supplementary materials
A second monoclinic polymorph of N-(pyrazin-2-yl)aniline
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.
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.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 Å) and
were included in the refinement in the riding model approximation, with
U(H) fixed at 1.2U(C). The amino H-atom was located in a
difference Fourier map, and was freely refined.
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).
N-(pyrazin-2-yl)aniline
top
Crystal data top
| C10H9N3 | F(000) = 360 |
| Mr = 171.20 | Dx = 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 | Rint = 0.045 |
| graphite | θmax = 27.5°, θmin = 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(Fo2) + (0.0547P)2 + 0.1331P]
where P = (Fo2 + 2Fc2)/3 |
| 1922 reflections | (Δ/σ)max = 0.001 |
| 122 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
| C10H9N3 | V = 836.56 (5) Å3 |
| Mr = 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 | Rint = 0.045 |
| 1922 independent reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.113 | Δρmax = 0.20 e Å−3 |
| S = 1.03 | Δρmin = −0.22 e Å−3 |
| 1922 reflections | Absolute structure: ? |
| 122 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| 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, °) 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, °) 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 codes: (i) −x+5/2, y−1/2, −z+3/2. |
Table 1
Hydrogen-bond geometry (Å, °) 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 codes: (i) −x+5/2, y−1/2, −z+3/2. |
The authors thank the University of Malaya for supporting this study (grant No.
F2358/2008A).
Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wan Saffiee, W. A. M., Idris, A., Abdullah, Z., Aiyub, Z. & Ng, S. W. (2008). Acta Cryst. E64, o0000. [pk2121]
Westrip, S. P. (2008). publCIF. In preparation.
![[Figure 1]](./pk2124fig1thm.gif)
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)°.