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Crystal structure of 3-bromo­pyridine N-oxide

aDepartment of Chemistry and Physics, Armstrong State University, Savannah, GA 31419, USA
*Correspondence e-mail: clifford.padgett@armstrong.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 23 September 2015; accepted 9 October 2015; online 24 October 2015)

In the title compound, C5H4BrNO, there are two mol­ecules in the asymmetric unit that are related by a pseudo-inversion center. The two independent mol­ecules are approximately planar, with an observed (ring–ring) angle of 5.49 (13)°. The crystal structure exhibits a herringbone pattern with the zigzag running along the b-axis direction. The least-squares plane containing the rings of both asymmetric molecules and the plane containing the symmetrically related mol­ecules make a plane–plane angle of 66.69 (10)°, which makes the bend of the herringbone pattern. The bromo group on one mol­ecule points to the bromo group on the neighboring mol­ecule, with a Br⋯Br inter­molecular distance of 4.0408 (16) Å. The herringbone layer-to-layer distance is 3.431 (4) Å with a shift of 1.742 (7) Å. There are no short contacts, hydrogen bonds, or ππ inter­actions.

1. Related literature

For the synthesis of pyridine N-oxide-related compounds, see: Rousseau & Robins (1965[Rousseau, R. J. & Robins, R. K. (1965). J. Heterocycl. Chem. 2, 196-201.]). For an example of the chemistry of the title compound and its use in catalysed cyclization of alkynyl oxiranes and oxetanes, see: Gronnier et al. (2012[Gronnier, C., Kramer, S., Odabachian, Y. & Gagosz, F. (2012). J. Am. Chem. Soc. 134, 828-831.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C5H4BrNO

  • Mr = 174.00

  • Monoclinic, P 21 /n

  • a = 7.832 (5) Å

  • b = 18.398 (10) Å

  • c = 8.298 (5) Å

  • β = 92.906 (5)°

  • V = 1194.2 (12) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 6.77 mm−1

  • T = 173 K

  • 0.3 × 0.3 × 0.2 mm

2.2. Data collection

  • Rigaku XtaLAB mini diffractometer

  • Absorption correction: multi-scan (REQAB; Rigaku, 1998[Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.189, Tmax = 0.257

  • 12561 measured reflections

  • 2732 independent reflections

  • 1881 reflections with I > 2σ(I)

  • Rint = 0.056

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.092

  • S = 1.09

  • 2732 reflections

  • 146 parameters

  • H-atom parameters constrained

  • Δρmax = 0.50 e Å−3

  • Δρmin = −0.67 e Å−3

Data collection: CrystalClear-SM Expert (Rigaku, 2011[Rigaku (2011). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]); molecular graphics: OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]); software used to prepare material for publication: OLEX2.

Supporting information


Structural commentary top

Details of the synthesis pyridine N-oxide related compounds appears in the literature Rousseau & Robins (1965). The title compound is used in the catalyzed cyclization of alkynyl oxiranes and oxetanes Gronnier, et al. (2012). The asymmetric unit of the title compound is shown in Fig. 1. There are two molecules in the asymmetric unit that are related by a pseudo-inversion center. The inversion symmetry is broken by the nonplanar arrangement of the two molecules. The two independent molecules are found to be nearly planar with an observed twist angle of 5.49 (13)° and a fold angle of 1.40 (13)°. The distance between O2···Br1 is 4.307 (3) Å and the distance between O1···Br2 is 4.196 (3) Å. The structure exhibits a herringbone pattern with the zigzag running along the b axis. The least-squares plane containing both rings of the asymmetric unit and the plane containing the symmetrically-related molecules have a plane-plane angle of 66.69 (10)°, which makes the bend of the herringbone pattern. The bromo group on one molecule points to the bromo group on the neighboring molecule with the Br1···Br2 inter­molecular distance at 4.0408 (16) Å. The herringbone layer-to-layer distance is 3.431 (4) Å with a shift of 1.742 (7) Å.

Synthesis and crystallization top

3-Bromo­pyridine N-oxide was purchased from Sigma-Aldrich and 0.10 g was dissolved in approximately 50 mL of methanol. Diffraction quality crystals were obtained by slow evaporation of the solvent.

Refinement top

H atoms were placed in calculated positions with C–H = 0.93Å and Uiso(H) = 1.2Ueq(C).

Related literature top

For the synthesis of pyridine N-oxide-related compounds, see: Rousseau & Robins (1965). For an example of the chemistry of the title compound and its use in catalysed cyclization of alkynyl oxiranes and oxetanes, see: Gronnier et al. (2012).

Structure description top

Details of the synthesis pyridine N-oxide related compounds appears in the literature Rousseau & Robins (1965). The title compound is used in the catalyzed cyclization of alkynyl oxiranes and oxetanes Gronnier, et al. (2012). The asymmetric unit of the title compound is shown in Fig. 1. There are two molecules in the asymmetric unit that are related by a pseudo-inversion center. The inversion symmetry is broken by the nonplanar arrangement of the two molecules. The two independent molecules are found to be nearly planar with an observed twist angle of 5.49 (13)° and a fold angle of 1.40 (13)°. The distance between O2···Br1 is 4.307 (3) Å and the distance between O1···Br2 is 4.196 (3) Å. The structure exhibits a herringbone pattern with the zigzag running along the b axis. The least-squares plane containing both rings of the asymmetric unit and the plane containing the symmetrically-related molecules have a plane-plane angle of 66.69 (10)°, which makes the bend of the herringbone pattern. The bromo group on one molecule points to the bromo group on the neighboring molecule with the Br1···Br2 inter­molecular distance at 4.0408 (16) Å. The herringbone layer-to-layer distance is 3.431 (4) Å with a shift of 1.742 (7) Å.

For the synthesis of pyridine N-oxide-related compounds, see: Rousseau & Robins (1965). For an example of the chemistry of the title compound and its use in catalysed cyclization of alkynyl oxiranes and oxetanes, see: Gronnier et al. (2012).

Synthesis and crystallization top

3-Bromo­pyridine N-oxide was purchased from Sigma-Aldrich and 0.10 g was dissolved in approximately 50 mL of methanol. Diffraction quality crystals were obtained by slow evaporation of the solvent.

