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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1968.
Published online 2009 July 25. doi:  10.1107/S1600536809028554
PMCID: PMC2977195

5-Bromo-N 3-phenyl­pyrazine-2,3-diamine

Abstract

In the title compound, C10H9BrN4, the dihedral angle between the benzene and pyrazine rings is 61.34 (5)°. Inter­molecular N—H(...)N hydrogen bonds and N—H(...)π inter­actions assemble the mol­ecules into a three-dimensional network structure.

Related literature

For Cu or Pd catalysed C–N cross-coupling reactions, see: Fors et al. (2009 [triangle]); Liu et al. (2007 [triangle]).

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Object name is e-65-o1968-scheme1.jpg

Experimental

Crystal data

  • C10H9BrN4
  • M r = 265.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1968-efi1.jpg
  • a = 7.4834 (8) Å
  • b = 15.4038 (17) Å
  • c = 9.2079 (10) Å
  • β = 91.307 (2)°
  • V = 1061.1 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.85 mm−1
  • T = 293 K
  • 0.15 × 0.12 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.596, T max = 0.700
  • 5494 measured reflections
  • 1871 independent reflections
  • 1555 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.059
  • S = 1.00
  • 1871 reflections
  • 140 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028554/gk2218sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028554/gk2218Isup2.hkl

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

supplementary crystallographic information

Comment

Cu or Pd catalyzed C—N cross-coupling reactions were studied recently (Liu et al., 2007; Fors et al., 2009), which reported that catalysts using certain ligands allow for the C—N cross-coupling reactions. Different to them, we got a cross-coupling product with high selectivity under microwave without catalyst.

Here we report the crystal structure of the title compound. In (I) (Fig.1), the bond length to the bridging NH group are 1.377 (3) and 1.420 (3) Å. Moreover, intermolecular typical N—H···N (N···N 3.084 (3) Å) hydrogen bonds and N—H···π [H···π 2.633 (2) Å] interaction assemble molecules into a two-dimensional network structure.

Experimental

5-Bromo-2-aminopyrazine (10 mmol) and aniline (40 mmol) were added to a reaction kettle, then reacted 2 h at 413 K under microwave operation. The product was purified on a SiO2 flash column to give a title product (yield 31%). Crystals of the title compound suitable for X-ray analysis were grown from a dichloromethane solution.

Refinement

The C–H and N–H hydrogen atoms were placed in calculated positions, with distances C—H = 0.93 Å, N—H = 0.87 Å. and Uiso(H) = 1.2 Ueq (C, N). Initially positions of the amino H atoms were refined but in the final cycles the N—H distances were constrained to 0.87 Å and all H atoms were treated as riding with Uiso(H) values of 1.5Ueq(C,N).

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
Fig. 2.
The two-dimensional network structure formed by N—H···N hydrogen bonds and N—H···π interactions.

Crystal data

C10H9BrN4F(000) = 528
Mr = 265.12Dx = 1.660 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2474 reflections
a = 7.4834 (8) Åθ = 2.6–27.6°
b = 15.4038 (17) ŵ = 3.85 mm1
c = 9.2079 (10) ÅT = 293 K
β = 91.307 (2)°Block, colorless
V = 1061.1 (2) Å30.15 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer1871 independent reflections
Radiation source: fine-focus sealed tube1555 reflections with I > 2σ(I)
graphiteRint = 0.022
[var phi] and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −8→8
Tmin = 0.596, Tmax = 0.700k = −17→18
5494 measured reflectionsl = −10→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.059w = 1/[σ2(Fo2) + (0.025P)2 + 0.6504P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.002
1871 reflectionsΔρmax = 0.33 e Å3
140 parametersΔρmin = −0.33 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0241 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 (Å2)

xyzUiso*/Ueq
Br1−0.05901 (4)0.351301 (18)1.09071 (3)0.05020 (14)
N10.1466 (3)0.39455 (14)0.4791 (2)0.0455 (5)
H1A0.10000.43880.43340.046 (8)*
H1B0.24000.36760.44720.075 (11)*
N2−0.0254 (3)0.43567 (13)0.6710 (2)0.0404 (5)
N30.1484 (2)0.31467 (12)0.84959 (19)0.0319 (4)
N40.3193 (3)0.27272 (13)0.6497 (2)0.0420 (5)
H40.29800.25950.55910.063 (9)*
C10.1017 (3)0.38587 (14)0.6195 (2)0.0317 (5)
C20.1899 (3)0.32331 (14)0.7117 (2)0.0302 (5)
C30.0152 (3)0.36556 (15)0.8955 (2)0.0343 (5)
C4−0.0699 (3)0.42447 (16)0.8104 (3)0.0423 (6)
H4A−0.16080.45790.84880.051*
C50.4259 (3)0.21097 (15)0.7267 (2)0.0365 (6)
C60.4269 (4)0.12553 (16)0.6809 (3)0.0446 (6)
H60.35650.10840.60140.054*
C70.5329 (4)0.06590 (19)0.7538 (3)0.0564 (8)
H70.53380.00840.72290.068*
C80.6367 (4)0.0902 (2)0.8710 (3)0.0613 (8)
H80.70560.04910.92090.074*
C90.6390 (4)0.1748 (2)0.9145 (3)0.0589 (8)
H90.71080.19160.99340.071*
C100.5348 (3)0.23602 (18)0.8419 (3)0.0468 (6)
H100.53830.29380.87090.056*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0541 (2)0.0615 (2)0.03565 (17)0.00683 (14)0.01461 (11)0.00123 (12)
N10.0648 (15)0.0406 (12)0.0314 (11)0.0182 (11)0.0047 (10)0.0082 (9)
N20.0466 (13)0.0353 (11)0.0392 (12)0.0102 (9)0.0014 (9)0.0047 (9)
N30.0345 (11)0.0327 (10)0.0288 (10)0.0035 (8)0.0036 (8)0.0018 (8)
N40.0504 (13)0.0451 (12)0.0310 (11)0.0194 (10)0.0094 (9)0.0070 (9)
C10.0369 (13)0.0262 (11)0.0320 (12)0.0014 (10)−0.0003 (10)−0.0008 (9)
C20.0330 (13)0.0265 (11)0.0312 (12)0.0008 (9)0.0013 (10)0.0001 (9)
C30.0375 (13)0.0359 (13)0.0297 (12)−0.0004 (10)0.0048 (10)−0.0004 (10)
C40.0433 (15)0.0400 (14)0.0440 (15)0.0124 (11)0.0085 (11)0.0005 (11)
C50.0339 (13)0.0404 (14)0.0356 (12)0.0084 (10)0.0107 (10)0.0087 (11)
C60.0408 (15)0.0416 (15)0.0516 (16)0.0068 (11)0.0040 (12)0.0028 (12)
C70.0502 (17)0.0404 (15)0.079 (2)0.0149 (13)0.0099 (15)0.0084 (14)
C80.0492 (18)0.069 (2)0.066 (2)0.0229 (15)0.0049 (15)0.0211 (16)
C90.0419 (16)0.084 (2)0.0504 (17)0.0121 (15)−0.0041 (13)0.0015 (15)
C100.0438 (15)0.0478 (15)0.0489 (15)0.0067 (12)0.0064 (12)−0.0016 (13)

