organic compounds
N-oxide
of 3-bromopyridineaDepartment of Chemistry and Physics, Armstrong State University, Savannah, GA 31419, USA
*Correspondence e-mail: clifford.padgett@armstrong.edu
In the title compound, C5H4BrNO, there are two molecules in the 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 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 π–π interactions.
Keywords: crystal structure; 3-bromopyridine N-oxide; herringbone pattern.
CCDC reference: 1430552
1. Related literature
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 of alkynyl oxiranes and oxetanes, see: Gronnier et al. (2012).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; 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.
Supporting information
CCDC reference: 1430552
https://doi.org/10.1107/S205698901501909X/lh5792sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901501909X/lh5792Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698901501909X/lh5792Isup3.cml
Details of the synthesis pyridine N-oxide related compounds appears in the literature Rousseau & Robins (1965). The title compound is used in the catalyzed
of alkynyl oxiranes and oxetanes Gronnier, et al. (2012). The of the title compound is shown in Fig. 1. There are two molecules in the 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 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.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.
Details of the synthesis pyridine N-oxide related compounds appears in the literature Rousseau & Robins (1965). The title compound is used in the catalyzed
of alkynyl oxiranes and oxetanes Gronnier, et al. (2012). The of the title compound is shown in Fig. 1. There are two molecules in the 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 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
of alkynyl oxiranes and oxetanes, see: Gronnier et al. (2012).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.
detailsH atoms were placed in calculated positions with C–H = 0.93Å and Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear-SM Expert (Rigaku, 2011); cell
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).Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. |
C5H4BrNO | F(000) = 672 |
Mr = 174.00 | Dx = 1.936 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.832 (5) Å | Cell parameters from 2269 reflections |
b = 18.398 (10) Å | θ = 1.6–27.4° |
c = 8.298 (5) Å | µ = 6.77 mm−1 |
β = 92.906 (5)° | T = 173 K |
V = 1194.2 (12) Å3 | Prism, colorless |
Z = 8 | 0.3 × 0.3 × 0.2 mm |
Rigaku XtaLAB mini diffractometer | 2732 independent reflections |
Radiation source: Sealed Tube | 1881 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.056 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 2.7° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | k = −23→23 |
Tmin = 0.189, Tmax = 0.257 | l = −10→10 |
12561 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.09 | Δρmax = 0.50 e Å−3 |
2732 reflections | Δρmin = −0.67 e Å−3 |
