2-(Naphthalen-2-yl­oxy)-5-nitro­pyridine

Nasir, S.B.; Fairuz, Z.A.; Abdullah, Z.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536811044060

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3079

doi:10.1107/S1600536811044060

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2-(Naphthalen-2-yloxy)-5-nitropyridine

Shah Bakhtiar Nasir,^a Zainal Abidin Fairuz,^a Zanariah Abdullah,^a ‡ Seik Weng Ng ^a,^b and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^bChemistry 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; online 29 October 2011)

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⋯π(pyridine) interactions [3.547 (4) Å]. Further consolidation of the crystal packing is afforded by weak π–π interactions [centroid–centroid distances = 3.9576 (16) and 3.9822 (16) Å].

Related literature

For the structure of a related nitropyridine derivative, see: Nasir et al. (2010 ). For discussion on nitro-O⋯π interactions, see: Huang et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₀N₂O₃
M_r = 266.25
Monoclinic, P 2₁ /c
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
Mo Kα radiation
μ = 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 ) T_min = 0.976, T_max = 0.985
6512 measured reflections
2224 independent reflections
1052 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.193
S = 0.94
2224 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.18 e Å⁻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, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811044060/hg5118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044060/hg5118Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044060/hg5118Isup3.cml

checkCIF report

Comment top

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.

Related literature top

For the structure of a related nitropyridine derivative, see: Nasir et al. (2010). For discussion on nitro-O···π interactions, see: Huang et al. (2008).

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	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 top

Crystal data top

C₁₅H₁₀N₂O₃	F(000) = 552
M_r = 266.25	D_x = 1.400 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1499 reflections
a = 6.7389 (12) Å	θ = 2.5–21.3°
b = 8.9182 (16) Å	µ = 0.10 mm⁻¹
c = 21.072 (4) Å	T = 293 K
β = 94.289 (3)°	Block, colourless
V = 1262.9 (4) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2224 independent reflections
Radiation source: fine-focus sealed tube	1052 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→7
T_min = 0.976, T_max = 0.985	k = −9→10
6512 measured reflections	l = −23→25

Refinement top

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(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max = 0.001
2224 reflections	Δρ_max = 0.26 e Å⁻³
158 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.024 (5)

Crystal data top

C₁₅H₁₀N₂O₃	V = 1262.9 (4) Å³
M_r = 266.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7389 (12) Å	µ = 0.10 mm⁻¹
b = 8.9182 (16) Å	T = 293 K
c = 21.072 (4) Å	0.25 × 0.20 × 0.15 mm
β = 94.289 (3)°

Data collection top

Bruker SMART APEX diffractometer	2224 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1052 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.985	R_int = 0.052
6512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.193	H-atom parameters constrained
S = 0.94	Δρ_max = 0.26 e Å⁻³
2224 reflections	Δρ_min = −0.18 e Å⁻³
158 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.5816 (3)	0.6709 (3)	0.69203 (11)	0.0864 (8)
O2	0.8327 (5)	0.2782 (3)	0.47200 (13)	0.1210 (11)
O3	0.5363 (6)	0.1958 (4)	0.48260 (14)	0.1319 (12)
N1	0.4532 (4)	0.4809 (3)	0.62772 (12)	0.0709 (8)
N2	0.6776 (7)	0.2766 (4)	0.49811 (14)	0.0929 (10)
C1	0.6029 (5)	0.5686 (4)	0.64546 (14)	0.0662 (8)
C2	0.7856 (5)	0.5678 (4)	0.61964 (15)	0.0796 (10)
H2	0.8868	0.6323	0.6347	0.096*
C3	0.8131 (5)	0.4702 (4)	0.57165 (15)	0.0804 (10)
H3	0.9339	0.4653	0.5531	0.097*
C4	0.6578 (6)	0.3793 (3)	0.55143 (13)	0.0663 (9)
C5	0.4845 (6)	0.3863 (3)	0.58025 (15)	0.0747 (10)
H5	0.3819	0.3219	0.5662	0.090*
C6	0.41265 (19)	0.58487 (18)	0.78172 (8)	0.0638 (8)
H6	0.5213	0.5246	0.7941	0.077*
C7	0.4128 (2)	0.6695 (2)	0.72633 (7)	0.0638 (8)
C8	0.2505 (3)	0.75959 (18)	0.70776 (6)	0.0727 (9)
H8	0.2506	0.8162	0.6707	0.087*
C9	0.0879 (2)	0.76505 (16)	0.74459 (7)	0.0740 (9)
H9	−0.0208	0.8253	0.7322	0.089*
C10	0.08767 (17)	0.68042 (13)	0.79997 (6)	0.0565 (8)
C11	0.25006 (17)	0.59033 (13)	0.81854 (6)	0.0521 (7)
C12	0.2499 (3)	0.50569 (17)	0.87393 (7)	0.0714 (9)
H12	0.3585	0.4454	0.8863	0.086*
C13	0.0873 (3)	0.5111 (2)	0.91075 (7)	0.0822 (10)
H13	0.0872	0.4545	0.9478	0.099*
C14	−0.0751 (3)	0.6012 (2)	0.89219 (8)	0.0864 (11)
H14	−0.1839	0.6049	0.9168	0.104*
C15	−0.07492 (19)	0.6859 (2)	0.83680 (9)	0.0745 (10)
H15	−0.1836	0.7461	0.8244	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0829 (16)	0.0914 (17)	0.0898 (16)	−0.0342 (13)	0.0385 (13)	−0.0301 (14)
O2	0.158 (3)	0.121 (2)	0.089 (2)	0.032 (2)	0.0437 (19)	−0.0121 (16)
O3	0.164 (3)	0.118 (2)	0.110 (2)	−0.007 (2)	−0.016 (2)	−0.0479 (19)
N1	0.0775 (18)	0.0660 (17)	0.0704 (17)	−0.0159 (14)	0.0136 (14)	−0.0087 (14)
N2	0.133 (3)	0.083 (2)	0.062 (2)	0.023 (2)	0.000 (2)	−0.0026 (18)
C1	0.074 (2)	0.067 (2)	0.0588 (19)	−0.0110 (17)	0.0132 (16)	−0.0046 (16)
C2	0.073 (2)	0.094 (2)	0.074 (2)	−0.0240 (19)	0.0173 (18)	−0.012 (2)
C3	0.085 (3)	0.095 (3)	0.063 (2)	0.000 (2)	0.0180 (19)	0.003 (2)
C4	0.089 (3)	0.063 (2)	0.0475 (18)	0.0060 (18)	0.0089 (17)	0.0015 (15)
C5	0.092 (3)	0.065 (2)	0.067 (2)	−0.0149 (18)	0.0039 (19)	−0.0038 (17)
C6	0.0594 (19)	0.0561 (18)	0.075 (2)	0.0043 (14)	0.0001 (16)	−0.0062 (16)
C7	0.068 (2)	0.0581 (19)	0.066 (2)	−0.0146 (15)	0.0123 (16)	−0.0168 (16)
C8	0.090 (2)	0.061 (2)	0.064 (2)	−0.0162 (18)	−0.0125 (18)	0.0053 (16)
C9	0.064 (2)	0.069 (2)	0.086 (2)	0.0077 (16)	−0.0115 (18)	0.0010 (18)
C10	0.0562 (18)	0.0519 (17)	0.0608 (18)	0.0013 (14)	0.0011 (15)	−0.0056 (14)
C11	0.0529 (17)	0.0497 (16)	0.0535 (17)	0.0008 (13)	0.0023 (13)	−0.0044 (14)
C12	0.083 (2)	0.065 (2)	0.066 (2)	0.0065 (16)	0.0013 (18)	0.0028 (16)
C13	0.114 (3)	0.073 (2)	0.061 (2)	−0.008 (2)	0.016 (2)	0.0011 (17)
C14	0.077 (3)	0.094 (3)	0.092 (3)	−0.009 (2)	0.026 (2)	−0.022 (2)
C15	0.062 (2)	0.077 (2)	0.085 (2)	0.0101 (16)	0.0050 (18)	−0.0151 (19)

Geometric parameters (Å, º) top

O1—C1	1.355 (3)	C6—H6	0.9300
O1—C7	1.393 (2)	C7—C8	1.3900
O2—N2	1.217 (4)	C8—C9	1.3900
O3—N2	1.219 (4)	C8—H8	0.9300
N1—C1	1.309 (4)	C9—C10	1.3900
N1—C5	1.337 (4)	C9—H9	0.9300
N2—C4	1.463 (4)	C10—C11	1.3900
C1—C2	1.383 (4)	C10—C15	1.3900
C2—C3	1.358 (4)	C11—C12	1.3900
C2—H2	0.9300	C12—C13	1.3900
C3—C4	1.366 (4)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.3900
C4—C5	1.358 (4)	C13—H13	0.9300
C5—H5	0.9300	C14—C15	1.3900
C6—C7	1.3900	C14—H14	0.9300
C6—C11	1.3900	C15—H15	0.9300

C1—O1—C7	120.3 (2)	C8—C7—O1	120.35 (16)
C1—N1—C5	115.4 (3)	C7—C8—C9	120.0
O2—N2—O3	124.5 (4)	C7—C8—H8	120.0
O2—N2—C4	118.0 (4)	C9—C8—H8	120.0
O3—N2—C4	117.5 (4)	C10—C9—C8	120.0
N1—C1—O1	119.2 (3)	C10—C9—H9	120.0
N1—C1—C2	125.1 (3)	C8—C9—H9	120.0
O1—C1—C2	115.7 (3)	C9—C10—C11	120.0
C3—C2—C1	118.1 (3)	C9—C10—C15	120.0
C3—C2—H2	120.9	C11—C10—C15	120.0
C1—C2—H2	120.9	C12—C11—C10	120.0
C2—C3—C4	118.0 (3)	C12—C11—C6	120.0
C2—C3—H3	121.0	C10—C11—C6	120.0
C4—C3—H3	121.0	C13—C12—C11	120.0
C5—C4—C3	119.8 (3)	C13—C12—H12	120.0
C5—C4—N2	120.2 (4)	C11—C12—H12	120.0
C3—C4—N2	119.9 (3)	C12—C13—C14	120.0
N1—C5—C4	123.6 (3)	C12—C13—H13	120.0
N1—C5—H5	118.2	C14—C13—H13	120.0
C4—C5—H5	118.2	C15—C14—C13	120.0
C7—C6—C11	120.0	C15—C14—H14	120.0
C7—C6—H6	120.0	C13—C14—H14	120.0
C11—C6—H6	120.0	C14—C15—C10	120.0
C6—C7—C8	120.0	C14—C15—H15	120.0
C6—C7—O1	119.52 (16)	C10—C15—H15	120.0

C5—N1—C1—O1	178.1 (3)	C1—O1—C7—C8	−94.2 (3)
C5—N1—C1—C2	−1.0 (5)	C6—C7—C8—C9	0.0
C7—O1—C1—N1	8.4 (4)	O1—C7—C8—C9	−175.77 (15)
C7—O1—C1—C2	−172.4 (3)	C7—C8—C9—C10	0.0
N1—C1—C2—C3	0.8 (5)	C8—C9—C10—C11	0.0
O1—C1—C2—C3	−178.3 (3)	C8—C9—C10—C15	180.0
C1—C2—C3—C4	0.5 (5)	C9—C10—C11—C12	180.0
C2—C3—C4—C5	−1.4 (5)	C15—C10—C11—C12	0.0
C2—C3—C4—N2	177.5 (3)	C9—C10—C11—C6	0.0
O2—N2—C4—C5	177.1 (3)	C15—C10—C11—C6	180.0
O3—N2—C4—C5	−2.4 (5)	C7—C6—C11—C12	180.0
O2—N2—C4—C3	−1.8 (4)	C7—C6—C11—C10	0.0
O3—N2—C4—C3	178.7 (3)	C10—C11—C12—C13	0.0
C1—N1—C5—C4	−0.1 (5)	C6—C11—C12—C13	180.0
C3—C4—C5—N1	1.3 (5)	C11—C12—C13—C14	0.0
N2—C4—C5—N1	−177.6 (3)	C12—C13—C14—C15	0.0
C11—C6—C7—C8	0.0	C13—C14—C15—C10	0.0
C11—C6—C7—O1	175.81 (15)	C9—C10—C15—C14	180.0
C1—O1—C7—C6	90.0 (3)	C11—C10—C15—C14	0.0

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀N₂O₃
M_r	266.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.7389 (12), 8.9182 (16), 21.072 (4)
β (°)	94.289 (3)
V (Å³)	1262.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.976, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	6512, 2224, 1052
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.193, 0.94
No. of reflections	2224
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Footnotes

‡Additional correspondence author, e-mail: zana@um.edu.my.

Acknowledgements

We thank the University of Malaya (grant No. RG027/09AFR) for supporting this study.

References

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