Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Pages o1350-o1351
https://doi.org/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. Pittaa and Carlos A. de Simonec*

aLaboratório de Síntese e Planejamento de Fármacos, Departamento de Antibióticos, Universidade Federal de Pernambuco, 50670-910 Recife, PE, Brazil, bLaboratório de Síntese e Vetorização de Moléculas Bioativas, Universidade Estadual da Paraíba, 58020-540 João Pessoa, PB, Brazil, and cDepartamento de Física e Informática, Instituto de Física de São Carlos, Universidade de São Paulo - USP, 13560-970 - São Carlos, SP, Brazil
*Correspondence e-mail: casimone@ifsc.usp.br

(Received 3 May 2010; accepted 10 May 2010; online 15 May 2010)

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[Campaigne, E. (1984). Comprehensive Heterocyclic Chemistry, Vol. 4, edited by A. R. Katritzky & C. W. Rees, pp. 863-934. Oxford: Pergamon.]); Kleemann et al. (2006[Kleemann, A., Engel, J. B., Kutscher, B. & Reichert, D. (2006). Pharmaceutical Substances. New York, Stuttgart: Georg Thieme Verlag.]). For the biological activity of 2-amino thio­phene derivatives, see: Chakrabarti et al. (1982[Chakrabarti, J. K., Hotten, T. M., Morgan, S. E., Pullar, I. A., Rackham, D. M., Risius, F. C., Wedley, S., Chaney, M. & Jones, N. D. (1982). J. Med. Chem. 25, 1133-1140.]); Calligaro et al. (1997[Calligaro, D. O., Fairhurst, J., Hotten, T. M., Moore, N. A. & Tupper, D. E. (1997). Bioorg. Med. Chem. Lett. 7, 25-30.]); Nikolakopoulos et al. (2006[Nikolakopoulos, G., Figler, H., Linden, J. & Scammells, P. J. (2006). Bioorg. Med. Chem. 14, 2358-2365.]). For the synthesis of 2-amino thio­phenes, see: Gewald (1965[Gewald, K. (1965). Chem. Ber. 98, 3571-3577.]); Gewald et al. (1966[Gewald, K., Schinke, E. & Bottcher, H. (1966). Chem. Ber. 99, 99-100.]); Sridhar et al. (2007[Sridhar, M., Rao, R. M., Baba, N. H. K. & Kumbhare, R. M. (2007). Tetrahedron Lett. 48, 3171-3172.]). For related structures, see: Stephenson et al. (1995[Stephenson, G. A., Borchardt, T. B., Byrn, S. R., Bowyer, J., Bunnell, C. A., Snorek, S. V. & Yu, L. (1995). J. Pharm. Sci. 84, 1385-1386.]); Yu (2002[Yu, L. (2002). J. Phys. Chem. A, 106, 544-550.]); Chen et al. (2005[Chen, S., Guzei, I. A. & Yu, L. (2005). J. Am. Chem. Soc. 127, 9881-9885.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. J. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19]). For puckering parameters, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data

  • C16H15N3O2S

  • Mr = 313.37

  • Monoclinic, P 21 /c

  • 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)

  • Rint = 0.046
Refinement

  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.162

  • S = 1.07

  • 3147 reflections

  • 200 parameters

  • H-atom parameters constrained

  • Δρmax = 0.29 e Å−3

  • Δρmin = −0.31 e Å−3

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

Data collection: COLLECT (Nonius, 1997[Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017149/dn2562Isup2.hkl

checkCIF report


Comment top

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, QT = 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).

Related literature top

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 top

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.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(C or N).The maximum and minimum residual electron density peaks were located 1.10 and 0.78 Å, from the H4A and S1 atoms respectively.

Structure description top

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, QT = 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).

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).

Computing details top

Data collection: COLLECT (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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).

