2-Iodo-3-nitro­pyridine

Mao, L.-H.; Chen, Y.

doi:10.1107/S1600536809018534

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1428

doi:10.1107/S1600536809018534

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2-Iodo-3-nitropyridine

Li-Hua Mao ^a ^* and Yan Chen ^b

^aSchool of City Development, University of Jinan, Jinan 250002, People's Republic of China, and ^bShandong Blood Center, Jinan 250014, People's Republic of China
^*Correspondence e-mail: lihuamao2009@yahoo.cn

(Received 3 May 2009; accepted 16 May 2009; online 29 May 2009)

In the crystal structure of the title compound, C₅H₃IN₂O₂, intermolecular C—H⋯N hydrogen-bonding interactions link the molecules into one-dimensional chains along the b axis.

Related literature

For the applications of 2-iodo-3-nitropyridine in organic synthesis, see: Baik et al. (2005 ); Choi-Sledeski et al. (2003 ). For the crystal structure of related compounds, see: Holmes et al. (2002 ); Saha et al. (2006 ).

Experimental

Crystal data

C₅H₃IN₂O₂
M_r = 249.99
Monoclinic, P 2₁ /c
a = 8.0169 (15) Å
b = 12.313 (2) Å
c = 8.0999 (15) Å
β = 119.66 (2)°
V = 694.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.54 mm⁻¹
T = 298 K
0.60 × 0.30 × 0.21 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.147, T_max = 0.385
3615 measured reflections
1345 independent reflections
1267 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.075
S = 1.12
1345 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯N2ⁱ	0.93	2.61	3.529 (5)	172
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018534/rz2322sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018534/rz2322Isup2.hkl

checkCIF report

Comment top

In this paper, we report the crystal structure of the title compound, 2-iodo-3-nitropyridine, which is an important intermediate in organic synthesis (Baik et al., 2005; Choi-Sledeski et al., 2003).

In the molecule of the title compound (Fig. 1), all bond lengths are normal and in a good agreement with those reported previously for 2,6-diiodopyridine (Holmes et al., 2002) and 2-iodo-3hydroxypyridine (Saha et al., 2006). Atoms I1 and N1 are slightly displaced on opposite sides of the pyridine ring by 0.0719 (3) and 0.015 (4) Å, respectively. The nitro group is tilted by 34.6 (3)° with respect to the pyridine ring. The crystal structure is stabilized by intermolecular C—H···N hydrogen bonds (Table 1) linking the molecules into one dimension chains along the b axis (Fig. 2).

Related literature top

For the applications of 2-iodo-3-nitropyridine in organic synthesis, see: Baik et al. (2005); Choi-Sledeski et al. (2003). For the crystal structure of related compounds, see: Holmes et al. (2002); Saha et al. (2006).

Experimental top

The title compound was prepared by reaction of 2-amino-3-nitropyridine (1.1 g, 5 mmol), KNO₃ (1.01 g, 10 mmol), HI (6.6 g, 25 mmol, 50% aqueous solution), CuI (0.48 g, 2.5 mmol) and DMSO (60 ml) at 333K. After neutralizing with an alkaline solution, the reaction mixture was extracted several times with diethyl ether. The combined ethereal extracts were washed with water, dried over anhydrous sodium sulfate and concentrated to afford the crude product. Purification by flash chromatography gave 2-iodo-3-nitropyridine as a yellow solid in 70% isolated yield (0.875 g). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a methanol solution at room temperature over a period of one week.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. A partial packing diagram of the title compound viewed along the c axis. Intermolecular H bonds are shown as dashed lines.

2-Iodo-3-nitropyridine top

Crystal data top

C₅H₃IN₂O₂	F(000) = 464
M_r = 249.99	D_x = 2.390 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1077 reflections
a = 8.0169 (15) Å	θ = 2.5–25.9°
b = 12.313 (2) Å	µ = 4.54 mm⁻¹
c = 8.0999 (15) Å	T = 298 K
β = 119.66 (2)°	Block, yellow
V = 694.8 (3) Å³	0.60 × 0.30 × 0.21 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1345 independent reflections
Radiation source: fine-focus sealed tube	1267 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.147, T_max = 0.385	k = −15→14
3615 measured reflections	l = −9→9

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0401P)² + 0.1824P] where P = (F_o² + 2F_c²)/3
1345 reflections	(Δ/σ)_max = 0.001
91 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −1.09 e Å⁻³

Crystal data top

C₅H₃IN₂O₂	V = 694.8 (3) Å³
M_r = 249.99	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0169 (15) Å	µ = 4.54 mm⁻¹
b = 12.313 (2) Å	T = 298 K
c = 8.0999 (15) Å	0.60 × 0.30 × 0.21 mm
β = 119.66 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1345 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1267 reflections with I > 2σ(I)
T_min = 0.147, T_max = 0.385	R_int = 0.037
3615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.12	Δρ_max = 0.50 e Å⁻³
1345 reflections	Δρ_min = −1.09 e Å⁻³
91 parameters

Special details top

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.

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 > σ(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
I1	0.59372 (3)	0.162020 (19)	0.16542 (4)	0.03968 (14)
O1	0.7237 (5)	0.5149 (2)	0.3364 (5)	0.0601 (9)
O2	0.5036 (5)	0.4081 (3)	0.1331 (6)	0.0635 (9)
N1	0.6704 (5)	0.4373 (3)	0.2292 (5)	0.0395 (7)
C1	0.8177 (5)	0.3758 (3)	0.2090 (5)	0.0304 (7)
C2	0.9711 (5)	0.4353 (3)	0.2237 (6)	0.0378 (8)
H2A	0.9807	0.5095	0.2477	0.045*
C3	1.1084 (6)	0.3811 (4)	0.2019 (6)	0.0443 (10)
H3A	1.2127	0.4180	0.2084	0.053*
C4	1.0884 (5)	0.2712 (4)	0.1703 (6)	0.0465 (11)
H4A	1.1812	0.2349	0.1544	0.056*
N2	0.9430 (5)	0.2136 (2)	0.1610 (5)	0.0389 (7)
C5	0.8074 (5)	0.2654 (3)	0.1774 (5)	0.0300 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0391 (2)	0.0313 (2)	0.0496 (2)	−0.00698 (8)	0.02262 (15)	−0.00258 (9)
O1	0.073 (2)	0.0392 (16)	0.074 (2)	0.0116 (15)	0.0408 (19)	−0.0131 (16)
O2	0.0423 (18)	0.0458 (17)	0.107 (3)	0.0055 (15)	0.0404 (19)	0.0006 (19)
N1	0.043 (2)	0.0296 (16)	0.053 (2)	0.0098 (14)	0.0293 (17)	0.0093 (16)
C1	0.0318 (18)	0.0274 (17)	0.0322 (17)	0.0040 (14)	0.0161 (14)	0.0012 (15)
C2	0.040 (2)	0.0275 (17)	0.045 (2)	−0.0054 (15)	0.0204 (18)	−0.0024 (17)
C3	0.038 (2)	0.040 (2)	0.057 (2)	−0.0087 (17)	0.0248 (19)	−0.003 (2)
C4	0.038 (2)	0.043 (2)	0.067 (3)	0.0012 (16)	0.033 (2)	−0.0095 (19)
N2	0.0402 (17)	0.0257 (15)	0.0535 (19)	0.0024 (13)	0.0253 (15)	−0.0042 (15)
C5	0.0270 (16)	0.0306 (18)	0.0291 (16)	−0.0016 (14)	0.0114 (14)	0.0006 (14)

Geometric parameters (Å, º) top

I1—C5	2.097 (3)	C2—H2A	0.9300
O1—N1	1.217 (4)	C3—C4	1.371 (8)
O2—N1	1.222 (5)	C3—H3A	0.9300
N1—C1	1.478 (4)	C4—N2	1.335 (5)
C1—C5	1.378 (5)	C4—H4A	0.9300
C1—C2	1.385 (5)	N2—C5	1.322 (4)
C2—C3	1.372 (6)

O1—N1—O2	124.9 (3)	C4—C3—H3A	120.8
O1—N1—C1	117.6 (3)	C2—C3—H3A	120.8
O2—N1—C1	117.5 (3)	N2—C4—C3	123.6 (3)
C5—C1—C2	120.5 (3)	N2—C4—H4A	118.2
C5—C1—N1	123.2 (3)	C3—C4—H4A	118.2
C2—C1—N1	116.3 (3)	C5—N2—C4	118.5 (3)
C3—C2—C1	117.8 (4)	N2—C5—C1	121.2 (3)
C3—C2—H2A	121.1	N2—C5—I1	113.3 (2)
C1—C2—H2A	121.1	C1—C5—I1	125.4 (2)
C4—C3—C2	118.5 (3)

O1—N1—C1—C5	146.8 (4)	C3—C4—N2—C5	2.2 (6)
O2—N1—C1—C5	−35.1 (5)	C4—N2—C5—C1	−1.9 (5)
O1—N1—C1—C2	−33.1 (5)	C4—N2—C5—I1	−178.8 (3)
O2—N1—C1—C2	145.0 (4)	C2—C1—C5—N2	0.2 (5)
C5—C1—C2—C3	1.3 (6)	N1—C1—C5—N2	−179.7 (3)
N1—C1—C2—C3	−178.7 (4)	C2—C1—C5—I1	176.6 (3)
C1—C2—C3—C4	−1.2 (6)	N1—C1—C5—I1	−3.3 (5)
C2—C3—C4—N2	−0.6 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2ⁱ	0.93	2.61	3.529 (5)	172

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₃IN₂O₂
M_r	249.99
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.0169 (15), 12.313 (2), 8.0999 (15)
β (°)	119.66 (2)
V (Å³)	694.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.54
Crystal size (mm)	0.60 × 0.30 × 0.21

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.147, 0.385
No. of measured, independent and observed [I > 2σ(I)] reflections	3615, 1345, 1267
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.075, 1.12
No. of reflections	1345
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −1.09

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N2ⁱ	0.93	2.61	3.529 (5)	172.4

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 40672158) and the PhD Fund of the University of Jinan (No. B0640).

References

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