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ISSN: 2056-9890

2-[(6-Bromo-2-pyrid­yl)amino]pyridine N-oxide

aZhejiang Hisun Pharmaceutical Co. Ltd, JiangXi Province Key Laboratory of Coordination Chemistry, 343009 Ji'an, JiangXi, People's Republic of China, and bCollege of Chemistry and Chemical Engineering, JiangXi Province Key Laboratory of Coordination Chemistry, JingGangShan University, 343009 Ji'an, JiangXi, People's Republic of China
*Correspondence e-mail: xiruizeng@hotmail.com

(Received 25 April 2008; accepted 15 July 2008; online 19 July 2008)

In the crystal structure of the title compound, C10H8BrN3O, the dihedral angle between the two pyridine rings is 2.48 (2)°. A weak intramolecular N—H⋯O hydrogen bond is present.

Related literature

For similar structures, see: Wu (2007[Wu, J. (2007). Acta Cryst. E63, o4413.]); Liu & Wen (2007[Liu, Y.-Q. & Wen, H.-R. (2007). Acta Cryst. E63, o4690.]).

[Scheme 1]

Experimental

Crystal data
  • C10H8BrN3O

  • Mr = 266.09

  • Monoclinic, P 21 /n

  • a = 13.402 (3) Å

  • b = 5.3016 (10) Å

  • c = 14.562 (3) Å

  • β = 103.498 (3)°

  • V = 1006.1 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 4.06 mm−1

  • T = 298 (2) K

  • 0.52 × 0.13 × 0.11 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.545, Tmax = 0.650

  • 5867 measured reflections

  • 1850 independent reflections

  • 1263 reflections with I > 2σ(I)

  • Rint = 0.049

Refinement
  • R[F2 > 2σ(F2)] = 0.029

  • wR(F2) = 0.054

  • S = 0.98

  • 1850 reflections

  • 139 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.40 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯O1 0.899 (10) 2.12 (2) 2.542 (3) 107.8 (19)

Data collection: SMART (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The structure determination was performed as a part of a project on the synthesis, structures and properties of new polypyridylamine N-oxides. In the crystal structure both pyridine rings are nearly coplanar with an dihedral angle of 2.48 (2) /%. The molecules are connected into dimers via intermolecular N-H···O hydrogen bonding and the dimers are stacked in the direction of the crystallographic b-axis in a sandwich-herringbone structure.

Related literature top

For a similar structure, see: Liu et al. (2007).

Experimental top

A mixture of 2.56 g 6-bromo-N-(pyridin-2-yl)pyridin-2-amine (0.01 mol), 8 ml of H2O2(30%), 8 ml of acetic acid and 30 ml of methanol were heated under reflux for about six hours. Afterwards the methanol was removed under reduced pressure. The crude yellow coloured product was recrystallized from methanol.

