228 (8)	0.0220 (8)	0.0284 (8)	−0.0016 (6)	0.0047 (6)	−0.0049 (6)
C10	0.0202 (8)	0.0241 (8)	0.0307 (9)	0.0032 (6)	0.0043 (6)	−0.0041 (7)

Geometric parameters (Å, º) top

N1—C7	1.3681 (19)	C3—H3	0.9500
N1—C1	1.4061 (19)	C4—C5	1.385 (2)
N1—H1	0.897 (18)	C4—H4	0.9500
N2—C7	1.3330 (18)	C5—C6	1.389 (2)
N2—C10	1.3438 (19)	C5—H5	0.9500
N3—C8	1.3171 (19)	C6—H6	0.9500
N3—C9	1.3494 (19)	C7—C8	1.415 (2)
C1—C6	1.393 (2)	C8—H8	0.9500
C1—C2	1.395 (2)	C9—C10	1.370 (2)
C2—C3	1.379 (2)	C9—H9	0.9500
C2—H2	0.9500	C10—H10	0.9500
C3—C4	1.385 (2)

C7—N1—C1	128.94 (13)	C4—C5—H5	119.4
C7—N1—H1	114.0 (12)	C6—C5—H5	119.4
C1—N1—H1	116.7 (11)	C5—C6—C1	119.86 (14)
C7—N2—C10	115.67 (13)	C5—C6—H6	120.1
C8—N3—C9	116.12 (13)	C1—C6—H6	120.1
C6—C1—C2	118.72 (13)	N2—C7—N1	121.09 (13)
C6—C1—N1	123.92 (13)	N2—C7—C8	120.79 (13)
C2—C1—N1	117.35 (13)	N1—C7—C8	118.11 (13)
C3—C2—C1	120.88 (14)	N3—C8—C7	122.74 (13)
C3—C2—H2	119.6	N3—C8—H8	118.6
C1—C2—H2	119.6	C7—C8—H8	118.6
C2—C3—C4	120.52 (14)	N3—C9—C10	121.23 (14)
C2—C3—H3	119.7	N3—C9—H9	119.4
C4—C3—H3	119.7	C10—C9—H9	119.4
C5—C4—C3	118.88 (14)	N2—C10—C9	123.44 (14)
C5—C4—H4	120.6	N2—C10—H10	118.3
C3—C4—H4	120.6	C9—C10—H10	118.3
C4—C5—C6	121.11 (14)

C7—N1—C1—C6	21.9 (2)	C10—N2—C7—N1	178.88 (14)
C7—N1—C1—C2	−159.27 (15)	C10—N2—C7—C8	0.2 (2)
C6—C1—C2—C3	−1.0 (2)	C1—N1—C7—N2	2.9 (2)
N1—C1—C2—C3	−179.81 (14)	C1—N1—C7—C8	−178.36 (14)
C1—C2—C3—C4	−0.3 (2)	C9—N3—C8—C7	0.0 (2)
C2—C3—C4—C5	1.0 (2)	N2—C7—C8—N3	−0.2 (2)
C3—C4—C5—C6	−0.5 (2)	N1—C7—C8—N3	−178.92 (13)
C4—C5—C6—C1	−0.8 (2)	C8—N3—C9—C10	0.1 (2)
C2—C1—C6—C5	1.5 (2)	C7—N2—C10—C9	0.0 (2)
N1—C1—C6—C5	−179.75 (13)	N3—C9—C10—N2	−0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N3ⁱ	0.90 (2)	2.17 (2)	3.062 (2)	175 (2)

Symmetry code: (i) −x+5/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃
M_r	171.20
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.2194 (3), 8.8851 (3), 11.8395 (4)
β (°)	104.643 (2)
V (Å³)	836.56 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.25 × 0.05 × 0.03

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7621, 1922, 1389
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.03
No. of reflections	1922
No. of parameters	122
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.23

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	0.90 (2)	2.17 (2)	3.062 (2)	175 (2)

Symmetry code: (i) −x+5/2, y−1/2, −z+3/2.

Acknowledgements

The authors thank the University of Malaya for supporting this study (grant Nos. FS 358/2008A and FA 067/2006A).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wan Saffiee, W. A. M., Idris, A., Abdullah, Z., Aiyub, Z. & Ng, S. W. (2008). Acta Cryst. E64, o2105. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar