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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o94.
Published online 2007 December 6. doi:  10.1107/S160053680706285X
PMCID: PMC2915049

2-Acetyl­pyrazine 4-methyl­thio­semi­carbazone

Abstract

The title compound, C8H11N5S, has been prepared by the reaction of 2-acetyl­pyrazine with 4-methyl-3-thio­semi­carbazide. It exists in the thione form and adopts the E configuration. The mol­ecules are connected by the inter­molecular N—H(...)N and N—H(...)S inter­actions.

Related literature

For related literature, see: Hong et al. (2004 [triangle]); Latheef et al. (2006 [triangle]); Liberta & West (1992 [triangle]); Mendes et al. (2001 [triangle]); Padhye & Kauffman (1985 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00o94-scheme1.jpg

Experimental

Crystal data

  • C8H11N5S
  • M r = 209.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o94-efi1.jpg
  • a = 9.870 (8) Å
  • b = 5.976 (5) Å
  • c = 17.517 (14) Å
  • β = 91.251 (9)°
  • V = 1032.8 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 296 (2) K
  • 0.20 × 0.18 × 0.16 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 9944 measured reflections
  • 1919 independent reflections
  • 1595 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.100
  • S = 1.05
  • 1919 reflections
  • 129 parameters
  • H-atom parameters constrained
  • Δρmax = 0.22 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680706285X/at2513sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680706285X/at2513Isup2.hkl

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

Acknowledgments

This work was financially supported by the Foundation of the Education Department of Henan Province (No. 2007150012)

supplementary crystallographic information

Comment

Thiosemicarbazone and its derivatives have attracted interest in recent years due to their beneficial biological applications (Padhye & Kauffman, 1985). The presence of alkyl groups at the terminal N(4) position can increase the biological activity (Liberta & West, 1992). So we report here the crystal structure of N(4)-methyl thiosemicarbazones derived from 2-acetylpyrazine.

The geometry of the title compound (I) is well planar (Fig. 1). The molecular exists in the E conformation about the C3—N3 bond as confirmed by the C5—C3—N3—N2 torsion angle of 179.6 °. The C—S bond distance of 1.679 (2) Å, which is much short than C—S single bond (Latheef et al., 2006), shows that the title compound adopts the thione form. The bond length of C3—N3 is 1.283 (2) Å, which is within the range of typical bond length of C?N double bond. The bond length of N2—N3 is 1.368 (2) Å, accepted as typical for a single N—N bond, and in accordance with those of other thiosemicarbazone (Mendes et al., 2001; Hong et al., 2004).

In the crystal packing, the molecules are connected through an extended network of intermolecular hydrogen bonds involving the nitrogen atoms N1, N2, N4 and sulfur atom S1.

Experimental

All reagents were commercially available and of analytical grade. 2-Acetylpyrazine (0.24 g, 2 mmol) and 4-methyl-3-thiosemicarbazide (0.21 g, 2 mmol) were mixed in ethanol (30 ml). Eight drops of acetic acid were added and the solution was refluxed for 4 h. Crystals of (I) suitable for X-ray diffraction analysis were obtained from the filtrate by slow evaporation at room temperature.

Refinement

All H atoms were positioned geometrically and refined as riding with C—H = 0.96 Å (methyl) or 0.93 Å (aromatic), N—H = 0.86 Å and with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(C) for methyl groups.

Figures

Fig. 1.
The molecular structure of (I), showing atom displacement ellipsoids drawn at the 50% probability level.

Crystal data

C8H11N5SF000 = 440
Mr = 209.28Dx = 1.346 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3140 reflections
a = 9.870 (8) Åθ = 2.3–26.0º
b = 5.976 (5) ŵ = 0.28 mm1
c = 17.517 (14) ÅT = 296 (2) K
β = 91.251 (9)ºBlock, colourless
V = 1032.8 (14) Å30.20 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer1595 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Monochromator: graphiteθmax = 25.5º
T = 296(2) Kθmin = 2.1º
0.3° wide ω scansh = −11→11
Absorption correction: nonek = −7→7
9944 measured reflectionsl = −21→21
1919 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.100  w = 1/[σ2(Fo2) + (0.0519P)2 + 0.2669P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1919 reflectionsΔρmax = 0.22 e Å3
129 parametersΔρmin = −0.19 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
S10.53153 (5)0.14546 (9)0.39197 (3)0.0578 (2)
C10.3602 (2)0.1901 (4)0.24436 (12)0.0638 (6)
H1A0.29450.18580.20310.096*
H1B0.44830.15670.22520.096*
H1C0.36100.33650.26690.096*
C20.39403 (17)−0.0043 (3)0.36625 (9)0.0403 (4)
C30.20657 (16)−0.4638 (3)0.43186 (9)0.0381 (4)
C40.27288 (19)−0.5396 (3)0.50496 (10)0.0517 (5)
H4A0.3690−0.51660.50260.078*
H4B0.2547−0.69580.51250.078*
H4C0.2376−0.45520.54670.078*
C50.08835 (16)−0.5912 (3)0.40117 (9)0.0373 (4)
C60.01556 (17)−0.5220 (3)0.33622 (9)0.0457 (4)
H6A0.0401−0.38870.31290.055*
C7−0.1190 (2)−0.8254 (3)0.34285 (11)0.0549 (5)
H7A−0.1901−0.91290.32400.066*
C8−0.0499 (2)−0.8930 (4)0.40744 (12)0.0626 (6)
H8A−0.0764−1.02440.43130.075*
N10.32507 (15)0.0258 (3)0.30149 (8)0.0480 (4)
H1D0.2552−0.05700.29280.058*
N20.35053 (14)−0.1701 (2)0.41299 (8)0.0453 (4)
H2A0.3907−0.19410.45630.054*
N30.24209 (14)−0.2982 (2)0.39019 (8)0.0416 (4)
N4−0.08728 (15)−0.6382 (3)0.30628 (9)0.0517 (4)
N50.05389 (16)−0.7775 (3)0.43754 (9)0.0536 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0550 (3)0.0710 (4)0.0472 (3)−0.0316 (3)−0.0039 (2)−0.0010 (2)
C10.0728 (14)0.0604 (13)0.0579 (12)−0.0125 (11)−0.0085 (10)0.0176 (10)
C20.0397 (9)0.0426 (10)0.0385 (9)−0.0058 (7)0.0000 (7)−0.0041 (7)
C30.0383 (9)0.0405 (9)0.0352 (8)−0.0057 (7)−0.0026 (7)−0.0030 (7)
C40.0545 (11)0.0562 (12)0.0439 (10)−0.0144 (9)−0.0136 (8)0.0051 (9)
C50.0384 (9)0.0394 (9)0.0339 (8)−0.0053 (7)−0.0001 (7)−0.0016 (7)
C60.0470 (10)0.0499 (11)0.0397 (9)−0.0115 (8)−0.0073 (8)0.0044 (8)
C70.0489 (11)0.0626 (13)0.0532 (11)−0.0211 (9)−0.0035 (9)−0.0084 (10)
C80.0685 (14)0.0562 (13)0.0627 (13)−0.0295 (11)−0.0104 (10)0.0107 (10)
N10.0479 (9)0.0490 (9)0.0466 (9)−0.0134 (7)−0.0081 (7)0.0070 (7)
N20.0457 (8)0.0504 (9)0.0393 (8)−0.0180 (7)−0.0099 (6)0.0051 (7)
N30.0392 (8)0.0452 (8)0.0402 (8)−0.0113 (6)−0.0050 (6)−0.0007 (6)
N40.0468 (9)0.0641 (11)0.0435 (8)−0.0125 (8)−0.0099 (7)−0.0018 (8)
N50.0572 (10)0.0522 (9)0.0509 (9)−0.0197 (8)−0.0109 (7)0.0117 (8)

Geometric parameters (Å, °)

S1—C21.6789 (19)C5—N51.331 (2)
C1—N11.449 (2)C5—C61.395 (2)
C1—H1A0.9600C6—N41.328 (2)
C1—H1B0.9600C6—H6A0.9300
C1—H1C0.9600C7—N41.330 (3)
C2—N11.322 (2)C7—C81.369 (3)
C2—N21.361 (2)C7—H7A0.9300
C3—N31.283 (2)C8—N51.334 (2)
C3—C51.484 (2)C8—H8A0.9300
C3—C41.496 (2)N1—H1D0.8600
C4—H4A0.9600N2—N31.368 (2)
C4—H4B0.9600N2—H2A0.8600
C4—H4C0.9600
N1—C1—H1A109.5C6—C5—C3122.00 (15)
N1—C1—H1B109.5N4—C6—C5122.84 (17)
H1A—C1—H1B109.5N4—C6—H6A118.6
N1—C1—H1C109.5C5—C6—H6A118.6
H1A—C1—H1C109.5N4—C7—C8121.85 (17)
H1B—C1—H1C109.5N4—C7—H7A119.1
N1—C2—N2116.88 (15)C8—C7—H7A119.1
N1—C2—S1123.73 (14)N5—C8—C7122.59 (18)
N2—C2—S1119.38 (13)N5—C8—H8A118.7
N3—C3—C5114.34 (14)C7—C8—H8A118.7
N3—C3—C4126.94 (15)C2—N1—C1123.93 (16)
C5—C3—C4118.71 (15)C2—N1—H1D118.0
C3—C4—H4A109.5C1—N1—H1D118.0
C3—C4—H4B109.5C2—N2—N3119.13 (14)
H4A—C4—H4B109.5C2—N2—H2A120.4
C3—C4—H4C109.5N3—N2—H2A120.4
H4A—C4—H4C109.5C3—N3—N2119.15 (14)
H4B—C4—H4C109.5C6—N4—C7115.83 (16)
N5—C5—C6120.41 (15)C5—N5—C8116.45 (16)
N5—C5—C3117.58 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1D···N4i0.862.423.137 (3)141
N2—H2A···S1ii0.862.773.588 (3)161

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2513).

References

  • Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hong, W. S., Wu, C. Y., Lee, C. S., Hwang, W. S. & Chiang, M. Y. (2004). J. Organomet. Chem.689, 277–285.
  • Latheef, L., Manoj, E. & Prathapachandra Kurup, M. R. (2006). Acta Cryst. C62, o16–o18. [PubMed]
  • Liberta, A. E. & West, D. X. (1992). Biometals, 5, 121–126. [PubMed]
  • Mendes, I. C., Teixeira, L. R., Lima, R., Beraldo, H., Speziali, N. L. & West, D. X. (2001). J. Mol. Struct.559, 355–360.
  • Padhye, S. B. & Kauffman, G. B. (1985). Coord. Chem. Rev.63, 127–160.
  • Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography