 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
access2-[(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
In the 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.
![[Scheme 1]](nc2103scheme1.gif)
Experimental
Crystal data
|
Refinement
|
| |||||||||||||||||
Data collection: SMART (Bruker, 1997![[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]](../../../../../../logos/arrows/e_arr.gif "Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.")
); cell SAINT (Bruker, 1997); 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: SHELXTL.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536808022058/nc2103sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808022058/nc2103Isup2.hkl
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.
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.
Data collection: SMART (Bruker, 1997); cell 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).
![[Figure 1]](./nc2103fig1thm.gif) | Fig. 1. The molecular structure of (I) with labelling and displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./nc2103fig2thm.gif) | Fig. 2. Crystal structure of the title compound, viewed along the c axis. Hydrogen bonding is shown as dashed lines. |
| C10H8BrN3O | F(000) = 528.0 |
| Mr = 266.09 | Dx = 1.757 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2721 reflections |
| a = 13.402 (3) Å | θ = 2.4–26.8° |
| b = 5.3016 (10) Å | µ = 4.06 mm−1 |
| c = 14.562 (3) Å | T = 298 K |
| β = 103.498 (3)° | Block, yellow |
| V = 1006.1 (4) Å3 | 0.52 × 0.13 × 0.11 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1850 independent reflections |
| Radiation source: sealed tube | 1263 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.049 |
| ϕ and ω scans | θmax = 25.5°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −16→15 |
| Tmin = 0.545, Tmax = 0.650 | k = −6→6 |
| 5867 measured reflections | l = −17→17 |
| 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.054 | H 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 parameters | Δρmax = 0.40 e Å−3 |
| 1 restraint | Δρmin = −0.28 e Å−3 |
| C10H8BrN3O | V = 1006.1 (4) Å3 |
| Mr = 266.09 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 13.402 (3) Å | µ = 4.06 mm−1 |
| b = 5.3016 (10) Å | T = 298 K |
| c = 14.562 (3) Å | 0.52 × 0.13 × 0.11 mm |
| β = 103.498 (3)° |
| 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 = 0.650 | Rint = 0.049 |
| 5867 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 1 restraint |
| wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.98 | Δρmax = 0.40 e Å−3 |
| 1850 reflections | Δρmin = −0.28 e Å−3 |
| 139 parameters |
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. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.92158 (2) | 1.17815 (7) | −0.12095 (2) | 0.06564 (15) | |
| C1 | 0.7817 (2) | 1.1290 (5) | −0.11489 (19) | 0.0432 (7) | |
| C2 | 0.7096 (2) | 1.2903 (6) | −0.1629 (2) | 0.0517 (8) | |
| H2 | 0.7262 | 1.4226 | −0.1986 | 0.062* | |
| C3 | 0.6096 (2) | 1.2463 (6) | −0.1558 (2) | 0.0539 (8) | |
| H3 | 0.5567 | 1.3500 | −0.1874 | 0.065* | |
| C4 | 0.5892 (2) | 1.0499 (5) | −0.1021 (2) | 0.0478 (7) | |
| H4 | 0.5224 | 1.0174 | −0.0973 | 0.057* | |
| C5 | 0.6696 (2) | 0.9003 (5) | −0.05497 (18) | 0.0387 (7) | |
| C6 | 0.7173 (2) | 0.5429 (5) | 0.05848 (18) | 0.0395 (7) | |
| C7 | 0.8226 (2) | 0.5275 (5) | 0.07141 (19) | 0.0475 (7) | |
| H7 | 0.8566 | 0.6394 | 0.0401 | 0.057* | |
| C8 | 0.8775 (2) | 0.3478 (6) | 0.1303 (2) | 0.0512 (8) | |
| H8 | 0.9484 | 0.3392 | 0.1390 | 0.061* | |
| C9 | 0.8273 (2) | 0.1797 (6) | 0.1766 (2) | 0.0510 (7) | |
| H9 | 0.8636 | 0.0556 | 0.2158 | 0.061* | |
| C10 | 0.7240 (2) | 0.1999 (6) | 0.1637 (2) | 0.0489 (7) | |
| H10 | 0.6898 | 0.0883 | 0.1950 | 0.059* | |
| H2A | 0.5830 (5) | 0.675 (5) | −0.0026 (18) | 0.059* | |
| N1 | 0.76650 (17) | 0.9372 (4) | −0.06143 (15) | 0.0429 (6) | |
| N2 | 0.65001 (17) | 0.7072 (4) | 0.00308 (17) | 0.0451 (6) | |
| N3 | 0.66939 (17) | 0.3773 (4) | 0.10671 (16) | 0.0426 (6) | |
| O1 | 0.57060 (15) | 0.3965 (4) | 0.09841 (14) | 0.0631 (6) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0485 (2) | 0.0779 (3) | 0.0748 (2) | −0.01014 (19) | 0.02297 (15) | 0.0068 (2) |
| C1 | 0.0412 (17) | 0.048 (2) | 0.0399 (17) | −0.0028 (14) | 0.0086 (13) | −0.0046 (15) |
| C2 | 0.052 (2) | 0.050 (2) | 0.0534 (19) | −0.0026 (16) | 0.0119 (15) | 0.0078 (16) |
| C3 | 0.053 (2) | 0.053 (2) | 0.0493 (19) | 0.0087 (15) | 0.0006 (15) | 0.0044 (15) |
| C4 | 0.0362 (17) | 0.0498 (19) | 0.0561 (19) | 0.0003 (15) | 0.0085 (14) | 0.0016 (16) |
| C5 | 0.0397 (17) | 0.0356 (18) | 0.0400 (16) | −0.0020 (13) | 0.0077 (13) | −0.0041 (13) |
| C6 | 0.0430 (17) | 0.0347 (17) | 0.0404 (16) | −0.0026 (14) | 0.0088 (13) | −0.0023 (14) |
| C7 | 0.0388 (17) | 0.0476 (19) | 0.0568 (19) | −0.0020 (14) | 0.0128 (14) | 0.0059 (16) |
| C8 | 0.0418 (17) | 0.053 (2) | 0.058 (2) | 0.0003 (16) | 0.0086 (14) | 0.0043 (18) |
| C9 | 0.052 (2) | 0.0442 (18) | 0.0530 (19) | 0.0030 (17) | 0.0042 (14) | 0.0027 (16) |
| C10 | 0.057 (2) | 0.0437 (19) | 0.0451 (18) | −0.0067 (17) | 0.0110 (14) | 0.0077 (16) |
| N1 | 0.0427 (15) | 0.0405 (15) | 0.0463 (15) | −0.0035 (11) | 0.0121 (11) | 0.0023 (12) |
| N2 | 0.0317 (13) | 0.0451 (15) | 0.0590 (15) | −0.0018 (12) | 0.0112 (11) | 0.0079 (13) |
| N3 | 0.0393 (15) | 0.0444 (16) | 0.0453 (14) | −0.0050 (12) | 0.0125 (11) | −0.0004 (12) |
| O1 | 0.0411 (13) | 0.0767 (17) | 0.0725 (15) | −0.0049 (11) | 0.0153 (11) | 0.0112 (11) |
| Br1—C1 | 1.916 (3) | C6—N3 | 1.374 (3) |
| C1—N1 | 1.325 (3) | C6—C7 | 1.382 (3) |
| C1—C2 | 1.356 (4) | C7—C8 | 1.374 (4) |
| C2—C3 | 1.388 (4) | C7—H7 | 0.9300 |
| C2—H2 | 0.9300 | C8—C9 | 1.383 (4) |
| C3—C4 | 1.367 (4) | C8—H8 | 0.9300 |
| C3—H3 | 0.9300 | C9—C10 | 1.357 (4) |
| C4—C5 | 1.384 (4) | C9—H9 | 0.9300 |
| C4—H4 | 0.9300 | C10—N3 | 1.351 (3) |
| C5—N1 | 1.338 (3) | C10—H10 | 0.9300 |
| C5—N2 | 1.391 (3) | N2—H2A | 0.899 (10) |
| C6—N2 | 1.372 (3) | N3—O1 | 1.305 (3) |
| N1—C1—C2 | 126.8 (3) | C8—C7—H7 | 119.8 |
| N1—C1—Br1 | 114.7 (2) | C6—C7—H7 | 119.8 |
| C2—C1—Br1 | 118.5 (2) | C7—C8—C9 | 120.1 (3) |
| C1—C2—C3 | 116.1 (3) | C7—C8—H8 | 120.0 |
| C1—C2—H2 | 122.0 | C9—C8—H8 | 120.0 |
| C3—C2—H2 | 122.0 | C10—C9—C8 | 118.5 (3) |
| C4—C3—C2 | 119.7 (3) | C10—C9—H9 | 120.7 |
| C4—C3—H3 | 120.1 | C8—C9—H9 | 120.7 |
| C2—C3—H3 | 120.1 | N3—C10—C9 | 121.9 (3) |
| C3—C4—C5 | 118.9 (3) | N3—C10—H10 | 119.0 |
| C3—C4—H4 | 120.5 | C9—C10—H10 | 119.0 |
| C5—C4—H4 | 120.5 | C1—N1—C5 | 116.0 (2) |
| N1—C5—C4 | 122.5 (3) | C6—N2—C5 | 129.2 (2) |
| N1—C5—N2 | 118.3 (2) | C6—N2—H2A | 116.1 (17) |
| C4—C5—N2 | 119.1 (3) | C5—N2—H2A | 114.2 (17) |
| N2—C6—N3 | 112.6 (2) | O1—N3—C10 | 120.2 (2) |
| N2—C6—C7 | 128.9 (3) | O1—N3—C6 | 119.2 (2) |
| N3—C6—C7 | 118.5 (3) | C10—N3—C6 | 120.5 (2) |
| C8—C7—C6 | 120.4 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1 | 0.90 (1) | 2.12 (2) | 2.542 (3) | 108 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C10H8BrN3O |
| Mr | 266.09 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 298 |
| a, b, c (Å) | 13.402 (3), 5.3016 (10), 14.562 (3) |
| β (°) | 103.498 (3) |
| V (Å3) | 1006.1 (4) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 4.06 |
| Crystal size (mm) | 0.52 × 0.13 × 0.11 |
| Data collection | |
| Diffractometer | Bruker SMART CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
| Tmin, Tmax | 0.545, 0.650 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5867, 1850, 1263 |
| Rint | 0.049 |
| (sin θ/λ)max (Å−1) | 0.606 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.054, 0.98 |
| No. of reflections | 1850 |
| No. of parameters | 139 |
| No. of restraints | 1 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.40, −0.28 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···O1 | 0.899 (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
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liu, Y.-Q. & Wen, H.-R. (2007). Acta Cryst. E63, o4690. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, J. (2007). Acta Cryst. E63, o4413. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
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.