2-(4-Methyl­phen­oxy)-5-nitro­pyridine

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

doi:10.1107/S1600536811044047

organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3077

doi:10.1107/S1600536811044047

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2-(4-Methylphenoxy)-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)

The title molecule, C₁₂H₁₀N₂O₃, is twisted, the dihedral angle between the rings being 61.16 (13)°. The nitro group is approximately coplanar with the pyridine ring to which it is attached [O—N—C—C torsion angle = −178.1 (3)°]. Supramolecular chains along [010] and mediated by C—H⋯O and π–π [centroid(pyridyl)–(benzene) distance = 3.8259 (18) Å] contacts feature in the crystal packing.

Related literature

For the structure of a related nitro-pyridine derivative, see: Nasir et al. (2010 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₃
M_r = 230.22
Orthorhombic, P b c a
a = 7.2818 (18) Å
b = 11.977 (2) Å
c = 25.362 (5) Å
V = 2211.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.07 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.670, T_max = 0.746
15887 measured reflections
1951 independent reflections
1089 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.147
S = 1.02
1951 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O(3)ⁱ	0.93	2.43	3.135 (3)	132
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

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/S1600536811044047/hg5116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044047/hg5116Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044047/hg5116Isup3.cml

checkCIF report

Comment top

The synthesis and crystal structure determination of the title compound, (I), was determined in connection with studies of related species (Nasir et al., 2010). In (I), the dihedral angle formed between the pyridyl and benzene rings is 61.16 (13)°, indicating significant twisting in the molecule. The nitro group is co-planar with the pyridyl ring to which it is connected as seen in the value of the O2—N2—C4—C3 torsion angle of -178.1 (3)°.

The most prominent features in the crystal packing are the formation of C—H···O, Table 1, and π–π interactions. The latter occur between the pyridyl and benzene rings with the separation between the ring centroids being 3.8259 (18) Å for symmetry operation 3/2 - x, 1/2 + y, z. These interactions lead to supramolecular chains along the b axis, Fig. 2, which pack as shown in Fig. 3.

Related literature top

For the structure of a related nitro-pyridine derivative, see: Nasir et al. (2010).

Experimental top

p-Cresol (2.16 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 5 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. Supramolecular chain along [010] in (I) sustained by C—H···O and π–π interactions, shown as orange and purple dashed lines, respectively.
	Fig. 3. Unit-cell contents for (I) shown in projection down the b axis highlighting the packing of supramolecular chains.

2-(4-Methylphenoxy)-5-nitropyridine top

Crystal data top

C₁₂H₁₀N₂O₃	F(000) = 960
M_r = 230.22	D_x = 1.383 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1038 reflections
a = 7.2818 (18) Å	θ = 3.2–19.7°
b = 11.977 (2) Å	µ = 0.10 mm⁻¹
c = 25.362 (5) Å	T = 293 K
V = 2211.9 (8) Å³	Block, colourless
Z = 8	0.20 × 0.18 × 0.07 mm

Data collection top

Bruker SMART APEX diffractometer	1951 independent reflections
Radiation source: fine-focus sealed tube	1089 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.670, T_max = 0.746	k = −14→14
15887 measured reflections	l = −30→30

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.147	w = 1/[σ²(F_o²) + (0.0643P)² + 0.2807P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
1951 reflections	Δρ_max = 0.15 e Å⁻³
156 parameters	Δρ_min = −0.13 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: 0.0060 (13)

Crystal data top

C₁₂H₁₀N₂O₃	V = 2211.9 (8) Å³
M_r = 230.22	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.2818 (18) Å	µ = 0.10 mm⁻¹
b = 11.977 (2) Å	T = 293 K
c = 25.362 (5) Å	0.20 × 0.18 × 0.07 mm

Data collection top

Bruker SMART APEX diffractometer	1951 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1089 reflections with I > 2σ(I)
T_min = 0.670, T_max = 0.746	R_int = 0.074
15887 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.02	Δρ_max = 0.15 e Å⁻³
1951 reflections	Δρ_min = −0.13 e Å⁻³
156 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.5542 (3)	0.41426 (14)	0.32750 (7)	0.0725 (6)
O2	0.8217 (3)	0.59307 (19)	0.54024 (9)	0.1039 (8)
O3	0.7135 (4)	0.74378 (19)	0.50863 (8)	0.1135 (9)
N1	0.6779 (3)	0.41528 (17)	0.41124 (9)	0.0699 (7)
N2	0.7486 (4)	0.6456 (2)	0.50490 (10)	0.0758 (7)
C1	0.6005 (4)	0.4707 (2)	0.37191 (11)	0.0595 (7)
C2	0.5682 (3)	0.5841 (2)	0.37215 (10)	0.0613 (7)
H2	0.5145	0.6191	0.3433	0.074*
C3	0.6168 (4)	0.6439 (2)	0.41563 (10)	0.0648 (7)
H3	0.5978	0.7206	0.4173	0.078*
C4	0.6950 (4)	0.5868 (2)	0.45701 (10)	0.0576 (7)
C5	0.7247 (4)	0.4751 (2)	0.45359 (11)	0.0675 (8)
H5	0.7798	0.4389	0.4819	0.081*
C6	0.5381 (4)	0.2976 (2)	0.32825 (10)	0.0588 (7)
C7	0.6205 (4)	0.2394 (2)	0.28825 (9)	0.0625 (7)
H7	0.6943	0.2759	0.2638	0.075*
C8	0.5920 (4)	0.1252 (2)	0.28494 (10)	0.0639 (7)
H8	0.6459	0.0857	0.2574	0.077*
C9	0.4864 (4)	0.0685 (2)	0.32118 (10)	0.0601 (7)
C10	0.4088 (4)	0.1301 (2)	0.36136 (11)	0.0675 (8)
H10	0.3393	0.0936	0.3868	0.081*
C11	0.4313 (4)	0.2442 (2)	0.36485 (10)	0.0685 (8)
H11	0.3747	0.2844	0.3917	0.082*
C12	0.4559 (4)	−0.0556 (2)	0.31771 (12)	0.0854 (9)
H12A	0.4765	−0.0888	0.3517	0.128*
H12B	0.5397	−0.0871	0.2926	0.128*
H12C	0.3320	−0.0700	0.3067	0.128*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0976 (16)	0.0589 (12)	0.0612 (11)	0.0000 (10)	−0.0111 (11)	0.0016 (9)
O2	0.142 (2)	0.0885 (16)	0.0806 (14)	0.0159 (14)	−0.0259 (15)	−0.0119 (13)
O3	0.210 (3)	0.0523 (12)	0.0784 (14)	−0.0020 (15)	0.0069 (16)	−0.0057 (11)
N1	0.0881 (17)	0.0516 (13)	0.0699 (14)	0.0073 (11)	−0.0110 (14)	−0.0033 (12)
N2	0.104 (2)	0.0597 (16)	0.0639 (15)	−0.0023 (14)	0.0124 (14)	−0.0004 (13)
C1	0.0622 (17)	0.0557 (16)	0.0607 (16)	0.0015 (13)	0.0020 (14)	0.0036 (14)
C2	0.0640 (18)	0.0586 (17)	0.0615 (16)	0.0076 (13)	0.0040 (14)	0.0104 (14)
C3	0.0754 (19)	0.0496 (15)	0.0695 (17)	0.0059 (14)	0.0120 (16)	0.0042 (14)
C4	0.0645 (17)	0.0508 (16)	0.0574 (15)	−0.0002 (13)	0.0085 (14)	−0.0002 (13)
C5	0.081 (2)	0.0566 (17)	0.0650 (17)	0.0056 (15)	−0.0076 (15)	0.0019 (14)
C6	0.0642 (18)	0.0568 (17)	0.0555 (16)	0.0006 (13)	−0.0087 (14)	−0.0002 (13)
C7	0.0632 (17)	0.0729 (18)	0.0513 (15)	−0.0010 (14)	−0.0007 (13)	0.0029 (14)
C8	0.0646 (17)	0.0730 (19)	0.0541 (15)	0.0055 (15)	−0.0050 (14)	−0.0100 (14)
C9	0.0536 (16)	0.0654 (18)	0.0614 (16)	−0.0024 (14)	−0.0105 (14)	−0.0089 (14)
C10	0.0596 (17)	0.075 (2)	0.0683 (18)	−0.0082 (14)	0.0032 (15)	0.0007 (15)
C11	0.0697 (19)	0.0705 (19)	0.0651 (17)	0.0041 (15)	0.0042 (15)	−0.0086 (15)
C12	0.088 (2)	0.071 (2)	0.098 (2)	−0.0109 (16)	−0.0140 (19)	−0.0137 (17)

Geometric parameters (Å, º) top

O1—C1	1.356 (3)	C6—C11	1.369 (3)
O1—C6	1.403 (3)	C6—C7	1.369 (3)
O2—N2	1.217 (3)	C7—C8	1.386 (4)
O3—N2	1.208 (3)	C7—H7	0.9300
N1—C1	1.324 (3)	C8—C9	1.377 (3)
N1—C5	1.336 (3)	C8—H8	0.9300
N2—C4	1.457 (3)	C9—C10	1.379 (3)
C1—C2	1.379 (3)	C9—C12	1.505 (3)
C2—C3	1.361 (3)	C10—C11	1.380 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.376 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.358 (3)	C12—H12B	0.9600
C5—H5	0.9300	C12—H12C	0.9600

C1—O1—C6	120.4 (2)	C7—C6—O1	117.4 (2)
C1—N1—C5	116.4 (2)	C6—C7—C8	118.8 (3)
O3—N2—O2	122.5 (3)	C6—C7—H7	120.6
O3—N2—C4	118.6 (3)	C8—C7—H7	120.6
O2—N2—C4	118.8 (2)	C9—C8—C7	122.0 (2)
N1—C1—O1	118.8 (2)	C9—C8—H8	119.0
N1—C1—C2	124.3 (3)	C7—C8—H8	119.0
O1—C1—C2	116.9 (2)	C8—C9—C10	117.3 (2)
C3—C2—C1	118.5 (2)	C8—C9—C12	122.0 (2)
C3—C2—H2	120.7	C10—C9—C12	120.7 (3)
C1—C2—H2	120.7	C9—C10—C11	121.9 (3)
C2—C3—C4	117.7 (2)	C9—C10—H10	119.0
C2—C3—H3	121.2	C11—C10—H10	119.0
C4—C3—H3	121.2	C6—C11—C10	119.1 (3)
C5—C4—C3	120.4 (3)	C6—C11—H11	120.4
C5—C4—N2	119.1 (3)	C10—C11—H11	120.4
C3—C4—N2	120.5 (2)	C9—C12—H12A	109.5
N1—C5—C4	122.7 (3)	C9—C12—H12B	109.5
N1—C5—H5	118.7	H12A—C12—H12B	109.5
C4—C5—H5	118.7	C9—C12—H12C	109.5
C11—C6—C7	120.9 (2)	H12A—C12—H12C	109.5
C11—C6—O1	121.5 (2)	H12B—C12—H12C	109.5

C5—N1—C1—O1	178.5 (2)	C3—C4—C5—N1	−1.2 (4)
C5—N1—C1—C2	0.7 (4)	N2—C4—C5—N1	179.4 (2)
C6—O1—C1—N1	18.3 (4)	C1—O1—C6—C11	52.0 (3)
C6—O1—C1—C2	−163.8 (2)	C1—O1—C6—C7	−133.5 (2)
N1—C1—C2—C3	−0.7 (4)	C11—C6—C7—C8	0.9 (4)
O1—C1—C2—C3	−178.6 (2)	O1—C6—C7—C8	−173.7 (2)
C1—C2—C3—C4	−0.2 (4)	C6—C7—C8—C9	−1.2 (4)
C2—C3—C4—C5	1.1 (4)	C7—C8—C9—C10	0.0 (4)
C2—C3—C4—N2	−179.4 (2)	C7—C8—C9—C12	−179.8 (2)
O3—N2—C4—C5	−176.4 (3)	C8—C9—C10—C11	1.6 (4)
O2—N2—C4—C5	1.3 (4)	C12—C9—C10—C11	−178.6 (3)
O3—N2—C4—C3	4.1 (4)	C7—C6—C11—C10	0.7 (4)
O2—N2—C4—C3	−178.1 (3)	O1—C6—C11—C10	175.0 (2)
C1—N1—C5—C4	0.2 (4)	C9—C10—C11—C6	−1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O(3)ⁱ	0.93	2.43	3.135 (3)	132

Symmetry code: (i) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₃
M_r	230.22
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	7.2818 (18), 11.977 (2), 25.362 (5)
V (Å³)	2211.9 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.18 × 0.07

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.670, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	15887, 1951, 1089
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.147, 1.02
No. of reflections	1951
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13

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).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O(3)ⁱ	0.93	2.43	3.135 (3)	132

Symmetry code: (i) −x+3/2, y−1/2, z.

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

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Nasir, S. B., Abdullah, Z., Fairuz, Z. A., Ng, S. W. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2428. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar