1-[2-(Pyrazin-2-ylsulfan­yl)eth­yl]pyrazine-2(1H)-thione

Zhao, X.-Z.; Jia, J.-J.; Ou-Yang, M.; Huang, F.-P.; Jiang, Y.-M.

doi:10.1107/S1600536811001474

organic compounds

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Volume 67| Part 2| February 2011| Page o418

doi:10.1107/S1600536811001474

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1-[2-(Pyrazin-2-ylsulfanyl)ethyl]pyrazine-2(1H)-thione

Xi-Zai Zhao,^a Jing-Jing Jia,^a Miao Ou-Yang,^b Fu-Ping Huang ^a and Yi-Min Jiang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004, People's Republic of China, and ^bDepartment of Chemistry and Life Science, Hechi University, Yizhou, Guangxi 546300, People's Republic of China
^*Correspondence e-mail: zhaoxizai203887@163.com

(Received 1 November 2010; accepted 11 January 2011; online 15 January 2011)

The title multifunctional twisted organic ligand, C₁₀H₁₀N₄S₂, contains a short C=S bond [1.671 (2) Å]. The dihedral angle between the two pyrazine rings is 39.83 (6)°. In the crystal, intermolecular C—H⋯N and C—H⋯S hydrogen bonds result in the formation of a supramolecular network.

Related literature

The assembly of molecular units in predefined arrangements is a key goal in the synthesis of crystal structures by design, see: Zheng et al. (2003 ). For bond lengths and angles in the ligand, see: Etter et al. (1992 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For versatile ligands, see: Devel et al. (2003 ).

Experimental

Crystal data

C₁₀H₁₀N₄S₂
M_r = 250.34
Monoclinic, P 2₁ /n
a = 9.762 (7) Å
b = 11.737 (9) Å
c = 10.129 (8) Å
β = 92.628 (9)°
V = 1159.2 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 296 K
0.32 × 0.20 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.873, T_max = 0.966
6280 measured reflections
2160 independent reflections
1879 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.085
S = 1.06
2160 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯N4ⁱ	0.93	2.56	3.298 (3)	137
C2—H2⋯S2ⁱⁱ	0.93	2.99	3.544 (3)	119
C3—H3⋯S2ⁱⁱⁱ	0.93	2.92	3.741 (3)	148
C8—H8⋯S1^iv	0.93	2.97	3.738 (3)	140
C9—H9⋯S1^v	0.93	2.98	3.897 (3)	169
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+2, -y, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) x, y+1, z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001474/bv2167sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001474/bv2167Isup2.hkl

checkCIF report

Comment top

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Zheng et al., 2003). Pyrazine-2-thiol is a versatile ligand which may adopt a variety of bonding modes in its coordination compounds. We originally attempted to synthesize complexes featuring Co metal chains by reaction of the Co(II) ion with pyrazine-2-thiol ligand. Unfortunately, we obtained only the title ligand, and we report herein its crystal structure. In I (Fig. 1), the ligand bond lengths and angles are within normal ranges (Etter et al., 1992). The C=S bond length was compared with the mean C—S and C=S bond lengths retrieved from a search of thiol and thione crystal structures from the CSD (Allen, 2002). X-ray data from I give a C=S bond length of 1.671 (2) Å, which is shorter than the value of 1.698 (2) Å for 2-thiopyridone and indicates a C=S rather than C-S bond. In the crystal structure, intermolecular C—H···N and C—H···S hydrogen bonds (Table 1 and Fig. 2) result in the formation of a supramolecular network structure.

