5-Bromo-N3-phenyl­pyrazine-2,3-diamine

Zhu, X.

doi:10.1107/S1600536809028554

organic compounds

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Volume 65| Part 8| August 2009| Page o1968

doi:10.1107/S1600536809028554

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5-Bromo-N³-phenylpyrazine-2,3-diamine

Xiaohui Zhu ^a ^*

^aSchool of Chemistry and Chemical Engineering, Taishan Medical University, Tai'an 271016, People's Republic of China
^*Correspondence e-mail: zhuxh007@163.com

(Received 15 June 2009; accepted 20 July 2009; online 25 July 2009)

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 ); Liu et al. (2007 ).

Experimental

Crystal data

C₁₀H₉BrN₄
M_r = 265.12
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.025
wR(F²) = 0.059
S = 1.00
1871 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cg1ⁱ	0.86	2.63	3.436 (3)	157
N1—H1A⋯N2ⁱⁱ	0.86	2.22	3.084 (3)	169
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z+1. Cg1 is the centroid of the C5–C10 ring.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For Cu or Pd catalysed C–N cross-coupling reactions, see: Fors et al. (2009); Liu et al. (2007). Cg1 is the centroid of [please define].

Experimental top

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.

Computing details top

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

Figures top

	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.

5-Bromo-N³-phenylpyrazine-2,3-diamine top

Crystal data top

C₁₀H₉BrN₄	F(000) = 528
M_r = 265.12	D_x = 1.660 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2474 reflections
a = 7.4834 (8) Å	θ = 2.6–27.6°
b = 15.4038 (17) Å	µ = 3.85 mm⁻¹
c = 9.2079 (10) Å	T = 293 K
β = 91.307 (2)°	Block, colorless
V = 1061.1 (2) Å³	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	1871 independent reflections
Radiation source: fine-focus sealed tube	1555 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.596, T_max = 0.700	k = −17→18
5494 measured reflections	l = −10→10

Refinement top

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)] = 0.025	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.025P)² + 0.6504P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.002
1871 reflections	Δρ_max = 0.33 e Å⁻³
140 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0241 (11)

Crystal data top

C₁₀H₉BrN₄	V = 1061.1 (2) Å³
M_r = 265.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4834 (8) Å	µ = 3.85 mm⁻¹
b = 15.4038 (17) Å	T = 293 K
c = 9.2079 (10) Å	0.15 × 0.12 × 0.10 mm
β = 91.307 (2)°

Data collection top

Bruker SMART APEX diffractometer	1871 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1555 reflections with I > 2σ(I)
T_min = 0.596, T_max = 0.700	R_int = 0.022
5494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.00	Δρ_max = 0.33 e Å⁻³
1871 reflections	Δρ_min = −0.33 e Å⁻³
140 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	−0.05901 (4)	0.351301 (18)	1.09071 (3)	0.05020 (14)
N1	0.1466 (3)	0.39455 (14)	0.4791 (2)	0.0455 (5)
H1A	0.1000	0.4388	0.4334	0.046 (8)*
H1B	0.2400	0.3676	0.4472	0.075 (11)*
N2	−0.0254 (3)	0.43567 (13)	0.6710 (2)	0.0404 (5)
N3	0.1484 (2)	0.31467 (12)	0.84959 (19)	0.0319 (4)
N4	0.3193 (3)	0.27272 (13)	0.6497 (2)	0.0420 (5)
H4	0.2980	0.2595	0.5591	0.063 (9)*
C1	0.1017 (3)	0.38587 (14)	0.6195 (2)	0.0317 (5)
C2	0.1899 (3)	0.32331 (14)	0.7117 (2)	0.0302 (5)
C3	0.0152 (3)	0.36556 (15)	0.8955 (2)	0.0343 (5)
C4	−0.0699 (3)	0.42447 (16)	0.8104 (3)	0.0423 (6)
H4A	−0.1608	0.4579	0.8488	0.051*
C5	0.4259 (3)	0.21097 (15)	0.7267 (2)	0.0365 (6)
C6	0.4269 (4)	0.12553 (16)	0.6809 (3)	0.0446 (6)
H6	0.3565	0.1084	0.6014	0.054*
C7	0.5329 (4)	0.06590 (19)	0.7538 (3)	0.0564 (8)
H7	0.5338	0.0084	0.7229	0.068*
C8	0.6367 (4)	0.0902 (2)	0.8710 (3)	0.0613 (8)
H8	0.7056	0.0491	0.9209	0.074*
C9	0.6390 (4)	0.1748 (2)	0.9145 (3)	0.0589 (8)
H9	0.7108	0.1916	0.9934	0.071*
C10	0.5348 (3)	0.23602 (18)	0.8419 (3)	0.0468 (6)
H10	0.5383	0.2938	0.8709	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0541 (2)	0.0615 (2)	0.03565 (17)	0.00683 (14)	0.01461 (11)	0.00123 (12)
N1	0.0648 (15)	0.0406 (12)	0.0314 (11)	0.0182 (11)	0.0047 (10)	0.0082 (9)
N2	0.0466 (13)	0.0353 (11)	0.0392 (12)	0.0102 (9)	0.0014 (9)	0.0047 (9)
N3	0.0345 (11)	0.0327 (10)	0.0288 (10)	0.0035 (8)	0.0036 (8)	0.0018 (8)
N4	0.0504 (13)	0.0451 (12)	0.0310 (11)	0.0194 (10)	0.0094 (9)	0.0070 (9)
C1	0.0369 (13)	0.0262 (11)	0.0320 (12)	0.0014 (10)	−0.0003 (10)	−0.0008 (9)
C2	0.0330 (13)	0.0265 (11)	0.0312 (12)	0.0008 (9)	0.0013 (10)	0.0001 (9)
C3	0.0375 (13)	0.0359 (13)	0.0297 (12)	−0.0004 (10)	0.0048 (10)	−0.0004 (10)
C4	0.0433 (15)	0.0400 (14)	0.0440 (15)	0.0124 (11)	0.0085 (11)	0.0005 (11)
C5	0.0339 (13)	0.0404 (14)	0.0356 (12)	0.0084 (10)	0.0107 (10)	0.0087 (11)
C6	0.0408 (15)	0.0416 (15)	0.0516 (16)	0.0068 (11)	0.0040 (12)	0.0028 (12)
C7	0.0502 (17)	0.0404 (15)	0.079 (2)	0.0149 (13)	0.0099 (15)	0.0084 (14)
C8	0.0492 (18)	0.069 (2)	0.066 (2)	0.0229 (15)	0.0049 (15)	0.0211 (16)
C9	0.0419 (16)	0.084 (2)	0.0504 (17)	0.0121 (15)	−0.0041 (13)	0.0015 (15)
C10	0.0438 (15)	0.0478 (15)	0.0489 (15)	0.0067 (12)	0.0064 (12)	−0.0016 (13)

