organic compounds
4-(5-Chlorothiophen-2-yl)-1,2,3-selenadiazole
aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, bDepartment of Chemistry, Sri Sarada College for Women (Autonomus), Fairlands, Salem 636 016, India, and cDepartment of Industrial Chemistry, Alagappa University, Karaikudi 630 003, India
*Correspondence e-mail: mnpsy2004@yahoo.com
In the title compound, C6H3ClN2SSe, the selenadiazole and chlorothiophene rings are almost coplanar [dihedral angle = 5.24 (15)°]. In the crystal, C—H⋯N interactions link the molecules into chains extending along the b-axis direction. C—H⋯π interactions also occur.
Related literature
For the biological activity of selenadiazole derivatives, see: El-Bahaie et al. (1990); El-Kashef et al. (1986); Padmavathi et al. (2002); Plano et al. (2010); Stadtman (1991); Velusamy et al. (2005). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812049549/bt6854sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049549/bt6854Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812049549/bt6854Isup3.cml
A mixture of 2-acetyl-5-chlorothiophene (1 mmol), semicarbazide hydrochloride (2 mmol) and sodium acetate (3 mmol) in ethanol (10 ml) was refluxed for 4 hrs. After completion of the reaction as monitored by TLC, the mixture was poured into ice cold water and the resulting semicarbazone was filtered off. Then, a mixture of semicarbazone (1 mmol) and SeO2 (2 mmol) in tetrahydrofuran (10 ml) were refluxed on a water bath for 1 h. The selenium deposited on cooling was removed by filtration, and the filtrate was poured into crushed ice, extracted with dichloromethane, and purified by
using silica gel (60–120 mesh) with 97:3 petroleum ether: ethyl acetate as to give 4-(5-chloro-2,5-dihydrothiophen-2-yl)-1,2,3-selenadiazole.H atoms were positioned geometrically (C–H =0.93–0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) set to 1.2Ueq(C).
Selenium containing compounds, like 1,2,3-selenadiazoles are of increasing interest because of their chemical properties and biological applications such as anti-bacterial (El-Kashef et al., 1986), anti-microbial (El-Bahaie et al., 1990),anti-cancer (Plano et al., 2010) and insecticidal (Padmavathi et al., 2002) activities. It has been found that the introduction of 1,2,3-selenadiazole ring system increase the biological activity. Selenium atom has a much larger size and less
than the sulfur atom, selenium containig compounds influence the electro-optical properties of the small molecules (Velusamy et al., 2005).Glutathione peroxidases(GPx) are the antioxidant selenoenzymes protecting various organisms from oxidative stress by catalyzing the reduction of
at the expense of glutathione(GSH) (Stadtman, 1991). In view of the growing importance of selenium containing compounds, the of the title compound has been carried out.The ORTEP plot of the molecule is shown in Fig. 1. The bond lengths [Se1—N1] 1.870 (3) Å and [Se1—C1] 1.825 (4) Å are comparable with the values reported in the literature (Allen et al., 1987). The selenadiazole ring is planar [with the maximum deviation for atom C2 of 0.004 (3)°]. Both the selenadiazole ring and chlorothiophene ring are lie in a common plane, the corresponding torsion angle is [C4—C3—C2—N2] 175.5 (3)°.
The packing of the molecules is shown in Fig. 2. The crystal packing is stabilized by C—H···N intermolecular interactions, linking the molecules to chains extending along the b axis.
For the biological activity of selenadiazole derivatives, see: El-Bahaie et al. (1990); El-Kashef et al. (1986); Padmavathi et al. (2002); Plano et al. (2010); Stadtman (1991); Velusamy et al. (2005). For bond-length data, see: Allen et al. (1987).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level. | |
Fig. 2. The crystal packing. |
C6H3ClN2SSe | F(000) = 480 |
Mr = 249.57 | Dx = 2.074 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1558 reflections |
a = 6.0412 (3) Å | θ = 2.1–28.3° |
b = 19.5870 (11) Å | µ = 5.22 mm−1 |
c = 7.2010 (4) Å | T = 293 K |
β = 110.257 (3)° | Black, white crystalline |
V = 799.38 (7) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 4 |
Bruker SMART APEX CCD detector diffractometer | 1978 independent reflections |
Radiation source: fine-focus sealed tube | 1558 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −8→6 |
Tmin = 0.330, Tmax = 0.391 | k = −25→26 |
7064 measured reflections | l = −9→9 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0716P)2 + 0.3075P] where P = (Fo2 + 2Fc2)/3 |
1978 reflections | (Δ/σ)max = 0.001 |
100 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.52 e Å−3 |
C6H3ClN2SSe | V = 799.38 (7) Å3 |
Mr = 249.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.0412 (3) Å | µ = 5.22 mm−1 |
b = 19.5870 (11) Å | T = 293 K |
c = 7.2010 (4) Å | 0.22 × 0.20 × 0.18 mm |
β = 110.257 (3)° |
Bruker SMART APEX CCD detector diffractometer | 1978 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 1558 reflections with I > 2σ(I) |
Tmin = 0.330, Tmax = 0.391 | Rint = 0.044 |
7064 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.44 e Å−3 |
1978 reflections | Δρmin = −0.52 e Å−3 |
100 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3771 (6) | 0.60797 (19) | 0.2132 (5) | 0.0397 (7) | |
H1 | 0.5288 | 0.6078 | 0.2081 | 0.048* | |
C2 | 0.2578 (6) | 0.55180 (18) | 0.2343 (4) | 0.0333 (7) | |
C3 | 0.3344 (6) | 0.48114 (17) | 0.2494 (5) | 0.0328 (7) | |
C4 | 0.5358 (6) | 0.45391 (19) | 0.2353 (5) | 0.0412 (8) | |
H4 | 0.6532 | 0.4799 | 0.2134 | 0.049* | |
C5 | 0.5478 (6) | 0.38256 (19) | 0.2573 (5) | 0.0413 (8) | |
H5 | 0.6726 | 0.3562 | 0.2502 | 0.050* | |
C6 | 0.3579 (6) | 0.35688 (18) | 0.2896 (5) | 0.0376 (7) | |
Cl1 | 0.29911 (17) | 0.27326 (5) | 0.32523 (15) | 0.0529 (3) | |
N1 | −0.0347 (5) | 0.62617 (17) | 0.2239 (5) | 0.0482 (8) | |
N2 | 0.0334 (5) | 0.56419 (16) | 0.2406 (4) | 0.0428 (7) | |
S1 | 0.15880 (15) | 0.41890 (5) | 0.29606 (14) | 0.0408 (2) | |
Se1 | 0.19762 (7) | 0.684213 (19) | 0.19625 (6) | 0.04757 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0304 (16) | 0.0409 (19) | 0.0469 (18) | 0.0004 (14) | 0.0120 (14) | −0.0018 (15) |
C2 | 0.0271 (15) | 0.0379 (18) | 0.0349 (15) | −0.0008 (12) | 0.0107 (12) | −0.0014 (13) |
C3 | 0.0286 (15) | 0.0333 (16) | 0.0368 (15) | −0.0044 (13) | 0.0120 (13) | −0.0002 (13) |
C4 | 0.0325 (17) | 0.0404 (19) | 0.056 (2) | −0.0015 (14) | 0.0216 (15) | 0.0038 (16) |
C5 | 0.0336 (17) | 0.042 (2) | 0.055 (2) | 0.0011 (14) | 0.0232 (16) | −0.0024 (16) |
C6 | 0.0353 (17) | 0.0351 (18) | 0.0427 (17) | −0.0030 (14) | 0.0138 (14) | −0.0027 (14) |
Cl1 | 0.0501 (6) | 0.0375 (5) | 0.0727 (6) | −0.0066 (4) | 0.0234 (5) | 0.0031 (4) |
N1 | 0.0335 (15) | 0.0461 (19) | 0.068 (2) | 0.0029 (13) | 0.0221 (15) | 0.0005 (15) |
N2 | 0.0308 (14) | 0.0443 (18) | 0.0577 (18) | −0.0008 (13) | 0.0208 (13) | −0.0007 (14) |
S1 | 0.0289 (4) | 0.0409 (5) | 0.0559 (5) | −0.0041 (3) | 0.0190 (4) | 0.0004 (4) |
Se1 | 0.0375 (2) | 0.0371 (3) | 0.0659 (3) | 0.00047 (14) | 0.01514 (19) | 0.00089 (16) |
C1—C2 | 1.352 (5) | C4—H4 | 0.9300 |
C1—Se1 | 1.825 (4) | C5—C6 | 1.345 (5) |
C1—H1 | 0.9300 | C5—H5 | 0.9300 |
C2—N2 | 1.394 (4) | C6—Cl1 | 1.714 (4) |