146 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0059 (6) |
Primary atom site location: structure-invariant direct methods |
C5H4BrNO | V = 1194.2 (12) Å3 |
Mr = 174.00 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.832 (5) Å | µ = 6.77 mm−1 |
b = 18.398 (10) Å | T = 173 K |
c = 8.298 (5) Å | 0.3 × 0.3 × 0.2 mm |
β = 92.906 (5)° |
Rigaku XtaLAB mini diffractometer | 2732 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku, 1998) | 1881 reflections with I > 2σ(I) |
Tmin = 0.189, Tmax = 0.257 | Rint = 0.056 |
12561 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.50 e Å−3 |
2732 reflections | Δρmin = −0.67 e Å−3 |
146 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. |
x | y | z | Uiso*/Ueq | ||
Br2 | 0.67164 (6) | 0.60185 (3) | 0.12441 (6) | 0.0635 (2) | |
Br1 | 0.49425 (6) | 0.20942 (3) | 0.64430 (6) | 0.0639 (2) | |
O2 | 0.3319 (3) | 0.40963 (15) | 0.4152 (4) | 0.0529 (8) | |
N2 | 0.3246 (4) | 0.46580 (17) | 0.3178 (4) | 0.0405 (7) | |
O1 | 0.8214 (4) | 0.41613 (18) | 0.3888 (4) | 0.0688 (10) | |
N1 | 0.8315 (4) | 0.36058 (18) | 0.4861 (4) | 0.0458 (8) | |
C6 | 0.4715 (5) | 0.4993 (2) | 0.2786 (4) | 0.0399 (9) | |
H6 | 0.5765 | 0.4832 | 0.3222 | 0.048* | |
C2 | 0.6948 (5) | 0.2634 (2) | 0.6143 (4) | 0.0423 (9) | |
C1 | 0.6861 (5) | 0.3230 (2) | 0.5159 (5) | 0.0439 (9) | |
H1 | 0.5814 | 0.3380 | 0.4694 | 0.053* | |
C7 | 0.4632 (5) | 0.5572 (2) | 0.1741 (5) | 0.0419 (9) | |
C3 | 0.8487 (6) | 0.2403 (2) | 0.6878 (5) | 0.0494 (10) | |
H3 | 0.8548 | 0.1997 | 0.7547 | 0.059* | |
C10 | 0.1717 (5) | 0.4901 (2) | 0.2572 (5) | 0.0473 (10) | |
H10 | 0.0713 | 0.4681 | 0.2873 | 0.057* | |
C5 | 0.9832 (5) | 0.3399 (2) | 0.5567 (5) | 0.0500 (10) | |
H5 | 1.0818 | 0.3659 | 0.5372 | 0.060* | |
C4 | 0.9919 (5) | 0.2807 (2) | 0.6567 (5) | 0.0519 (11) | |
H4 | 1.0970 | 0.2673 | 0.7049 | 0.062* | |
C8 | 0.3107 (5) | 0.5830 (2) | 0.1079 (5) | 0.0525 (11) | |
H8 | 0.3062 | 0.6223 | 0.0375 | 0.063* | |
C9 | 0.1645 (5) | 0.5475 (3) | 0.1510 (5) | 0.0571 (12) | |
H9 | 0.0589 | 0.5628 | 0.1073 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br2 | 0.0504 (3) | 0.0630 (3) | 0.0777 (4) | −0.0142 (2) | 0.0089 (2) | 0.0102 (2) |
Br1 | 0.0534 (3) | 0.0706 (4) | 0.0674 (3) | −0.0198 (2) | 0.0011 (2) | 0.0044 (2) |
O2 | 0.0458 (17) | 0.0450 (17) | 0.0679 (19) | −0.0009 (13) | 0.0033 (15) | 0.0144 (14) |
N2 | 0.0385 (19) | 0.0358 (18) | 0.0471 (18) | 0.0008 (14) | 0.0014 (15) | 0.0007 (14) |
O1 | 0.0456 (19) | 0.072 (2) | 0.089 (2) | 0.0061 (15) | 0.0075 (17) | 0.0410 (18) |
N1 | 0.0341 (18) | 0.049 (2) | 0.055 (2) | 0.0025 (15) | 0.0058 (16) | 0.0087 (17) |
C6 | 0.030 (2) | 0.044 (2) | 0.046 (2) | −0.0008 (16) | −0.0014 (17) | −0.0017 (17) |
C2 | 0.039 (2) | 0.047 (2) | 0.041 (2) | −0.0045 (18) | 0.0027 (18) | −0.0059 (18) |
C1 | 0.034 (2) | 0.052 (3) | 0.046 (2) | 0.0011 (18) | −0.0014 (17) | −0.0006 (19) |
C7 | 0.039 (2) | 0.040 (2) | 0.047 (2) | −0.0015 (17) | 0.0039 (18) | −0.0035 (18) |
C3 | 0.053 (3) | 0.046 (2) | 0.048 (2) | −0.002 (2) | −0.009 (2) | 0.0049 (19) |
C10 | 0.028 (2) | 0.054 (3) | 0.060 (3) | 0.0035 (18) | 0.0047 (19) | 0.001 (2) |
C5 | 0.030 (2) | 0.061 (3) | 0.059 (3) | 0.0003 (19) | 0.0000 (19) | 0.006 (2) |
C4 | 0.041 (2) | 0.055 (3) | 0.058 (3) | 0.006 (2) | −0.008 (2) | 0.001 (2) |
C8 | 0.046 (3) | 0.052 (3) | 0.059 (3) | 0.010 (2) | 0.003 (2) | 0.018 (2) |
C9 | 0.039 (2) | 0.064 (3) | 0.067 (3) | 0.014 (2) | −0.006 (2) | 0.004 (2) |
Br2—C7 | 1.892 (4) | C1—H1 | 0.9300 |
Br1—C2 | 1.885 (4) | C7—C8 | 1.373 (5) |
O2—N2 | 1.312 (4) | C3—H3 | 0.9300 |
N2—C6 | 1.359 (5) | C3—C4 | 1.381 (6) |
N2—C10 | 1.351 (5) | C10—H10 | 0.9300 |
O1—N1 | 1.302 (4) | C10—C9 | 1.374 (6) |
N1—C1 | 1.365 (5) | C5—H5 | 0.9300 |
N1—C5 | 1.352 (5) | C5—C4 | 1.369 (6) |
C6—H6 | 0.9300 | C4—H4 | 0.9300 |
C6—C7 | 1.373 (5) | C8—H8 | 0.9300 |
C2—C1 | 1.367 (5) | C8—C9 | 1.380 (6) |
C2—C3 | 1.390 (5) | C9—H9 | 0.9300 |
O2—N2—C6 | 119.6 (3) | C2—C3—H3 | 121.7 |
O2—N2—C10 | 120.0 (3) | C4—C3—C2 | 116.7 (4) |
C10—N2—C6 | 120.4 (3) | C4—C3—H3 | 121.7 |
O1—N1—C1 | 119.0 (3) | N2—C10—H10 | 120.0 |
O1—N1—C5 | 120.9 (3) | N2—C10—C9 | 120.0 (4) |
C5—N1—C1 | 120.1 (3) | C9—C10—H10 | 120.0 |
N2—C6—H6 | 120.4 | N1—C5—H5 | 119.9 |
N2—C6—C7 | 119.2 (3) | N1—C5—C4 | 120.2 (4) |
C7—C6—H6 | 120.4 | C4—C5—H5 | 119.9 |
C1—C2—Br1 | 119.0 (3) | C3—C4—H4 | 119.2 |
C1—C2—C3 | 121.5 (4) | C5—C4—C3 | 121.7 (4) |
C3—C2—Br1 | 119.4 (3) | C5—C4—H4 | 119.2 |
N1—C1—C2 | 119.9 (4) | C7—C8—H8 | 121.7 |
N1—C1—H1 | 120.1 | C7—C8—C9 | 116.7 (4) |
C2—C1—H1 | 120.1 | C9—C8—H8 | 121.7 |
C6—C7—Br2 | 117.4 (3) | C10—C9—C8 | 121.4 (4) |
C6—C7—C8 | 122.3 (4) | C10—C9—H9 | 119.3 |
C8—C7—Br2 | 120.3 (3) | C8—C9—H9 | 119.3 |
Br2—C7—C8—C9 | −179.7 (3) | N1—C5—C4—C3 | 0.4 (7) |
Br1—C2—C1—N1 | −176.6 (3) | C6—N2—C10—C9 | 2.2 (6) |
Br1—C2—C3—C4 | 177.8 (3) | C6—C7—C8—C9 | −0.3 (6) |
O2—N2—C6—C7 | 178.8 (3) | C2—C3—C4—C5 | −0.8 (6) |
O2—N2—C10—C9 | −177.9 (4) | C1—N1—C5—C4 | 0.8 (6) |
N2—C6—C7—Br2 | 179.8 (3) | C1—C2—C3—C4 | 0.1 (6) |
N2—C6—C7—C8 | 0.4 (6) | C7—C8—C9—C10 | 1.1 (7) |
N2—C10—C9—C8 | −2.1 (7) | C3—C2—C1—N1 | 1.1 (6) |
O1—N1—C1—C2 | 178.3 (4) | C10—N2—C6—C7 | −1.4 (5) |
O1—N1—C5—C4 | −179.0 (4) | C5—N1—C1—C2 | −1.6 (6) |
Experimental details
Crystal data | |
Chemical formula | C5H4BrNO |
Mr | 174.00 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 7.832 (5), 18.398 (10), 8.298 (5) |
β (°) | 92.906 (5) |
V (Å3) | 1194.2 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 6.77 |
Crystal size (mm) | 0.3 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Rigaku XtaLAB mini |
Absorption correction | Multi-scan (REQAB; Rigaku, 1998) |
Tmin, Tmax | 0.189, 0.257 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12561, 2732, 1881 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.092, 1.09 |
No. of reflections | 2732 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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
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