2-(2-Nitro­anilino)-5,6,7,8-tetra­hydro-4H-cyclo­hepta­[b]thio­phene-3-carbonitrile

Maria do Carmo A de Lima; Francisco J B Mendonça Junior; Suely L Galdino; Ivan R Pitta; Carlos A de Simone

doi:10.1107/S1600536810017149

. 2010 May 15;66(Pt 6):o1350–o1351. doi: 10.1107/S1600536810017149

2-(2-Nitroanilino)-5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene-3-carbonitrile

Maria do Carmo A de Lima ^a, Francisco J B Mendonça Junior ^b, Suely L Galdino ^a, Ivan R Pitta ^a, Carlos A de Simone ^c,^*

PMCID: PMC2979624 PMID: 21579437

Abstract

The title compound, C₁₆H₁₅N₃O₂S, was synthesized by the reaction of 2-amino-5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene-3-carbonitrile and o-fluoronitrobenzene. The thiophene and nitrophenyl rings and amino and carbonitrile groups are coplanar with a maximum deviation of 0.046 (2) Å and a dihedral angle of 0.92 (6)° between the rings. The cyclohepta ring adopts a chair conformation. Intramolecular N—H⋯O and C—H⋯S interactions occur. In the crystal, the molecules form layers that are linked by π–π stacking interactions between the thiophene and benzene rings [centroid–centroid distances = 3.7089 (12) and 3.6170 (12) Å].

Related literature

For background to 2-substituted thiophenes, see: Campaigne (1984 ▶); Kleemann et al. (2006 ▶). For the biological activity of 2-amino thiophene derivatives, see: Chakrabarti et al. (1982 ▶); Calligaro et al. (1997 ▶); Nikolakopoulos et al. (2006 ▶). For the synthesis of 2-amino thiophenes, see: Gewald (1965 ▶); Gewald et al. (1966 ▶); Sridhar et al. (2007 ▶). For related structures, see: Stephenson et al. (1995 ▶); Yu (2002 ▶); Chen et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₆H₁₅N₃O₂S
M _r = 313.37
Monoclinic,
a = 7.0273 (3) Å
b = 14.4569 (6) Å
c = 14.8867 (7) Å
β = 97.571 (2)°
V = 1499.18 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.35 × 0.32 × 0.27 mm

Data collection

Nonius KappaCCD diffractometer
9360 measured reflections
3147 independent reflections
2452 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.162
S = 1.07
3147 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017149/dn2562sup1.cif

e-66-o1350-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017149/dn2562Isup2.hkl

e-66-o1350-Isup2.hkl^{(148.3KB, hkl)}

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
N1—H1⋯O1	0.86	1.89	2.593 (2)	138
C15—H15⋯S1	0.93	2.44	3.171 (2)	135

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Acknowledgments

This work has received partial support from CNPq, CAPES, FACEPE and FINEP.

supplementary crystallographic information

Comment

The various uses of 2-substituted thiophenes have been well documented (Campaigne, 1984; Kleemann et al., 2006). Amongst these appplications, are neuroleptics activities, as found for a series of thienobenzodiazepines (Chakrabarti et al., 1982; Calligaro et al., 1997; Nikolakopoulos et al., 2006). In this work, we report the structure of the title compound prepared by the reaction of 2-amino-5,6,7, 8-tetrahydro-4H-ciclohepta[b]thiophene-3- carbonitrile and o-fluoro- nitrobenzene.

As indicated in the literature, compounds that presents o-nitrophenyl group linked to 2-amino-thiophene ring have great potential to produce crystalline structures, as found in 5-methyl-2-[(2-nitrophenyl)-amino]- thiophene-3-carbonitrile (ROY), that presents seven polymorphs coexisting at room temperature (Stephenson et al., 1995; Yu, 2002; Chen et al., 2005).

In the title compound,the least squares plane passing through all atoms of thiophene and nitrophenyl rings, and amino and carbonitrile groups, show planarity with maximum deviation of [0.046 (2) Å] for atom N3 (Fig.1). Bond lengths and angles are in good agreement with the expected values reported in the literature (Allen et al., 1987). The cyclohepta ring adopts a chair conformation and the calculated puckering parameters are: q₂ = 0.175 (9) Å, q₃ = 0.619 (9) Å, Q_T = 0.643 (9) Å, θ = 15.8 (9)° , φ₂ = 56.1 (8)° and φ₃ = 78.4 (8)° (Cremer & Pople, 1975).

In the molecule there are, intramolecular N–H··· O, C—H··· O and C—H··· S interactions that are responsible for the roughly planar arrangement (Table 1). In the packing molecules form layers that extends along a direction parallel to the (100) plane, and are linked by π-π stacking interactions between thiophene [Cg1] and benzene [Cg2] rings(Table 2, Fig. 2).

Experimental

To a stirred suspension mixture of dry THF (20 ml) and NaH (0,105 mol) at 0 °C under nitrogen was added dropwise a solution of 2-amino-5,6,7,8- tetrahydro-4H-ciclohepta[b]thiophene-3-carbonitrile (0,07 mol), o-fluoro-nitrobenzene (0,07 mol) in 80 ml of dry THF. The reaction mixture was stirred under room temperature for 22 h. The resulting mixture was adjusted to pH = 5 with hydroclorid acid 2 N and them extracted with CHCl₃. The extracted was washed with aqueous Na₂CO₃, water, dried (CaCl₂) and evaporated under reduced pression. The dark red solid obtained was purified by recrystallization from absolute ethanol, affording the title compound as red crystals (21.4 g, (98%), m.p. 100-102 °C)(Gewald, 1965; Gewald et al., 1966; Sridhar et al., 2007). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation at room temperature of a solution of the pure title compound in ethanol/dichloromethane (1:1).

NMR ¹H (200 MHz, CDCl₃) δ : 1.60-1.70 (m, 4H), 1.80-1.90 (m, 2H), 2,70-2,80 (m, 4H), 6.90 (dt, 1H, J = 8.6, 1.6 Hz), 7.20 (dd, 1H, J = 8.6, 0.8 Hz), 7.5 (dt, 1H, J = 8.6, 8.2 Hz), 8.2 (dd, 1H, J = 8.4, 1.6 Hz), 9.6 (s, 1H).

NMR ¹³C (200 MHz, CDCl₃) δ : 27.2-31.9 (5 CH₂), 107.7, 113.9, 116.1, 119.5, 126.6, 133.9, 135.7, 136.1, 139.0, 141.4, 145.3.