Figures top
[Figure 1] Fig. 1. Molecular view of C16H15N3O2S, showing the atom labelling scheme. Ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. View showing π- π stacking interactions between the molecules. For the sake of clarity, H atoms have been omitted.
2-(2-Nitroanilino)-5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene- 3-carbonitrile top
Crystal data top
C16H15N3O2SF(000) = 656
Mr = 313.37Dx = 1.388 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6392 reflections
a = 7.0273 (3) Åθ = 2.9–26.7°
b = 14.4569 (6) ŵ = 0.23 mm−1
c = 14.8867 (7) ÅT = 295 K
β = 97.571 (2)°Prism, colorless
V = 1499.18 (11) Å30.35 × 0.32 × 0.27 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		2452 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590Rint = 0.046
Horizonally mounted graphite crystal monochromatorθmax = 26.6°, θmin = 3.1°
Detector resolution: 9 pixels mm-1h = −8→8
CCD rotation images,thick slices scansk = −15→18
9360 measured reflectionsl = −18→18
3147 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.1026P)2 + 0.1476P]
where P = (Fo2 + 2Fc2)/3
3147 reflections(Δ/σ)max = 0.001
200 parametersΔρmax = 0.29 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C16H15N3O2SV = 1499.18 (11) Å3
Mr = 313.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0273 (3) ŵ = 0.23 mm−1
b = 14.4569 (6) ÅT = 295 K
c = 14.8867 (7) Å0.35 × 0.32 × 0.27 mm
β = 97.571 (2)°
Data collection top
Nonius KappaCCD
diffractometer		2452 reflections with I > 2σ(I)
9360 measured reflectionsRint = 0.046
3147 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.162H-atom parameters constrained
S = 1.07Δρmax = 0.29 e Å−3
3147 reflectionsΔρmin = −0.31 e Å−3
200 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
xyzUiso*/Ueq
S10.29875 (7)0.33887 (3)0.05524 (3)0.0529 (2)
O10.1864 (3)0.64817 (11)−0.14472 (10)0.0763 (5)
O20.1729 (3)0.78484 (12)−0.09126 (12)0.0887 (6)
N10.2433 (2)0.50661 (11)−0.03762 (10)0.0531 (4)
H10.22770.5305−0.09100.064*
N20.1906 (2)0.70191 (13)−0.07994 (12)0.0594 (4)
N30.2128 (4)0.44432 (17)−0.26828 (13)0.0871 (7)
C10.2620 (2)0.41167 (13)−0.03697 (12)0.0474 (4)
C20.2544 (3)0.36042 (14)−0.11578 (12)0.0501 (4)
C30.2772 (3)0.26261 (14)−0.10156 (13)0.0527 (5)
C40.2731 (4)0.19525 (16)−0.17935 (14)0.0673 (6)
H4A0.40410.1775−0.18500.081*
H4B0.22210.2269−0.23480.081*
C50.1554 (3)0.10721 (16)−0.17147 (15)0.0688 (6)
H5A0.02710.1251−0.16090.083*
H5B0.14380.0750−0.22910.083*
C60.2345 (4)0.04019 (15)−0.09784 (16)0.0707 (6)
H6A0.36880.0293−0.10310.085*
H6B0.1677−0.0183−0.10860.085*
C70.2190 (4)0.07060 (16)−0.00136 (16)0.0710 (6)
H7A0.08720.08880.00210.085*
H7B0.24710.01790.03850.085*
C80.3487 (4)0.14916 (15)0.03367 (16)0.0669 (6)
H8A0.47980.13240.02700.080*
H8B0.34180.15640.09790.080*
C90.3044 (3)0.24118 (14)−0.01205 (13)0.0551 (5)
C100.2447 (2)0.57016 (13)0.03089 (12)0.0473 (4)
C110.2192 (3)0.66561 (13)0.01206 (13)0.0491 (4)
C120.2185 (3)0.73041 (15)0.08074 (14)0.0587 (5)
H120.20120.79270.06630.070*
C130.2430 (3)0.70360 (16)0.16918 (15)0.0635 (5)
H130.24270.74720.21510.076*
C140.2683 (3)0.61106 (16)0.18993 (14)0.0636 (5)
H140.28450.59240.25030.076*
C150.2700 (3)0.54584 (15)0.12264 (13)0.0594 (5)
H150.28840.48400.13860.071*
C160.2285 (3)0.40474 (15)−0.20159 (13)0.0594 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0672 (3)0.0504 (3)0.0413 (3)−0.00605 (19)0.0074 (2)0.00132 (18)
O10.1190 (14)0.0599 (10)0.0478 (8)−0.0002 (8)0.0034 (8)0.0025 (7)
O20.1394 (16)0.0503 (10)0.0753 (11)0.0042 (9)0.0103 (10)0.0123 (8)
N10.0707 (10)0.0480 (9)0.0407 (8)−0.0010 (7)0.0077 (7)0.0000 (7)
N20.0684 (10)0.0538 (10)0.0558 (10)−0.0019 (7)0.0072 (8)0.0042 (8)
N30.1274 (18)0.0861 (15)0.0481 (11)0.0209 (13)0.0123 (10)0.0112 (10)
C10.0508 (9)0.0485 (10)0.0427 (9)−0.0040 (7)0.0061 (7)0.0005 (7)
C20.0563 (10)0.0523 (10)0.0422 (9)−0.0028 (8)0.0078 (7)0.0000 (8)
C30.0604 (10)0.0505 (10)0.0475 (10)−0.0033 (8)0.0084 (8)−0.0032 (8)
C40.0929 (15)0.0587 (12)0.0513 (11)−0.0070 (11)0.0131 (10)−0.0077 (10)
C50.0836 (14)0.0569 (12)0.0647 (13)0.0012 (10)0.0048 (11)−0.0140 (10)
C60.0909 (16)0.0494 (12)0.0705 (14)−0.0006 (11)0.0057 (11)−0.0047 (10)
C70.0915 (15)0.0502 (12)0.0715 (14)−0.0034 (10)0.0116 (11)0.0040 (11)
C80.0859 (14)0.0559 (13)0.0566 (12)−0.0038 (10)0.0010 (10)0.0049 (9)
C90.0650 (11)0.0505 (11)0.0497 (10)−0.0063 (8)0.0069 (8)−0.0009 (8)
C100.0481 (9)0.0511 (10)0.0432 (9)−0.0042 (7)0.0081 (7)−0.0011 (8)
C110.0493 (9)0.0508 (11)0.0474 (10)−0.0045 (7)0.0071 (7)0.0001 (7)
C120.0653 (11)0.0520 (11)0.0597 (12)0.0000 (9)0.0120 (9)−0.0070 (9)
C130.0725 (13)0.0632 (13)0.0569 (11)−0.0048 (10)0.0169 (9)−0.0144 (10)
C140.0811 (13)0.0665 (13)0.0448 (11)−0.0042 (10)0.0147 (9)−0.0043 (9)
C150.0786 (13)0.0532 (11)0.0478 (11)−0.0023 (10)0.0134 (9)0.0008 (9)
C160.0750 (12)0.0587 (12)0.0442 (10)0.0058 (9)0.0066 (8)−0.0043 (9)
Geometric parameters (Å, º) top
S1—C11.7220 (18)C6—C71.520 (3)
S1—C91.735 (2)C6—H6A0.9700
O1—N21.236 (2)C6—H6B0.9700
O2—N21.215 (2)C7—C81.506 (3)
N1—C101.372 (2)C7—H7A0.9700
N1—C11.379 (2)C7—H7B0.9700
N1—H10.8600C8—C91.508 (3)
N2—C111.456 (2)C8—H8A0.9700
N3—C161.139 (3)C8—H8B0.9700
C1—C21.383 (2)C10—C151.399 (3)
C2—C161.419 (3)C10—C111.415 (3)
C2—C31.436 (3)C11—C121.387 (3)
C3—C91.357 (3)C12—C131.361 (3)
C3—C41.510 (3)C12—H120.9300
C4—C51.531 (3)C13—C141.379 (3)
C4—H4A0.9700C13—H130.9300
C4—H4B0.9700C14—C151.377 (3)
C5—C61.513 (3)C14—H140.9300
C5—H5A0.9700C15—H150.9300
C5—H5B0.9700
C1—S1—C992.84 (9)C8—C7—C6115.5 (2)
C10—N1—C1132.09 (16)C8—C7—H7A108.4
C10—N1—H1114.0C6—C7—H7A108.4
C1—N1—H1114.0C8—C7—H7B108.4
O2—N2—O1121.38 (19)C6—C7—H7B108.4
O2—N2—C11119.03 (18)H7A—C7—H7B107.5
O1—N2—C11119.59 (17)C7—C8—C9115.43 (19)
N1—C1—C2122.32 (17)C7—C8—H8A108.4
N1—C1—S1128.18 (14)C9—C8—H8A108.4
C2—C1—S1109.50 (14)C7—C8—H8B108.4
C1—C2—C16120.52 (18)C9—C8—H8B108.4
C1—C2—C3114.31 (17)H8A—C8—H8B107.5
C16—C2—C3125.17 (18)C3—C9—C8129.69 (19)
C9—C3—C2111.61 (17)C3—C9—S1111.73 (15)
C9—C3—C4126.28 (19)C8—C9—S1118.46 (15)
C2—C3—C4122.11 (18)N1—C10—C15123.03 (18)
C3—C4—C5115.66 (17)N1—C10—C11121.17 (16)
C3—C4—H4A108.4C15—C10—C11115.79 (17)
C5—C4—H4A108.4C12—C11—C10121.68 (18)
C3—C4—H4B108.4C12—C11—N2115.89 (18)
C5—C4—H4B108.4C10—C11—N2122.43 (16)
H4A—C4—H4B107.4C13—C12—C11120.6 (2)
C6—C5—C4115.93 (19)C13—C12—H12119.7
C6—C5—H5A108.3C11—C12—H12119.7
C4—C5—H5A108.3C12—C13—C14119.26 (19)
C6—C5—H5B108.3C12—C13—H13120.4
C4—C5—H5B108.3C14—C13—H13120.4
H5A—C5—H5B107.4C15—C14—C13120.97 (19)
C5—C6—C7115.73 (19)C15—C14—H14119.5
C5—C6—H6A108.3C13—C14—H14119.5
C7—C6—H6A108.3C14—C15—C10121.7 (2)
C5—C6—H6B108.3C14—C15—H15119.1
C7—C6—H6B108.3C10—C15—H15119.1
H6A—C6—H6B107.4N3—C16—C2176.3 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.892.593 (2)138
C12—H12···O20.932.332.657 (3)100
C15—H15···S10.932.443.171 (2)135

Experimental details

Crystal data
Chemical formulaC16H15N3O2S
Mr313.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)7.0273 (3), 14.4569 (6), 14.8867 (7)
β (°) 97.571 (2)
V (Å3)1499.18 (11)
Z4
Radiation typeMo Kα
µ (mm−1)0.23
Crystal size (mm)0.35 × 0.32 × 0.27
Data collection
DiffractometerNonius KappaCCD
Absorption correction–
No. of measured, independent and
observed [I > 2σ(I)] reflections		9360, 3147, 2452
Rint0.046
(sin θ/λ)max (Å−1)0.630
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.162, 1.07
No. of reflections3147
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.29, −0.31

Computer programs: COLLECT (Nonius, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.861.892.593 (2)138
C12—H12···O20.932.332.657 (3)100
C15—H15···S10.932.443.171 (2)135
π–π stacking interactions (Å, °) between the thiophene (Cg1) and benzene (Cg2) rings. top
Cg1···Cg2Cg1 to plane 2Cg2 to plane 1Offset
Cg1···Cg2i3.7089 (12)-3.5039 (9)-3.5021 (9)19.4
Cg1···Cg2ii3.6170 (12)3.4761 (9)3.4878 (9)16.0
Symmetry codes: (i) -x, 1-y, -z; (ii) 1-x, 1-y, -z.
 

Acknowledgements

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

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. J. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19  CrossRef Google Scholar
 First citationCalligaro, D. O., Fairhurst, J., Hotten, T. M., Moore, N. A. & Tupper, D. E. (1997). Bioorg. Med. Chem. Lett. 7, 25–30.  CrossRef CAS Web of Science Google Scholar
 First citationCampaigne, E. (1984). Comprehensive Heterocyclic Chemistry, Vol. 4, edited by A. R. Katritzky & C. W. Rees, pp. 863–934. Oxford: Pergamon.  Google Scholar
 First citationChakrabarti, J. K., Hotten, T. M., Morgan, S. E., Pullar, I. A., Rackham, D. M., Risius, F. C., Wedley, S., Chaney, M. & Jones, N. D. (1982). J. Med. Chem. 25, 1133–1140.  CrossRef CAS PubMed Web of Science Google Scholar
 First citationChen, S., Guzei, I. A. & Yu, L. (2005). J. Am. Chem. Soc. 127, 9881–9885.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationFarrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.  CrossRef CAS IUCr Journals Google Scholar
 First citationGewald, K. (1965). Chem. Ber. 98, 3571–3577.  CrossRef CAS Web of Science Google Scholar
 First citationGewald, K., Schinke, E. & Bottcher, H. (1966). Chem. Ber. 99, 99–100.  Google Scholar
 First citationKleemann, A., Engel, J. B., Kutscher, B. & Reichert, D. (2006). Pharmaceutical Substances. New York, Stuttgart: Georg Thieme Verlag.  Google Scholar
 First citationNikolakopoulos, G., Figler, H., Linden, J. & Scammells, P. J. (2006). Bioorg. Med. Chem. 14, 2358–2365.  Web of Science CrossRef PubMed CAS Google Scholar
 First citationNonius (1997). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSridhar, M., Rao, R. M., Baba, N. H. K. & Kumbhare, R. M. (2007). Tetrahedron Lett. 48, 3171–3172.  Web of Science CrossRef CAS Google Scholar
 First citationStephenson, G. A., Borchardt, T. B., Byrn, S. R., Bowyer, J., Bunnell, C. A., Snorek, S. V. & Yu, L. (1995). J. Pharm. Sci. 84, 1385–1386.  CrossRef CAS PubMed Web of Science Google Scholar
 First citationYu, L. (2002). J. Phys. Chem. A, 106, 544–550.  Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 6| June 2010| Pages o1350-o1351
https://doi.org/10.1107/S1600536810017149
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS