2-(Naphthalen-2-yl-oxy)-5-nitro-pyridine.

Abstract

A nearly orthogonal relationship is found for the ring systems in the title compound, C(15)H(10)N(2)O(3), with the dihedral angle between the rings being 86.13 (11)°. The nitro group is approximately coplanar with the pyridine ring to which it is connected [the O-N-C-C torsion angle = -1.8 (4)°]. This coplanarity allows for the close approach of these residues in the crystal structure enabling the formation of N-O⋯π(pyridine) inter-actions [3.547 (4) Å]. Further consolidation of the crystal packing is afforded by weak π-π inter-actions [centroid-centroid distances = 3.9576 (16) and 3.9822 (16) Å].

Full text

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2-(Naphthalen-2-yloxy)-5-nitropyridine
Shah Bakhtiar Nasir,aZainal Abidin Fairuz,aZanariah
Abdullah,a‡ Seik Weng Nga,band Edward R. T. Tiekinka*
aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia,
andbChemistry Department, Faculty of, Science, King Abdulaziz University, PO Box
80203 Jeddah, Saudi Arabia
Correspondence e-mail: edward.tiekink@gmail.com
Received 24 October 2011; accepted 24 October 2011
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.003 A ˚;
R factor = 0.054; wR factor = 0.193; data-to-parameter ratio = 14.1.
A nearly orthogonal relationship is found for the ring systems
in the title compound, C15H10N2O3, with the dihedral angle
between the rings being 86.13 (11)?. The nitro group is
approximately coplanar with the pyridine ring to which it is
connected [the O—N—C—C torsion angle = ?1.8 (4)?]. This
coplanarity allows for the close approach of these residues in
the crystal structure enabling the formation of N—
O????(pyridine) interactions [3.547 (4) A˚]. Further consolida-
tion of the crystal packing is afforded by weak ?–?
interactions [centroid–centroid distances = 3.9576 (16) and
3.9822 (16) A˚].
Related literature
For the structure of a related nitropyridine derivative, see:
Nasir et al. (2010). For discussion on nitro-O???? interactions,
see: Huang et al. (2008).
Experimental
Crystal data
C15H10N2O3
Mr= 266.25
Monoclinic, P21=c
a = 6.7389 (12) A˚
b = 8.9182 (16) A˚
c = 21.072 (4) A˚
? = 94.289 (3)?
V = 1262.9 (4) A˚3
Z = 4
Mo K? radiation
? = 0.10 mm?1
T = 293 K
0.25 ? 0.20 ? 0.15 mm
Data collection
Bruker SMART APEX
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin= 0.976, Tmax= 0.985
6512 measured reflections
2224 independent reflections
1052 reflections with I > 2?(I)
Rint= 0.052
Refinement
R[F2> 2?(F2)] = 0.054
wR(F2) = 0.193
S = 0.94
2224 reflections
158 parameters
H-atom parameters constrained
??max= 0.26 e A˚?3
??min= ?0.18 e A˚?3
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT
(Bruker, 2009); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure:SHELXL97(Sheldrick,
ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006);
software used to prepare material for publication: publCIF (Westrip,
2010).
2008);molecular graphics:
We thank the University of Malaya (grant No. RG027/
09AFR) for supporting this study.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HG5118).
References
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Huang, L., Massa, L. & Karle, J. (2008). Proc. Natl Acad. Sci. 105, 13720–
13723.
Nasir, S. B., Abdullah, Z., Fairuz, Z. A., Ng, S. W. & Tiekink, E. R. T. (2010).
Acta Cryst. E66, o2428.
Sheldrick, G. M. (1996). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
organic compounds
Acta Cryst. (2011). E67, o3079doi:10.1107/S1600536811044060Nasir et al.
o3079
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
‡ Additional correspondence author, e-mail: zana@um.edu.my.

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supplementary materials

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supplementary materials
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Acta Cryst. (2011). E67, o3079 [ doi:10.1107/S1600536811044060 ]
2-(Naphthalen-2-yloxy)-5-nitropyridine
S. B. Nasir, Z. A. Fairuz, Z. Abdullah, S. W. Ng and E. R. T. Tiekink
Comment
In continuation of structural studies of nitro-pyridine derivatives (Nasir et al., 2010), the title compound was synthesized and
characterized crystallographically. The molecule of (I), Fig. 1, is highly twisted as seen in the near orthogonal relationship
between the two ring systems with the dihedral angle formed between the nitro-pyridine ring and naphthalyl ring being
86.13 (11)°. The nitro group is co-planar with the pyridyl ring to which it is attached with the O2—N2—C4—C3 torsion
angle being -1.8 (4)°.
The most prominent feature of the crystal packing appears to be N—O···π interactions (Huang et al., 2008). The distance
between O3···π(pyridyl) = 3.547 (4) Å, with the N2—O3···ring centroid(pyridyl)i angle = 81.9 (2)° for symmetry operation
i: 1 - x, 1 - y, 1 - z. Similar interactions were reported in the crystal structure of 2-(4-methoxyphenoxy)-3-nitropyridine
(Nasir et al., 2010). In (I), the N—O···π interactions along with weak π–π interactions, whereby both rings of the naphthalyl
residue interact with the pyridyl ring, consolidate the crystal packing. The parameters associated with the π–π interactions
are ring centroid(pyridyl)···ring centroid(C6–C11) and (C10–C15) = 3.9822 (16) and 3.9576 (16) Å, respectively, for ii: 1
- x, -1/2 + y, 3/2 - z. A view of the crystal packing is shown in Fig. 2.
Experimental
2-Naphthol (2.88 g, 20 mmol) and sodium hydroxide (0.80 g, 20 mmol) were dissolved in water (50 ml) and to the solution
was added 2-chloro-5-nitropyridine (3.17 g, 20 mmol) dissolved in THF (50 ml). The mixture was heated for 7 h. Water
was added and the organic phase extracted with chloroform. The chloroform solution was dried over sodium sulfate; slow
evaporation led to the formation of colourless crystals.
Refinement
Hydrogen atoms were placed at calculated positions (C—H 0.93 Å) and were treated as riding on their parent carbon atoms,
with U(H) set to 1.2Ueq(C). The naphthalene fused-ring was refined as two fused hexagons with C≐C distances fixed at
1.39 Å.
Figures
Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement el-
lipsoids at the 35% probability level.

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Fig. 2. Unit-cell contents for (I) shown in projection down the a axis. The N—O···π and π–π
interactions are shown as orange and purple dashed lines, respectively.
2-(Naphthalen-2-yloxy)-5-nitropyridine
Crystal data
C15H10N2O3
F(000) = 552
Dx = 1.400 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 1499 reflections
θ = 2.5–21.3°
µ = 0.10 mm−1
T = 293 K
Block, colourless
Mr = 266.25
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 6.7389 (12) Å
b = 8.9182 (16) Å
c = 21.072 (4) Å
β = 94.289 (3)°
V = 1262.9 (4) Å3
Z = 4
0.25 × 0.20 × 0.15 mm
Data collection
Bruker SMART APEX
diffractometer
Radiation source: fine-focus sealed tube
graphite
ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.976, Tmax = 0.985
6512 measured reflections
2224 independent reflections
1052 reflections with I > 2σ(I)
Rint = 0.052
θmax = 25.0°, θmin = 1.9°
h = −8→7
k = −9→10
l = −23→25
Refinement
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)] = 0.054
H-atom parameters constrained
wR(F2) = 0.193
w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.26 e Å−3
Δρmin = −0.18 e Å−3
Extinction correction: SHELXL97 (Sheldrick, 2008),
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
S = 0.94
2224 reflections
158 parameters
0 restraints

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supplementary materials
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Primary atom site location: structure-invariant direct
methods
Extinction coefficient: 0.024 (5)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.5816 (3)
0.8327 (5)
0.5363 (6)
0.4532 (4)
0.6776 (7)
0.6029 (5)
0.7856 (5)
0.8868
0.8131 (5)
0.9339
0.6578 (6)
0.4845 (6)
0.3819
0.41265 (19)
0.5213
0.4128 (2)
0.2505 (3)
0.2506
0.0879 (2)
−0.0208
0.08767 (17)
0.25006 (17)
0.2499 (3)
0.3585
0.0873 (3)
0.0872
−0.0751 (3)
−0.1839
−0.07492 (19)
−0.1836
y
0.6709 (3)
0.2782 (3)
0.1958 (4)
0.4809 (3)
0.2766 (4)
0.5686 (4)
0.5678 (4)
0.6323
0.4702 (4)
0.4653
0.3793 (3)
0.3863 (3)
0.3219
0.58487 (18)
0.5246
0.6695 (2)
0.75959 (18)
0.8162
0.76505 (16)
0.8253
0.68042 (13)
0.59033 (13)
0.50569 (17)
0.4454
0.5111 (2)
0.4545
0.6012 (2)
0.6049
0.6859 (2)
0.7461
z
0.69203 (11)
0.47200 (13)
0.48260 (14)
0.62772 (12)
0.49811 (14)
0.64546 (14)
0.61964 (15)
0.6347
0.57165 (15)
0.5531
0.55143 (13)
0.58025 (15)
0.5662
0.78172 (8)
0.7941
0.72633 (7)
0.70776 (6)
0.6707
0.74459 (7)
0.7322
0.79997 (6)
0.81854 (6)
0.87393 (7)
0.8863
0.91075 (7)
0.9478
0.89219 (8)
0.9168
0.83680 (9)
0.8244
Uiso*/Ueq
0.0864 (8)
0.1210 (11)
0.1319 (12)
0.0709 (8)
0.0929 (10)
0.0662 (8)
0.0796 (10)
0.096*
0.0804 (10)
0.097*
0.0663 (9)
0.0747 (10)
0.090*
0.0638 (8)
0.077*
0.0638 (8)
0.0727 (9)
0.087*
0.0740 (9)
0.089*
0.0565 (8)
0.0521 (7)
0.0714 (9)
0.086*
0.0822 (10)
0.099*
0.0864 (11)
0.104*
0.0745 (10)
0.089*
O1
O2
O3
N1
N2
C1
C2
H2
C3
H3
C4
C5
H5
C6
H6
C7
C8
H8
C9
H9
C10
C11
C12
H12
C13
H13
C14
H14
C15
H15
Atomic displacement parameters (Å2)
U11
0.0829 (16)
0.158 (3)
0.164 (3)
0.0775 (18)
0.133 (3)
0.074 (2)
0.073 (2)
0.085 (3)
0.089 (3)
U22
0.0914 (17)
0.121 (2)
0.118 (2)
0.0660 (17)
0.083 (2)
0.067 (2)
0.094 (2)
0.095 (3)
0.063 (2)
U33
0.0898 (16)
0.089 (2)
0.110 (2)
0.0704 (17)
0.062 (2)
0.0588 (19)
0.074 (2)
0.063 (2)
0.0475 (18)
U12
−0.0342 (13)
0.032 (2)
−0.007 (2)
−0.0159 (14)
0.023 (2)
−0.0110 (17)
−0.0240 (19)
0.000 (2)
0.0060 (18)
U13
0.0385 (13)
0.0437 (19)
−0.016 (2)
0.0136 (14)
0.000 (2)
0.0132 (16)
0.0173 (18)
0.0180 (19)
0.0089 (17)
U23
−0.0301 (14)
−0.0121 (16)
−0.0479 (19)
−0.0087 (14)
−0.0026 (18)
−0.0046 (16)
−0.012 (2)
0.003 (2)
0.0015 (15)
O1
O2
O3
N1
N2
C1
C2
C3
C4