Geometric parameters (Å, º) top

Br1—C3	1.906 (2)	C4—H4A	0.9300
N1—C1	1.349 (3)	C5—C10	1.378 (4)
N1—H1A	0.8699	C5—C6	1.382 (3)
N1—H1B	0.8700	C6—C7	1.378 (4)
N2—C1	1.319 (3)	C6—H6	0.9300
N2—C4	1.344 (3)	C7—C8	1.368 (4)
N3—C2	1.320 (3)	C7—H7	0.9300
N3—C3	1.344 (3)	C8—C9	1.364 (4)
N4—C2	1.377 (3)	C8—H8	0.9300
N4—C5	1.420 (3)	C9—C10	1.385 (4)
N4—H4	0.8700	C9—H9	0.9300
C1—C2	1.436 (3)	C10—H10	0.9300
C3—C4	1.349 (3)

C1—N1—H1A	115.8	C3—C4—H4A	119.4
C1—N1—H1B	119.8	C10—C5—C6	119.6 (2)
H1A—N1—H1B	121.8	C10—C5—N4	120.8 (2)
C1—N2—C4	117.7 (2)	C6—C5—N4	119.5 (2)
C2—N3—C3	115.85 (19)	C7—C6—C5	119.5 (3)
C2—N4—C5	124.36 (19)	C7—C6—H6	120.2
C2—N4—H4	114.5	C5—C6—H6	120.2
C5—N4—H4	114.3	C8—C7—C6	120.8 (3)
N2—C1—N1	119.0 (2)	C8—C7—H7	119.6
N2—C1—C2	120.2 (2)	C6—C7—H7	119.6
N1—C1—C2	120.8 (2)	C9—C8—C7	119.7 (3)
N3—C2—N4	121.6 (2)	C9—C8—H8	120.1
N3—C2—C1	121.5 (2)	C7—C8—H8	120.1
N4—C2—C1	116.92 (19)	C8—C9—C10	120.4 (3)
N3—C3—C4	123.6 (2)	C8—C9—H9	119.8
N3—C3—Br1	117.62 (16)	C10—C9—H9	119.8
C4—C3—Br1	118.81 (18)	C5—C10—C9	119.8 (3)
N2—C4—C3	121.2 (2)	C5—C10—H10	120.1
N2—C4—H4A	119.4	C9—C10—H10	120.1

C4—N2—C1—N1	178.7 (2)	N3—C3—C4—N2	0.3 (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—C1	2.3 (3)	C2—N4—C5—C6	123.5 (3)
C5—N4—C2—N3	−3.5 (4)	C10—C5—C6—C7	1.9 (4)
C5—N4—C2—C1	176.6 (2)	N4—C5—C6—C7	178.8 (2)
N2—C1—C2—N3	−0.9 (3)	C5—C6—C7—C8	0.1 (4)
N1—C1—C2—N3	179.4 (2)	C6—C7—C8—C9	−1.6 (5)
N2—C1—C2—N4	179.0 (2)	C7—C8—C9—C10	0.9 (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—Br1	176.66 (16)	C8—C9—C10—C5	1.2 (4)
C1—N2—C4—C3	1.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cg1ⁱ	0.86	2.63	3.436 (3)	157
N1—H1A···N2ⁱⁱ	0.86	2.22	3.084 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrN₄
M_r	265.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4834 (8), 15.4038 (17), 9.2079 (10)
β (°)	91.307 (2)
V (Å³)	1061.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.85
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.596, 0.700
No. of measured, independent and observed [I > 2σ(I)] reflections	5494, 1871, 1555
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.059, 1.00
No. of reflections	1871
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.33

Computer programs: SMART (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cg1ⁱ	0.86	2.63	3.436 (3)	157
N1—H1A···N2ⁱⁱ	0.86	2.22	3.084 (3)	169

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

References

Bruker (2005). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fors, B. P., Davis, N. R. & Buchwald, S. L. (2009). J. Am. Chem. Soc. 131, 5766–5768. Web of Science CrossRef PubMed CAS Google Scholar
Liu, Y. F., Bai, Y. J., Zhang, J., Li, Y. Y., Jiao, J. P. & Qi, X. L. (2007). Eur. J. Org. Chem., 6084–6088. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1968

doi:10.1107/S1600536809028554

Open

access