Geometric parameters (Å, °)

Br1—C31.906 (2)C4—H4A0.9300
N1—C11.349 (3)C5—C101.378 (4)
N1—H1A0.8699C5—C61.382 (3)
N1—H1B0.8700C6—C71.378 (4)
N2—C11.319 (3)C6—H60.9300
N2—C41.344 (3)C7—C81.368 (4)
N3—C21.320 (3)C7—H70.9300
N3—C31.344 (3)C8—C91.364 (4)
N4—C21.377 (3)C8—H80.9300
N4—C51.420 (3)C9—C101.385 (4)
N4—H40.8700C9—H90.9300
C1—C21.436 (3)C10—H100.9300
C3—C41.349 (3)
C1—N1—H1A115.8C3—C4—H4A119.4
C1—N1—H1B119.8C10—C5—C6119.6 (2)
H1A—N1—H1B121.8C10—C5—N4120.8 (2)
C1—N2—C4117.7 (2)C6—C5—N4119.5 (2)
C2—N3—C3115.85 (19)C7—C6—C5119.5 (3)
C2—N4—C5124.36 (19)C7—C6—H6120.2
C2—N4—H4114.5C5—C6—H6120.2
C5—N4—H4114.3C8—C7—C6120.8 (3)
N2—C1—N1119.0 (2)C8—C7—H7119.6
N2—C1—C2120.2 (2)C6—C7—H7119.6
N1—C1—C2120.8 (2)C9—C8—C7119.7 (3)
N3—C2—N4121.6 (2)C9—C8—H8120.1
N3—C2—C1121.5 (2)C7—C8—H8120.1
N4—C2—C1116.92 (19)C8—C9—C10120.4 (3)
N3—C3—C4123.6 (2)C8—C9—H9119.8
N3—C3—Br1117.62 (16)C10—C9—H9119.8
C4—C3—Br1118.81 (18)C5—C10—C9119.8 (3)
N2—C4—C3121.2 (2)C5—C10—H10120.1
N2—C4—H4A119.4C9—C10—H10120.1
C4—N2—C1—N1178.7 (2)N3—C3—C4—N20.3 (4)
C4—N2—C1—C2−1.1 (3)Br1—C3—C4—N2−178.49 (19)
C3—N3—C2—N4−177.5 (2)C2—N4—C5—C10−59.7 (3)
C3—N3—C2—C12.3 (3)C2—N4—C5—C6123.5 (3)
C5—N4—C2—N3−3.5 (4)C10—C5—C6—C71.9 (4)
C5—N4—C2—C1176.6 (2)N4—C5—C6—C7178.8 (2)
N2—C1—C2—N3−0.9 (3)C5—C6—C7—C80.1 (4)
N1—C1—C2—N3179.4 (2)C6—C7—C8—C9−1.6 (5)
N2—C1—C2—N4179.0 (2)C7—C8—C9—C100.9 (5)
N1—C1—C2—N4−0.8 (3)C6—C5—C10—C9−2.6 (4)
C2—N3—C3—C4−2.1 (3)N4—C5—C10—C9−179.4 (2)
C2—N3—C3—Br1176.66 (16)C8—C9—C10—C51.2 (4)
C1—N2—C4—C31.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···Cg1i0.862.633.436 (3)157
N1—H1A···N2ii0.862.223.084 (3)169

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2218).

References

  • Bruker (2005). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fors, B. P., Davis, N. R. & Buchwald, S. L. (2009). J. Am. Chem. Soc.131, 5766–5768. [PMC free article] [PubMed]
  • Liu, Y. F., Bai, Y. J., Zhang, J., Li, Y. Y., Jiao, J. P. & Qi, X. L. (2007). Eur. J. Org. Chem., 6084–6088.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography