2-(2-Meth­oxy­phen­oxy)-3-nitro­pyridine

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

doi:10.1107/S1600536811045247

organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3174

https://doi.org/10.1107/S1600536811045247

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2-(2-Methoxyphenoxy)-3-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 28 October 2011; online 5 November 2011)

In the title compound, C₁₂H₁₀N₂O₄, the pyridine and benzene rings are almost orthogonal, forming a dihedral angle of 86.63 (6)°. Each of the nitro [O—N—C—C torsion angle = −6.45 (19)°] and methoxy [C—O—C—C torsion angle = 179.69 (11)°] groups is almost coplanar with the ring to which it is connected. Molecules are consolidated in the crystal structure via C—H⋯O interactions, forming a three-dimensional network.

Related literature

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

Experimental

Crystal data

C₁₂H₁₀N₂O₄
M_r = 246.22
Monoclinic, P 2₁ /n
a = 7.5017 (7) Å
b = 7.1542 (6) Å
c = 20.6369 (18) Å
β = 91.878 (1)°
V = 1106.96 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.35 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.961, T_max = 0.978
10026 measured reflections
2551 independent reflections
2103 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.103
S = 1.03
2551 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.95	2.58	3.4085 (17)	146
C9—H9⋯O4ⁱⁱ	0.95	2.55	3.2659 (16)	132
C12—H12a⋯O3ⁱⁱⁱ	0.98	2.52	3.3560 (18)	143
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, 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: https://doi.org/10.1107/S1600536811045247/hb6471sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045247/hb6471Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811045247/hb6471Isup3.cml

checkCIF report

Comment top

As a continuation of synthetic and structural studies of nitro-pyridine derivatives (Nasir et al., 2010), the title compound, (I), was investigated, Fig. 1. The dihedral angle formed between the pyridine and benzene rings is 86.63 (6)°, indicating an almost orthogonal relationship. Each of the nitro [the O3—N2—C2—C1 torsion angle is -6.45 (19)°] and methoxy [the C12—O2—C11—C6 torsion angle is 179.69 (11)°] groups is co-planar with the ring to which it is attached. Molecules are stabilized in the three-dimensional crystal structure by C—H···O interactions, Table 1. Globally, the nitro-pyridine residues pack into layers in the ab plane with the benzene rings projecting to either side, Fig.2.

Related literature top

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

Experimental top

o-Methoxyphenol (2.5 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-3-nitropyridine (3.17 g, 20 mmol) dissolved in THF (50 ml). The mixture was heated for 4 h. Water was added and the organic phase extracted with chloroform. The chloroform solution was dried over sodium sulfate and evaporation of the solvent yielded colourless blocks.

Structure description top

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

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 displacement ellipsoids at the 50% probability level.
	Fig. 2. Unit-cell contents for (I) shown in projection down the a axis. The C—H···O interactions are shown as orange dashed lines.

2-(2-Methoxyphenoxy)-3-nitropyridine top

Crystal data top

C₁₂H₁₀N₂O₄	F(000) = 512
M_r = 246.22	D_x = 1.477 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3556 reflections
a = 7.5017 (7) Å	θ = 2.9–28.2°
b = 7.1542 (6) Å	µ = 0.11 mm⁻¹
c = 20.6369 (18) Å	T = 100 K
β = 91.878 (1)°	Block, colourless
V = 1106.96 (17) Å³	0.35 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2551 independent reflections
Radiation source: fine-focus sealed tube	2103 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.961, T_max = 0.978	k = −9→9
10026 measured reflections	l = −23→26