Refinement top

The C-H H atoms were positioned with idealized geometry and refined isotropic with C-H = 0.93Å and Uiso(H) = 1.2 times Ueq(C); The H atoms of the amino groups was located in difference map and was refined isotropic with Uiso(H)= 1.2 times Ueq(N) and a N-H distance restrained to 0.90 Å.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with labelling and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal structure of the title compound, viewed along the c axis. Hydrogen bonding is shown as dashed lines.
2-[(6-Bromo-2-pyridyl)amino]pyridine N-oxide top
Crystal data top
C10H8BrN3OF(000) = 528.0
Mr = 266.09Dx = 1.757 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2721 reflections
a = 13.402 (3) Åθ = 2.4–26.8°
b = 5.3016 (10) ŵ = 4.06 mm1
c = 14.562 (3) ÅT = 298 K
β = 103.498 (3)°Block, yellow
V = 1006.1 (4) Å30.52 × 0.13 × 0.11 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
1850 independent reflections
Radiation source: sealed tube1263 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ϕ and ω scansθmax = 25.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1615
Tmin = 0.545, Tmax = 0.650k = 66
5867 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0029P)2 + 0.3286P]
where P = (Fo2 + 2Fc2)/3
1850 reflections(Δ/σ)max = 0.001
139 parametersΔρmax = 0.40 e Å3
1 restraintΔρmin = 0.28 e Å3
Crystal data top
C10H8BrN3OV = 1006.1 (4) Å3
Mr = 266.09Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.402 (3) ŵ = 4.06 mm1
b = 5.3016 (10) ÅT = 298 K
c = 14.562 (3) Å0.52 × 0.13 × 0.11 mm
β = 103.498 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1850 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1263 reflections with I > 2σ(I)
Tmin = 0.545, Tmax = 0.650Rint = 0.049
5867 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0291 restraint
wR(F2) = 0.054H atoms treated by a mixture of independent and constrained refinement
S = 0.98Δρmax = 0.40 e Å3
1850 reflectionsΔρmin = 0.28 e Å3
139 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
xyzUiso*/Ueq
Br10.92158 (2)1.17815 (7)0.12095 (2)0.06564 (15)
C10.7817 (2)1.1290 (5)0.11489 (19)0.0432 (7)
C20.7096 (2)1.2903 (6)0.1629 (2)0.0517 (8)
H20.72621.42260.19860.062*
C30.6096 (2)1.2463 (6)0.1558 (2)0.0539 (8)
H30.55671.35000.18740.065*
C40.5892 (2)1.0499 (5)0.1021 (2)0.0478 (7)
H40.52241.01740.09730.057*
C50.6696 (2)0.9003 (5)0.05497 (18)0.0387 (7)
C60.7173 (2)0.5429 (5)0.05848 (18)0.0395 (7)
C70.8226 (2)0.5275 (5)0.07141 (19)0.0475 (7)
H70.85660.63940.04010.057*
C80.8775 (2)0.3478 (6)0.1303 (2)0.0512 (8)
H80.94840.33920.13900.061*
C90.8273 (2)0.1797 (6)0.1766 (2)0.0510 (7)
H90.86360.05560.21580.061*
C100.7240 (2)0.1999 (6)0.1637 (2)0.0489 (7)
H100.68980.08830.19500.059*
H2A0.5830 (5)0.675 (5)0.0026 (18)0.059*
N10.76650 (17)0.9372 (4)0.06143 (15)0.0429 (6)
N20.65001 (17)0.7072 (4)0.00308 (17)0.0451 (6)
N30.66939 (17)0.3773 (4)0.10671 (16)0.0426 (6)
O10.57060 (15)0.3965 (4)0.09841 (14)0.0631 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0485 (2)0.0779 (3)0.0748 (2)0.01014 (19)0.02297 (15)0.0068 (2)
C10.0412 (17)0.048 (2)0.0399 (17)0.0028 (14)0.0086 (13)0.0046 (15)
C20.052 (2)0.050 (2)0.0534 (19)0.0026 (16)0.0119 (15)0.0078 (16)
C30.053 (2)0.053 (2)0.0493 (19)0.0087 (15)0.0006 (15)0.0044 (15)
C40.0362 (17)0.0498 (19)0.0561 (19)0.0003 (15)0.0085 (14)0.0016 (16)
C50.0397 (17)0.0356 (18)0.0400 (16)0.0020 (13)0.0077 (13)0.0041 (13)
C60.0430 (17)0.0347 (17)0.0404 (16)0.0026 (14)0.0088 (13)0.0023 (14)
C70.0388 (17)0.0476 (19)0.0568 (19)0.0020 (14)0.0128 (14)0.0059 (16)
C80.0418 (17)0.053 (2)0.058 (2)0.0003 (16)0.0086 (14)0.0043 (18)
C90.052 (2)0.0442 (18)0.0530 (19)0.0030 (17)0.0042 (14)0.0027 (16)
C100.057 (2)0.0437 (19)0.0451 (18)0.0067 (17)0.0110 (14)0.0077 (16)
N10.0427 (15)0.0405 (15)0.0463 (15)0.0035 (11)0.0121 (11)0.0023 (12)
N20.0317 (13)0.0451 (15)0.0590 (15)0.0018 (12)0.0112 (11)0.0079 (13)
N30.0393 (15)0.0444 (16)0.0453 (14)0.0050 (12)0.0125 (11)0.0004 (12)
O10.0411 (13)0.0767 (17)0.0725 (15)0.0049 (11)0.0153 (11)0.0112 (11)
Geometric parameters (Å, º) top
Br1—C11.916 (3)C6—N31.374 (3)
C1—N11.325 (3)C6—C71.382 (3)
C1—C21.356 (4)C7—C81.374 (4)
C2—C31.388 (4)C7—H70.9300
C2—H20.9300C8—C91.383 (4)
C3—C41.367 (4)C8—H80.9300
C3—H30.9300C9—C101.357 (4)
C4—C51.384 (4)C9—H90.9300
C4—H40.9300C10—N31.351 (3)
C5—N11.338 (3)C10—H100.9300
C5—N21.391 (3)N2—H2A0.899 (10)
C6—N21.372 (3)N3—O11.305 (3)
N1—C1—C2126.8 (3)C8—C7—H7119.8
N1—C1—Br1114.7 (2)C6—C7—H7119.8
C2—C1—Br1118.5 (2)C7—C8—C9120.1 (3)
C1—C2—C3116.1 (3)C7—C8—H8120.0
C1—C2—H2122.0C9—C8—H8120.0
C3—C2—H2122.0C10—C9—C8118.5 (3)
C4—C3—C2119.7 (3)C10—C9—H9120.7
C4—C3—H3120.1C8—C9—H9120.7
C2—C3—H3120.1N3—C10—C9121.9 (3)
C3—C4—C5118.9 (3)N3—C10—H10119.0
C3—C4—H4120.5C9—C10—H10119.0
C5—C4—H4120.5C1—N1—C5116.0 (2)
N1—C5—C4122.5 (3)C6—N2—C5129.2 (2)
N1—C5—N2118.3 (2)C6—N2—H2A116.1 (17)
C4—C5—N2119.1 (3)C5—N2—H2A114.2 (17)
N2—C6—N3112.6 (2)O1—N3—C10120.2 (2)
N2—C6—C7128.9 (3)O1—N3—C6119.2 (2)
N3—C6—C7118.5 (3)C10—N3—C6120.5 (2)
C8—C7—C6120.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.90 (1)2.12 (2)2.542 (3)108 (2)

Experimental details

Crystal data
Chemical formulaC10H8BrN3O
Mr266.09
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)13.402 (3), 5.3016 (10), 14.562 (3)
β (°) 103.498 (3)
V3)1006.1 (4)
Z4
Radiation typeMo Kα
µ (mm1)4.06
Crystal size (mm)0.52 × 0.13 × 0.11
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.545, 0.650
No. of measured, independent and
observed [I > 2σ(I)] reflections
5867, 1850, 1263
Rint0.049
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.054, 0.98
No. of reflections1850
No. of parameters139
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.40, 0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O10.899 (10)2.12 (2)2.542 (3)107.8 (19)
 

Acknowledgements

The authors are grateful for support from the Key Laboratory of Coordination Chemistry, JingGangShan University, China

References

First citationBruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationLiu, Y.-Q. & Wen, H.-R. (2007). Acta Cryst. E63, o4690.  Web of Science CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWu, J. (2007). Acta Cryst. E63, o4413.  Web of Science CSD CrossRef IUCr Journals

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
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