2-Iodo-5-nitro­thio­phene

Xu, X.Y.; Huang, G.; Zeng, X.C.; Hu, F.

doi:10.1107/S1600536810017356

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1407

https://doi.org/10.1107/S1600536810017356

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2-Iodo-5-nitrothiophene

Xing Yan Xu,^a Gang Huang,^a Xiang Chao Zeng ^a ^* and Fang Hu ^a

^aDepartment of Chemistry, Jinan University, Guangzhou, Guangdong 510632, People's Republic of China
^*Correspondence e-mail: xczeng@126.com

(Received 19 April 2010; accepted 11 May 2010; online 22 May 2010)

The title compound, C₄H₂INO₂S, was synthesized by nitration of iodothiophene with acetyl nitrate. The molecule is essentially planar, withthe nitro group tilted by 1.78 (19)° and the iodine atom displaced by 0.0233 (2) Å with respect to the thiophene ring. In the crystal structure, adjacent molecules are linked through weak I⋯O interactions [3.039 (2)Å], forming chains extending along the b axis.

Related literature

For the bioactivity of thiophene derivatives, see: Wilson et al. (2010 ); Rudra et al. (2007 ); Altman et al. (2008 ); Morley et al. (2006 ).

Experimental

Crystal data

C₄H₂INO₂S
M_r = 255.03
Monoclinic, P 2₁ /c
a = 9.195 (2) Å
b = 9.727 (2) Å
c = 7.6714 (17) Å
β = 105.043 (4)°
V = 662.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 5.07 mm⁻¹
T = 110 K
0.48 × 0.29 × 0.08 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.195, T_max = 0.687
3264 measured reflections
1419 independent reflections
1294 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.065
S = 1.09
1419 reflections
82 parameters
H-atom parameters constrained
Δρ_max = 1.65 e Å⁻³
Δρ_min = −1.07 e Å⁻³

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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: https://doi.org/10.1107/S1600536810017356/rz2440sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017356/rz2440Isup2.hkl

checkCIF report

Comment top

Many thiophene derivatives show important bioactivities and are employed as antibacterial (Morley et al., 2006), as inhibitors of Janus kinases (Wilson et al., 2010), in the identification of RBx 8700 (Rudra et al., 2007) and in the treatment of myeloproliferative disorders and cancers (Altman et al., 2008). This is the reason they have attracted our interest.

The molecule of the title compound (Fig. 1) is essentially planar, with the nitro group tilted by 1.78 (19)° and the iodine atom displaced by 0.0233 (2) Å with respect to the thiophene ring. In the crystal structure, adjacent molecules are linked through weak I···O interactions to form chains extending along the b axis. (Fig. 2).

Related literature top

For the bioactivity of thiophene derivatives, see: Wilson et al. (2010); Rudra et al. (2007); Altman et al. (2008); Morley et al. (2006).

Experimental top

Iodothiophene (6.5 g, 31 mmol) dissolved in 10 ml of acetic anhydride was introduced into a round flask, provided with a stirrer and a cooling device. Acetyl nitrate was added dropwise in forty-five minutes and the temperature was kept under 273 K. When the addition was over, the mixture was stirred for half an hour continuously at the same temperature. The nitrating flask was then surrounded with ice and kept in a refrigerator for 24 hours. The product was poured, with stirring, into finely crushed ice. After filtration, the precipitate was collected as a yellow solid. The impure product was dissolved in methanol, pale yellow monoclinic crystals suitable for X-ray analysis (m.p. 348 K, 67% yield) grew over a period of five days on slow evaporation of the solvent at room temperature.

Structure description top

For the bioactivity of thiophene derivatives, see: Wilson et al. (2010); Rudra et al. (2007); Altman et al. (2008); Morley et al. (2006).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (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. The molecular structure of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Crystal packing of the the title compound viewed along the c axis. Dashed lines indicate weak intermolecular interactions.

2-Iodo-5-nitrothiophene top

Crystal data top

C₄H₂INO₂S	F(000) = 472
M_r = 255.03	D_x = 2.556 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 348 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.195 (2) Å	Cell parameters from 2600 reflections
b = 9.727 (2) Å	θ = 2.3–27.0°
c = 7.6714 (17) Å	µ = 5.07 mm⁻¹
β = 105.043 (4)°	T = 110 K
V = 662.6 (2) Å³	Plate, pale yellow
Z = 4	0.48 × 0.29 × 0.08 mm

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1419 independent reflections
Radiation source: fine-focus sealed tube	1294 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→10
T_min = 0.195, T_max = 0.687	k = −12→6
3264 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0417P)² + 0.2502P] where P = (F_o² + 2F_c²)/3
1419 reflections	(Δ/σ)_max = 0.001
82 parameters	Δρ_max = 1.65 e Å⁻³
0 restraints	Δρ_min = −1.07 e Å⁻³