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.053P)² + 0.3772P] where P = (F_o² + 2F_c²)/3
2551 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₂H₁₀N₂O₄	V = 1106.96 (17) Å³
M_r = 246.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5017 (7) Å	µ = 0.11 mm⁻¹
b = 7.1542 (6) Å	T = 100 K
c = 20.6369 (18) Å	0.35 × 0.30 × 0.20 mm
β = 91.878 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2551 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2103 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.978	R_int = 0.029
10026 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.03	Δρ_max = 0.25 e Å⁻³
2551 reflections	Δρ_min = −0.25 e Å⁻³
164 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.36667 (12)	0.22735 (12)	0.12197 (4)	0.0182 (2)
O2	0.71311 (12)	0.13613 (14)	0.12236 (4)	0.0206 (2)
O3	0.20311 (15)	0.16998 (15)	0.01073 (5)	0.0316 (3)
O4	0.12030 (15)	0.40621 (16)	−0.04768 (5)	0.0323 (3)
N1	0.47657 (14)	0.52273 (15)	0.13850 (5)	0.0190 (2)
N2	0.20013 (15)	0.33758 (17)	−0.00044 (5)	0.0207 (3)
C1	0.38285 (16)	0.40572 (17)	0.10136 (6)	0.0150 (3)
C2	0.29836 (16)	0.46433 (18)	0.04319 (6)	0.0171 (3)
C3	0.30952 (18)	0.6508 (2)	0.02541 (7)	0.0235 (3)
H3	0.2519	0.6939	−0.0135	0.028*
C4	0.4052 (2)	0.7729 (2)	0.06477 (7)	0.0262 (3)
H4	0.4140	0.9017	0.0541	0.031*
C5	0.48791 (18)	0.70151 (19)	0.12028 (7)	0.0236 (3)
H5	0.5568	0.7842	0.1470	0.028*
C6	0.45474 (17)	0.18151 (17)	0.18111 (6)	0.0165 (3)
C7	0.35938 (17)	0.17835 (18)	0.23680 (6)	0.0198 (3)
H7	0.2382	0.2170	0.2360	0.024*
C8	0.44250 (18)	0.11778 (19)	0.29441 (7)	0.0217 (3)
H8	0.3787	0.1162	0.3334	0.026*
C9	0.61791 (18)	0.06017 (18)	0.29447 (6)	0.0196 (3)
H9	0.6736	0.0169	0.3337	0.024*
C10	0.71438 (17)	0.06438 (17)	0.23835 (6)	0.0179 (3)
H10	0.8354	0.0250	0.2392	0.022*
C11	0.63311 (17)	0.12668 (17)	0.18063 (6)	0.0160 (3)
C12	0.89664 (19)	0.0810 (2)	0.12152 (7)	0.0250 (3)
H12A	0.9384	0.0882	0.0771	0.038*
H12B	0.9088	−0.0477	0.1374	0.038*
H12C	0.9683	0.1646	0.1495	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0237 (5)	0.0134 (4)	0.0169 (5)	−0.0025 (4)	−0.0074 (4)	0.0026 (3)
O2	0.0236 (5)	0.0230 (5)	0.0152 (5)	0.0025 (4)	−0.0015 (4)	0.0007 (4)
O3	0.0442 (6)	0.0264 (6)	0.0235 (6)	−0.0106 (5)	−0.0096 (5)	0.0015 (4)
O4	0.0353 (6)	0.0440 (7)	0.0170 (5)	0.0105 (5)	−0.0087 (4)	0.0004 (5)
N1	0.0201 (5)	0.0141 (5)	0.0226 (6)	−0.0003 (4)	−0.0027 (4)	−0.0002 (4)
N2	0.0199 (5)	0.0292 (7)	0.0129 (5)	0.0011 (5)	−0.0003 (4)	0.0006 (5)
C1	0.0153 (6)	0.0132 (6)	0.0165 (6)	0.0011 (4)	0.0009 (5)	0.0009 (5)
C2	0.0167 (6)	0.0196 (7)	0.0149 (6)	0.0013 (5)	0.0006 (5)	0.0009 (5)
C3	0.0247 (7)	0.0230 (7)	0.0230 (7)	0.0054 (5)	0.0025 (5)	0.0084 (6)
C4	0.0311 (7)	0.0146 (6)	0.0332 (8)	0.0021 (5)	0.0042 (6)	0.0075 (6)
C5	0.0244 (7)	0.0144 (6)	0.0318 (8)	−0.0016 (5)	−0.0009 (6)	−0.0009 (6)
C6	0.0222 (6)	0.0105 (6)	0.0162 (6)	−0.0025 (5)	−0.0060 (5)	0.0009 (5)
C7	0.0194 (6)	0.0181 (6)	0.0216 (7)	−0.0023 (5)	−0.0020 (5)	0.0006 (5)
C8	0.0253 (7)	0.0216 (7)	0.0182 (7)	−0.0050 (5)	0.0004 (5)	0.0020 (5)
C9	0.0272 (7)	0.0156 (6)	0.0156 (6)	−0.0040 (5)	−0.0055 (5)	0.0027 (5)
C10	0.0219 (6)	0.0126 (6)	0.0189 (7)	−0.0003 (5)	−0.0041 (5)	0.0004 (5)
C11	0.0233 (6)	0.0096 (6)	0.0151 (6)	−0.0019 (5)	−0.0018 (5)	0.0002 (5)
C12	0.0243 (7)	0.0282 (8)	0.0226 (7)	0.0043 (6)	0.0004 (5)	0.0000 (6)

Geometric parameters (Å, º) top

O1—C1	1.3518 (15)	C5—H5	0.9500
O1—C6	1.4075 (14)	C6—C7	1.3735 (18)
O2—C11	1.3630 (15)	C6—C11	1.3947 (18)
O2—C12	1.4329 (16)	C7—C8	1.3934 (18)
O3—N2	1.2211 (16)	C7—H7	0.9500
O4—N2	1.2295 (14)	C8—C9	1.3788 (19)
N1—C1	1.3217 (16)	C8—H8	0.9500
N1—C5	1.3367 (17)	C9—C10	1.3860 (19)
N2—C2	1.4604 (17)	C9—H9	0.9500
C1—C2	1.4031 (17)	C10—C11	1.3935 (17)
C2—C3	1.3871 (19)	C10—H10	0.9500
C3—C4	1.378 (2)	C12—H12A	0.9800
C3—H3	0.9500	C12—H12B	0.9800
C4—C5	1.383 (2)	C12—H12C	0.9800
C4—H4	0.9500

C1—O1—C6	116.64 (9)	C11—C6—O1	118.84 (11)
C11—O2—C12	116.62 (10)	C6—C7—C8	119.22 (12)
C1—N1—C5	118.72 (12)	C6—C7—H7	120.4
O3—N2—O4	123.18 (12)	C8—C7—H7	120.4
O3—N2—C2	119.18 (11)	C9—C8—C7	119.61 (12)
O4—N2—C2	117.63 (12)	C9—C8—H8	120.2
N1—C1—O1	117.84 (11)	C7—C8—H8	120.2
N1—C1—C2	121.57 (12)	C8—C9—C10	121.14 (12)
O1—C1—C2	120.57 (11)	C8—C9—H9	119.4
C3—C2—C1	118.97 (12)	C10—C9—H9	119.4
C3—C2—N2	117.89 (11)	C9—C10—C11	119.70 (12)
C1—C2—N2	123.14 (11)	C9—C10—H10	120.1
C4—C3—C2	119.24 (13)	C11—C10—H10	120.1
C4—C3—H3	120.4	O2—C11—C10	125.24 (12)
C2—C3—H3	120.4	O2—C11—C6	116.28 (11)
C3—C4—C5	117.71 (13)	C10—C11—C6	118.47 (12)
C3—C4—H4	121.1	O2—C12—H12A	109.5
C5—C4—H4	121.1	O2—C12—H12B	109.5
N1—C5—C4	123.76 (13)	H12A—C12—H12B	109.5
N1—C5—H5	118.1	O2—C12—H12C	109.5
C4—C5—H5	118.1	H12A—C12—H12C	109.5
C7—C6—C11	121.84 (11)	H12B—C12—H12C	109.5
C7—C6—O1	119.13 (11)

C5—N1—C1—O1	−177.26 (11)	C3—C4—C5—N1	−1.7 (2)
C5—N1—C1—C2	1.09 (19)	C1—O1—C6—C7	98.47 (13)
C6—O1—C1—N1	−1.12 (16)	C1—O1—C6—C11	−86.40 (14)
C6—O1—C1—C2	−179.48 (11)	C11—C6—C7—C8	−0.36 (19)
N1—C1—C2—C3	−1.92 (19)	O1—C6—C7—C8	174.62 (11)
O1—C1—C2—C3	176.38 (11)	C6—C7—C8—C9	−0.73 (19)
N1—C1—C2—N2	177.31 (11)	C7—C8—C9—C10	1.1 (2)
O1—C1—C2—N2	−4.40 (18)	C8—C9—C10—C11	−0.40 (19)
O3—N2—C2—C3	172.79 (12)	C12—O2—C11—C10	−1.44 (18)
O4—N2—C2—C3	−6.00 (17)	C12—O2—C11—C6	179.69 (11)
O3—N2—C2—C1	−6.45 (19)	C9—C10—C11—O2	−179.52 (11)
O4—N2—C2—C1	174.76 (12)	C9—C10—C11—C6	−0.68 (18)
C1—C2—C3—C4	0.92 (19)	C7—C6—C11—O2	−179.99 (11)
N2—C2—C3—C4	−178.35 (12)	O1—C6—C11—O2	5.02 (16)
C2—C3—C4—C5	0.8 (2)	C7—C6—C11—C10	1.06 (18)
C1—N1—C5—C4	0.8 (2)	O1—C6—C11—C10	−173.93 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.58	3.4085 (17)	146
C9—H9···O4ⁱⁱ	0.95	2.55	3.2659 (16)	132
C12—H12a···O3ⁱⁱⁱ	0.98	2.52	3.3560 (18)	143

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₂O₄
M_r	246.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	7.5017 (7), 7.1542 (6), 20.6369 (18)
β (°)	91.878 (1)
V (Å³)	1106.96 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	10026, 2551, 2103
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.103, 1.03
No. of reflections	2551
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

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
C3—H3···O2ⁱ	0.95	2.58	3.4085 (17)	146
C9—H9···O4ⁱⁱ	0.95	2.55	3.2659 (16)	132
C12—H12a···O3ⁱⁱⁱ	0.98	2.52	3.3560 (18)	143

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x+1/2, −y+1/2, z+1/2; (iii) x+1, y, z.

Footnotes

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

Acknowledgements

We thank the University of Malaya (grant No. FP001/2010 A) for supporting this study.

References

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