2-Iodo-3-nitro­pyridine

Abstract

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,

• a = 8.0169 (15) Å

• b = 12.313 (2) Å

• c = 8.0999 (15) Å

• β = 119.66 (2)°

• V = 694.8 (3) ų

• 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[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were found on difference maps, with C—H = 0.93 Å and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C5H3IN2O2	F(000) = 464
Mr = 249.99	Dx = 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

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

Refinement

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(Fo2) + (0.0401P)2 + 0.1824P] where P = (Fo2 + 2Fc2)/3
1345 reflections	(Δ/σ)max = 0.001
91 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −1.09 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

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