Refinement details top

H atoms were placed in calculated positions with C–H = 0.93Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
3-Bromopyridine N-oxide top
Crystal data top
C5H4BrNOF(000) = 672
Mr = 174.00Dx = 1.936 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.832 (5) ÅCell parameters from 2269 reflections
b = 18.398 (10) Åθ = 1.6–27.4°
c = 8.298 (5) ŵ = 6.77 mm1
β = 92.906 (5)°T = 173 K
V = 1194.2 (12) Å3Prism, colorless
Z = 80.3 × 0.3 × 0.2 mm
Data collection top
Rigaku XtaLAB mini
diffractometer
2732 independent reflections
Radiation source: Sealed Tube1881 reflections with I > 2σ(I)
Graphite Monochromator monochromatorRint = 0.056
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 2.7°
ω scansh = 1010
Absorption correction: multi-scan
(REQAB; Rigaku, 1998)
k = 2323
Tmin = 0.189, Tmax = 0.257l = 1010
12561 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041 w = 1/[σ2(Fo2) + (0.0225P)2 + 1.184P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.092(Δ/σ)max < 0.001
S = 1.09Δρmax = 0.50 e Å3
2732 reflectionsΔρmin = 0.67 e Å3
146 parametersExtinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0059 (6)
Primary atom site location: structure-invariant direct methods
Crystal data top
C5H4BrNOV = 1194.2 (12) Å3
Mr = 174.00Z = 8
Monoclinic, P21/nMo Kα radiation
a = 7.832 (5) ŵ = 6.77 mm1
b = 18.398 (10) ÅT = 173 K
c = 8.298 (5) Å0.3 × 0.3 × 0.2 mm
β = 92.906 (5)°
Data collection top
Rigaku XtaLAB mini
diffractometer
2732 independent reflections
Absorption correction: multi-scan
(REQAB; Rigaku, 1998)
1881 reflections with I > 2σ(I)
Tmin = 0.189, Tmax = 0.257Rint = 0.056
12561 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 1.09Δρmax = 0.50 e Å3
2732 reflectionsΔρmin = 0.67 e Å3
146 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br20.67164 (6)0.60185 (3)0.12441 (6)0.0635 (2)
Br10.49425 (6)0.20942 (3)0.64430 (6)0.0639 (2)
O20.3319 (3)0.40963 (15)0.4152 (4)0.0529 (8)
N20.3246 (4)0.46580 (17)0.3178 (4)0.0405 (7)
O10.8214 (4)0.41613 (18)0.3888 (4)0.0688 (10)
N10.8315 (4)0.36058 (18)0.4861 (4)0.0458 (8)
C60.4715 (5)0.4993 (2)0.2786 (4)0.0399 (9)
H60.57650.48320.32220.048*
C20.6948 (5)0.2634 (2)0.6143 (4)0.0423 (9)
C10.6861 (5)0.3230 (2)0.5159 (5)0.0439 (9)
H10.58140.33800.46940.053*
C70.4632 (5)0.5572 (2)0.1741 (5)0.0419 (9)
C30.8487 (6)0.2403 (2)0.6878 (5)0.0494 (10)
H30.85480.19970.75470.059*
C100.1717 (5)0.4901 (2)0.2572 (5)0.0473 (10)
H100.07130.46810.28730.057*
C50.9832 (5)0.3399 (2)0.5567 (5)0.0500 (10)
H51.08180.36590.53720.060*
C40.9919 (5)0.2807 (2)0.6567 (5)0.0519 (11)
H41.09700.26730.70490.062*
C80.3107 (5)0.5830 (2)0.1079 (5)0.0525 (11)
H80.30620.62230.03750.063*
C90.1645 (5)0.5475 (3)0.1510 (5)0.0571 (12)
H90.05890.56280.10730.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br20.0504 (3)0.0630 (3)0.0777 (4)0.0142 (2)0.0089 (2)0.0102 (2)
Br10.0534 (3)0.0706 (4)0.0674 (3)0.0198 (2)0.0011 (2)0.0044 (2)
O20.0458 (17)0.0450 (17)0.0679 (19)0.0009 (13)0.0033 (15)0.0144 (14)
N20.0385 (19)0.0358 (18)0.0471 (18)0.0008 (14)0.0014 (15)0.0007 (14)
O10.0456 (19)0.072 (2)0.089 (2)0.0061 (15)0.0075 (17)0.0410 (18)
N10.0341 (18)0.049 (2)0.055 (2)0.0025 (15)0.0058 (16)0.0087 (17)
C60.030 (2)0.044 (2)0.046 (2)0.0008 (16)0.0014 (17)0.0017 (17)
C20.039 (2)0.047 (2)0.041 (2)0.0045 (18)0.0027 (18)0.0059 (18)
C10.034 (2)0.052 (3)0.046 (2)0.0011 (18)0.0014 (17)0.0006 (19)
C70.039 (2)0.040 (2)0.047 (2)0.0015 (17)0.0039 (18)0.0035 (18)
C30.053 (3)0.046 (2)0.048 (2)0.002 (2)0.009 (2)0.0049 (19)
C100.028 (2)0.054 (3)0.060 (3)0.0035 (18)0.0047 (19)0.001 (2)
C50.030 (2)0.061 (3)0.059 (3)0.0003 (19)0.0000 (19)0.006 (2)
C40.041 (2)0.055 (3)0.058 (3)0.006 (2)0.008 (2)0.001 (2)
C80.046 (3)0.052 (3)0.059 (3)0.010 (2)0.003 (2)0.018 (2)
C90.039 (2)0.064 (3)0.067 (3)0.014 (2)0.006 (2)0.004 (2)
Geometric parameters (Å, º) top
Br2—C71.892 (4)C1—H10.9300
Br1—C21.885 (4)C7—C81.373 (5)
O2—N21.312 (4)C3—H30.9300
N2—C61.359 (5)C3—C41.381 (6)
N2—C101.351 (5)C10—H100.9300
O1—N11.302 (4)C10—C91.374 (6)
N1—C11.365 (5)C5—H50.9300
N1—C51.352 (5)C5—C41.369 (6)
C6—H60.9300C4—H40.9300
C6—C71.373 (5)C8—H80.9300
C2—C11.367 (5)C8—C91.380 (6)
C2—C31.390 (5)C9—H90.9300
O2—N2—C6119.6 (3)C2—C3—H3121.7
O2—N2—C10120.0 (3)C4—C3—C2116.7 (4)
C10—N2—C6120.4 (3)C4—C3—H3121.7
O1—N1—C1119.0 (3)N2—C10—H10120.0
O1—N1—C5120.9 (3)N2—C10—C9120.0 (4)
C5—N1—C1120.1 (3)C9—C10—H10120.0
N2—C6—H6120.4N1—C5—H5119.9
N2—C6—C7119.2 (3)N1—C5—C4120.2 (4)
C7—C6—H6120.4C4—C5—H5119.9
C1—C2—Br1119.0 (3)C3—C4—H4119.2
C1—C2—C3121.5 (4)C5—C4—C3121.7 (4)
C3—C2—Br1119.4 (3)C5—C4—H4119.2
N1—C1—C2119.9 (4)C7—C8—H8121.7
N1—C1—H1120.1C7—C8—C9116.7 (4)
C2—C1—H1120.1C9—C8—H8121.7
C6—C7—Br2117.4 (3)C10—C9—C8121.4 (4)
C6—C7—C8122.3 (4)C10—C9—H9119.3
C8—C7—Br2120.3 (3)C8—C9—H9119.3
Br2—C7—C8—C9179.7 (3)N1—C5—C4—C30.4 (7)
Br1—C2—C1—N1176.6 (3)C6—N2—C10—C92.2 (6)
Br1—C2—C3—C4177.8 (3)C6—C7—C8—C90.3 (6)
O2—N2—C6—C7178.8 (3)C2—C3—C4—C50.8 (6)
O2—N2—C10—C9177.9 (4)C1—N1—C5—C40.8 (6)
N2—C6—C7—Br2179.8 (3)C1—C2—C3—C40.1 (6)
N2—C6—C7—C80.4 (6)C7—C8—C9—C101.1 (7)
N2—C10—C9—C82.1 (7)C3—C2—C1—N11.1 (6)
O1—N1—C1—C2178.3 (4)C10—N2—C6—C71.4 (5)
O1—N1—C5—C4179.0 (4)C5—N1—C1—C21.6 (6)

Experimental details

Crystal data
Chemical formulaC5H4BrNO
Mr174.00
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)7.832 (5), 18.398 (10), 8.298 (5)
β (°) 92.906 (5)
V3)1194.2 (12)
Z8
Radiation typeMo Kα
µ (mm1)6.77
Crystal size (mm)0.3 × 0.3 × 0.2
Data collection
DiffractometerRigaku XtaLAB mini
Absorption correctionMulti-scan
(REQAB; Rigaku, 1998)
Tmin, Tmax0.189, 0.257
No. of measured, independent and
observed [I > 2σ(I)] reflections
12561, 2732, 1881
Rint0.056
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.092, 1.09
No. of reflections2732
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.50, 0.67

Computer programs: CrystalClear-SM Expert (Rigaku, 2011), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009).

 

Acknowledgements

The authors acknowledge financial support from Armstrong State University.

References

First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationGronnier, C., Kramer, S., Odabachian, Y. & Gagosz, F. (2012). J. Am. Chem. Soc. 134, 828–831.  CrossRef CAS PubMed Google Scholar
First citationRigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (2011). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRousseau, R. J. & Robins, R. K. (1965). J. Heterocycl. Chem. 2, 196–201.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

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