2-Acetyl­pyrazine 4-methyl­thio­semi­carbazone

Zhou, J.; Wang, Y.-X.; Chen, C.-L.; Li, M.-X.

doi:10.1107/S160053680706285X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o94

https://doi.org/10.1107/S160053680706285X

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2-Acetylpyrazine 4-methylthiosemicarbazone

Jing Zhou,^a Yu-Xia Wang,^a Chun-Ling Chen ^a and Ming-Xue Li ^a ^*

^aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475001, People's Republic of China
^*Correspondence e-mail: limingxue@henu.edu.cn

(Received 22 November 2007; accepted 24 November 2007; online 6 December 2007)

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 ); Latheef et al. (2006 ); Liberta & West (1992 ); Mendes et al. (2001 ); Padhye & Kauffman (1985 ).

Experimental

Crystal data

C₈H₁₁N₅S
M_r = 209.28
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.05
1919 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯N4ⁱ	0.86	2.42	3.137 (3)	141
N2—H2A⋯S1ⁱⁱ	0.86	2.77	3.588 (3)	161
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706285X/at2513Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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.

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

Computing details top

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

Figures top

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

2-Acetylpyrazine 4-methylthiosemicarbazone top

Crystal data top

C₈H₁₁N₅S	F(000) = 440
M_r = 209.28	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3140 reflections
a = 9.870 (8) Å	θ = 2.3–26.0°
b = 5.976 (5) Å	µ = 0.28 mm⁻¹
c = 17.517 (14) Å	T = 296 K
β = 91.251 (9)°	Block, colourless
V = 1032.8 (14) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.5°, θ_min = 2.1°
0.3° wide ω scans	h = −11→11
9944 measured reflections	k = −7→7
1919 independent reflections	l = −21→21

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0519P)² + 0.2669P] where P = (F_o² + 2F_c²)/3
1919 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₈H₁₁N₅S	V = 1032.8 (14) Å³
M_r = 209.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.870 (8) Å	µ = 0.28 mm⁻¹
b = 5.976 (5) Å	T = 296 K
c = 17.517 (14) Å	0.20 × 0.18 × 0.16 mm
β = 91.251 (9)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 reflections with I > 2σ(I)
9944 measured reflections	R_int = 0.028
1919 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
1919 reflections	Δρ_min = −0.19 e Å⁻³
129 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
S1	0.53153 (5)	0.14546 (9)	0.39197 (3)	0.0578 (2)
C1	0.3602 (2)	0.1901 (4)	0.24436 (12)	0.0638 (6)
H1A	0.2945	0.1858	0.2031	0.096*
H1B	0.4483	0.1567	0.2252	0.096*
H1C	0.3610	0.3365	0.2669	0.096*
C2	0.39403 (17)	−0.0043 (3)	0.36625 (9)	0.0403 (4)
C3	0.20657 (16)	−0.4638 (3)	0.43186 (9)	0.0381 (4)
C4	0.27288 (19)	−0.5396 (3)	0.50496 (10)	0.0517 (5)
H4A	0.3690	−0.5166	0.5026	0.078*
H4B	0.2547	−0.6958	0.5125	0.078*
H4C	0.2376	−0.4552	0.5467	0.078*
C5	0.08835 (16)	−0.5912 (3)	0.40117 (9)	0.0373 (4)
C6	0.01556 (17)	−0.5220 (3)	0.33622 (9)	0.0457 (4)
H6A	0.0401	−0.3887	0.3129	0.055*
C7	−0.1190 (2)	−0.8254 (3)	0.34285 (11)	0.0549 (5)
H7A	−0.1901	−0.9129	0.3240	0.066*
C8	−0.0499 (2)	−0.8930 (4)	0.40744 (12)	0.0626 (6)
H8A	−0.0764	−1.0244	0.4313	0.075*
N1	0.32507 (15)	0.0258 (3)	0.30149 (8)	0.0480 (4)
H1D	0.2552	−0.0570	0.2928	0.058*
N2	0.35053 (14)	−0.1701 (2)	0.41299 (8)	0.0453 (4)
H2A	0.3907	−0.1941	0.4563	0.054*
N3	0.24209 (14)	−0.2982 (2)	0.39019 (8)	0.0416 (4)
N4	−0.08728 (15)	−0.6382 (3)	0.30628 (9)	0.0517 (4)
N5	0.05389 (16)	−0.7775 (3)	0.43754 (9)	0.0536 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0550 (3)	0.0710 (4)	0.0472 (3)	−0.0316 (3)	−0.0039 (2)	−0.0010 (2)
C1	0.0728 (14)	0.0604 (13)	0.0579 (12)	−0.0125 (11)	−0.0085 (10)	0.0176 (10)
C2	0.0397 (9)	0.0426 (10)	0.0385 (9)	−0.0058 (7)	0.0000 (7)	−0.0041 (7)
C3	0.0383 (9)	0.0405 (9)	0.0352 (8)	−0.0057 (7)	−0.0026 (7)	−0.0030 (7)
C4	0.0545 (11)	0.0562 (12)	0.0439 (10)	−0.0144 (9)	−0.0136 (8)	0.0051 (9)
C5	0.0384 (9)	0.0394 (9)	0.0339 (8)	−0.0053 (7)	−0.0001 (7)	−0.0016 (7)
C6	0.0470 (10)	0.0499 (11)	0.0397 (9)	−0.0115 (8)	−0.0073 (8)	0.0044 (8)
C7	0.0489 (11)	0.0626 (13)	0.0532 (11)	−0.0211 (9)	−0.0035 (9)	−0.0084 (10)
C8	0.0685 (14)	0.0562 (13)	0.0627 (13)	−0.0295 (11)	−0.0104 (10)	0.0107 (10)
N1	0.0479 (9)	0.0490 (9)	0.0466 (9)	−0.0134 (7)	−0.0081 (7)	0.0070 (7)
N2	0.0457 (8)	0.0504 (9)	0.0393 (8)	−0.0180 (7)	−0.0099 (6)	0.0051 (7)
N3	0.0392 (8)	0.0452 (8)	0.0402 (8)	−0.0113 (6)	−0.0050 (6)	−0.0007 (6)
N4	0.0468 (9)	0.0641 (11)	0.0435 (8)	−0.0125 (8)	−0.0099 (7)	−0.0018 (8)
N5	0.0572 (10)	0.0522 (9)	0.0509 (9)	−0.0197 (8)	−0.0109 (7)	0.0117 (8)

Geometric parameters (Å, º) top

S1—C2	1.6789 (19)	C5—N5	1.331 (2)
C1—N1	1.449 (2)	C5—C6	1.395 (2)
C1—H1A	0.9600	C6—N4	1.328 (2)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—N4	1.330 (3)
C2—N1	1.322 (2)	C7—C8	1.369 (3)
C2—N2	1.361 (2)	C7—H7A	0.9300
C3—N3	1.283 (2)	C8—N5	1.334 (2)
C3—C5	1.484 (2)	C8—H8A	0.9300
C3—C4	1.496 (2)	N1—H1D	0.8600
C4—H4A	0.9600	N2—N3	1.368 (2)
C4—H4B	0.9600	N2—H2A	0.8600
C4—H4C	0.9600

N1—C1—H1A	109.5	C6—C5—C3	122.00 (15)
N1—C1—H1B	109.5	N4—C6—C5	122.84 (17)
H1A—C1—H1B	109.5	N4—C6—H6A	118.6
N1—C1—H1C	109.5	C5—C6—H6A	118.6
H1A—C1—H1C	109.5	N4—C7—C8	121.85 (17)
H1B—C1—H1C	109.5	N4—C7—H7A	119.1
N1—C2—N2	116.88 (15)	C8—C7—H7A	119.1
N1—C2—S1	123.73 (14)	N5—C8—C7	122.59 (18)
N2—C2—S1	119.38 (13)	N5—C8—H8A	118.7
N3—C3—C5	114.34 (14)	C7—C8—H8A	118.7
N3—C3—C4	126.94 (15)	C2—N1—C1	123.93 (16)
C5—C3—C4	118.71 (15)	C2—N1—H1D	118.0
C3—C4—H4A	109.5	C1—N1—H1D	118.0
C3—C4—H4B	109.5	C2—N2—N3	119.13 (14)
H4A—C4—H4B	109.5	C2—N2—H2A	120.4
C3—C4—H4C	109.5	N3—N2—H2A	120.4
H4A—C4—H4C	109.5	C3—N3—N2	119.15 (14)
H4B—C4—H4C	109.5	C6—N4—C7	115.83 (16)
N5—C5—C6	120.41 (15)	C5—N5—C8	116.45 (16)
N5—C5—C3	117.58 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···N4ⁱ	0.86	2.42	3.137 (3)	141
N2—H2A···S1ⁱⁱ	0.86	2.77	3.588 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₈H₁₁N₅S
M_r	209.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.870 (8), 5.976 (5), 17.517 (14)
β (°)	91.251 (9)
V (Å³)	1032.8 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9944, 1919, 1595
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.05
No. of reflections	1919
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···N4ⁱ	0.86	2.42	3.137 (3)	140.9
N2—H2A···S1ⁱⁱ	0.86	2.77	3.588 (3)	160.6

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

Acknowledgements

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

References

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