Crystal data top

C₄H₂INO₂S	V = 662.6 (2) Å³
M_r = 255.03	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.195 (2) Å	µ = 5.07 mm⁻¹
b = 9.727 (2) Å	T = 110 K
c = 7.6714 (17) Å	0.48 × 0.29 × 0.08 mm
β = 105.043 (4)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1419 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1294 reflections with I > 2σ(I)
T_min = 0.195, T_max = 0.687	R_int = 0.022
3264 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.09	Δρ_max = 1.65 e Å⁻³
1419 reflections	Δρ_min = −1.07 e Å⁻³
82 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.742893 (19)	0.45070 (2)	−0.00911 (2)	0.01661 (11)
S1	0.63408 (8)	0.77403 (7)	−0.09375 (9)	0.01554 (17)
C1	0.7728 (3)	0.6618 (3)	0.0128 (3)	0.0154 (6)
O2	0.5694 (3)	1.06507 (19)	−0.1375 (3)	0.0224 (5)
N1	0.6975 (3)	1.0473 (2)	−0.0419 (3)	0.0173 (5)
C2	0.9003 (3)	0.7266 (3)	0.1129 (4)	0.0176 (6)
H2	0.9873	0.6796	0.1805	0.021*
C3	0.8865 (3)	0.8712 (3)	0.1034 (3)	0.0171 (6)
H3	0.9627	0.9336	0.1630	0.021*
O1	0.7865 (3)	1.1411 (2)	0.0229 (3)	0.0257 (5)
C4	0.7496 (3)	0.9090 (4)	−0.0027 (3)	0.0148 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02192 (16)	0.00881 (16)	0.01937 (15)	0.00103 (5)	0.00585 (10)	0.00003 (5)
S1	0.0171 (4)	0.0104 (3)	0.0176 (3)	0.0009 (2)	0.0018 (3)	−0.0006 (2)
C1	0.0216 (14)	0.0082 (14)	0.0184 (14)	0.0040 (10)	0.0087 (11)	0.0022 (9)
O2	0.0232 (12)	0.0178 (10)	0.0254 (11)	0.0056 (8)	0.0047 (9)	0.0048 (8)
N1	0.0215 (15)	0.0148 (13)	0.0163 (12)	0.0016 (9)	0.0060 (11)	0.0011 (8)
C2	0.0165 (14)	0.0168 (13)	0.0196 (14)	0.0021 (10)	0.0046 (11)	0.0006 (10)
C3	0.0176 (14)	0.0132 (13)	0.0201 (14)	−0.0027 (10)	0.0042 (11)	−0.0028 (10)
O1	0.0331 (12)	0.0094 (11)	0.0324 (12)	−0.0033 (9)	0.0044 (10)	−0.0019 (8)
C4	0.0206 (18)	0.0087 (16)	0.0167 (16)	−0.0007 (9)	0.0079 (13)	−0.0021 (8)

Geometric parameters (Å, º) top

I1—C1	2.073 (3)	N1—C4	1.433 (4)
S1—C1	1.716 (3)	C2—C3	1.412 (4)
S1—C4	1.719 (3)	C2—H2	0.9500
C1—C2	1.376 (4)	C3—C4	1.361 (4)
O2—N1	1.227 (4)	C3—H3	0.9500
N1—O1	1.241 (3)

C1—S1—C4	89.32 (14)	C1—C2—H2	124.0
C2—C1—S1	113.2 (2)	C3—C2—H2	124.0
C2—C1—I1	125.1 (2)	C4—C3—C2	110.9 (3)
S1—C1—I1	121.68 (16)	C4—C3—H3	124.5
O2—N1—O1	124.5 (2)	C2—C3—H3	124.5
O2—N1—C4	118.3 (2)	C3—C4—N1	125.9 (3)
O1—N1—C4	117.2 (3)	C3—C4—S1	114.5 (3)
C1—C2—C3	112.0 (3)	N1—C4—S1	119.59 (19)

C4—S1—C1—C2	0.2 (2)	O2—N1—C4—C3	−178.6 (2)
C4—S1—C1—I1	179.18 (13)	O1—N1—C4—C3	1.9 (4)
S1—C1—C2—C3	−0.2 (3)	O2—N1—C4—S1	1.5 (3)
I1—C1—C2—C3	−179.22 (17)	O1—N1—C4—S1	−178.06 (17)
C1—C2—C3—C4	0.2 (3)	C1—S1—C4—C3	0.0 (2)
C2—C3—C4—N1	180.0 (2)	C1—S1—C4—N1	179.92 (18)
C2—C3—C4—S1	−0.1 (3)

Experimental details

Crystal data
Chemical formula	C₄H₂INO₂S
M_r	255.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	110
a, b, c (Å)	9.195 (2), 9.727 (2), 7.6714 (17)
β (°)	105.043 (4)
V (Å³)	662.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.07
Crystal size (mm)	0.48 × 0.29 × 0.08

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.195, 0.687
No. of measured, independent and observed [I > 2σ(I)] reflections	3264, 1419, 1294
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 1.09
No. of reflections	1419
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.65, −1.07

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

Acknowledgements

We thank the Natural Science Foundation of Guangdong Province, China (No. 06300581) for generously supporting this study.

References

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