C2—C3 | 1.451 (5) | C6—S1 | 1.721 (4) |
C3—C4 | 1.364 (5) | N1—N2 | 1.274 (4) |
C3—S1 | 1.724 (3) | N1—Se1 | 1.870 (3) |
C4—C5 | 1.406 (5) | ||
C2—C1—Se1 | 110.2 (3) | C5—C4—H4 | 123.4 |
C2—C1—H1 | 124.9 | C6—C5—C4 | 112.2 (3) |
Se1—C1—H1 | 124.9 | C6—C5—H5 | 123.9 |
C1—C2—N2 | 115.1 (3) | C4—C5—H5 | 123.9 |
C1—C2—C3 | 128.0 (3) | C5—C6—Cl1 | 128.1 (3) |
N2—C2—C3 | 116.9 (3) | C5—C6—S1 | 112.7 (3) |
C4—C3—C2 | 129.5 (3) | Cl1—C6—S1 | 119.2 (2) |
C4—C3—S1 | 111.3 (3) | N2—N1—Se1 | 111.1 (2) |
C2—C3—S1 | 119.2 (2) | N1—N2—C2 | 116.7 (3) |
C3—C4—C5 | 113.1 (3) | C3—S1—C6 | 90.63 (17) |
C3—C4—H4 | 123.4 | C1—Se1—N1 | 86.89 (15) |
Se1—C1—C2—N2 | −0.7 (4) | C4—C5—C6—S1 | −0.4 (4) |
Se1—C1—C2—C3 | 178.8 (3) | Se1—N1—N2—C2 | −0.3 (4) |
C1—C2—C3—C4 | −4.0 (6) | C1—C2—N2—N1 | 0.7 (5) |
N2—C2—C3—C4 | 175.4 (3) | C3—C2—N2—N1 | −178.8 (3) |
C1—C2—C3—S1 | 174.7 (3) | C4—C3—S1—C6 | −1.4 (3) |
N2—C2—C3—S1 | −5.8 (4) | C2—C3—S1—C6 | 179.7 (3) |
C2—C3—C4—C5 | −179.7 (3) | C5—C6—S1—C3 | 1.0 (3) |
S1—C3—C4—C5 | 1.4 (4) | Cl1—C6—S1—C3 | −179.5 (2) |
C3—C4—C5—C6 | −0.7 (5) | C2—C1—Se1—N1 | 0.4 (3) |
C4—C5—C6—Cl1 | −179.8 (3) | N2—N1—Se1—C1 | −0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N1i | 0.93 | 2.62 | 3.545 (5) | 171 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C6H3ClN2SSe |
Mr | 249.57 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.0412 (3), 19.5870 (11), 7.2010 (4) |
β (°) | 110.257 (3) |
V (Å3) | 799.38 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.22 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.330, 0.391 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7064, 1978, 1558 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.121, 1.01 |
No. of reflections | 1978 |
No. of parameters | 100 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.52 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N1i | 0.93 | 2.62 | 3.545 (5) | 170.7 |
Symmetry code: (i) x+1, y, z. |
Acknowledgements
The authors thank the TBI Consultancy, University of Madras, India, for the data collection.
References
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Selenium containing compounds, like 1,2,3-selenadiazoles are of increasing interest because of their chemical properties and biological applications such as anti-bacterial (El-Kashef et al., 1986), anti-microbial (El-Bahaie et al., 1990),anti-cancer (Plano et al., 2010) and insecticidal (Padmavathi et al., 2002) activities. It has been found that the introduction of 1,2,3-selenadiazole ring system increase the biological activity. Selenium atom has a much larger size and less electronegativity than the sulfur atom, selenium containig compounds influence the electro-optical properties of the small molecules (Velusamy et al., 2005).
Glutathione peroxidases(GPx) are the antioxidant selenoenzymes protecting various organisms from oxidative stress by catalyzing the reduction of hydroperoxides at the expense of glutathione(GSH) (Stadtman, 1991). In view of the growing importance of selenium containing compounds, the crystal structure of the title compound has been carried out.
The ORTEP plot of the molecule is shown in Fig. 1. The bond lengths [Se1—N1] 1.870 (3) Å and [Se1—C1] 1.825 (4) Å are comparable with the values reported in the literature (Allen et al., 1987). The selenadiazole ring is planar [with the maximum deviation for atom C2 of 0.004 (3)°]. Both the selenadiazole ring and chlorothiophene ring are lie in a common plane, the corresponding torsion angle is [C4—C3—C2—N2] 175.5 (3)°.
The packing of the molecules is shown in Fig. 2. The crystal packing is stabilized by C—H···N intermolecular interactions, linking the molecules to chains extending along the b axis.