Related literature top

The assembly of molecular units in predefined arrangements is a key goal in the synthesis of crystal structures by design, see: Zheng et al. (2003). For bond lengths and angles in the ligand, see: Etter et al. (1992). For a description of the Cambridge Structural Database, see: Allen (2002). For related literature [on what subject?], see: Devel et al. (2003). AUTHOR: remember to subdivide the Related literature section in future submissions

Experimental top

For the preparation of (I), a solution of CoCl₂.6H₂O (47.9 mg, 0.2 mmol) in 5 ml distilled water was added dropwise to a solution of pyrazine-2-thiol (250 mg, 2 mmol) and 1,2-dibromoethane (0.09 ml, 1 mmol) in 15 ml sodium ethoxide/ethanol solution. The resulting solution was stirred at 352 K for 3 h, then cooled to room temperature and filtered. A yellow-block crystal suitable for X-ray diffraction were obtained by slow evaporation after several days.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, showing the atom-numbering scheme.
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

1-[2-(Pyrazin-2-ylsulfanyl)ethyl]pyrazine-2(1H)-thione top

Crystal data top

C₁₀H₁₀N₄S₂	F(000) = 520
M_r = 250.34	D_x = 1.434 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.762 (7) Å	Cell parameters from 3231 reflections
b = 11.737 (9) Å	θ = 2.7–27.9°
c = 10.129 (8) Å	µ = 0.44 mm⁻¹
β = 92.628 (9)°	T = 296 K
V = 1159.2 (15) Å³	Block, yellow
Z = 4	0.32 × 0.20 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2160 independent reflections
Radiation source: fine-focus sealed tube	1879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→11
T_min = 0.873, T_max = 0.966	k = −14→12
6280 measured reflections	l = −12→10

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.039P)² + 0.347P] where P = (F_o² + 2F_c²)/3
2160 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₁₀N₄S₂	V = 1159.2 (15) Å³
M_r = 250.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.762 (7) Å	µ = 0.44 mm⁻¹
b = 11.737 (9) Å	T = 296 K
c = 10.129 (8) Å	0.32 × 0.20 × 0.08 mm
β = 92.628 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2160 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1879 reflections with I > 2σ(I)
T_min = 0.873, T_max = 0.966	R_int = 0.024
6280 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
2160 reflections	Δρ_min = −0.22 e Å⁻³
145 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
C1	0.86032 (16)	0.00044 (13)	0.30816 (17)	0.0373 (4)
C2	0.83823 (17)	−0.05822 (14)	0.42873 (18)	0.0418 (4)
H2	0.8326	−0.1372	0.4242	0.050*
C3	0.83014 (18)	0.10299 (16)	0.54879 (19)	0.0464 (4)
H3	0.8205	0.1393	0.6295	0.056*
C4	0.84852 (16)	0.16689 (14)	0.44097 (18)	0.0413 (4)
H4	0.8502	0.2459	0.4481	0.050*
C5	0.8960 (2)	0.18947 (15)	0.20807 (19)	0.0460 (4)
H5A	0.8572	0.2646	0.2203	0.055*
H5B	0.8538	0.1572	0.1280	0.055*
C6	1.0492 (2)	0.20010 (15)	0.19297 (18)	0.0479 (4)
H6A	1.0649	0.2399	0.1111	0.058*
H6B	1.0879	0.1243	0.1861	0.058*
C7	1.08904 (17)	0.41615 (14)	0.29421 (17)	0.0373 (4)
C8	1.1302 (2)	0.49827 (17)	0.3863 (2)	0.0593 (5)
H8	1.1800	0.4757	0.4623	0.071*
C9	1.0294 (2)	0.63363 (17)	0.2595 (2)	0.0587 (5)
H9	1.0053	0.7093	0.2443	0.070*
C10	0.99020 (19)	0.55385 (15)	0.1681 (2)	0.0494 (5)
H10	0.9419	0.5771	0.0915	0.059*
N1	0.86480 (13)	0.11696 (11)	0.32118 (14)	0.0366 (3)
N2	0.82515 (15)	−0.01237 (13)	0.54431 (15)	0.0464 (4)
N3	1.01858 (15)	0.44304 (12)	0.18458 (15)	0.0435 (4)
N4	1.1012 (2)	0.60692 (15)	0.3698 (2)	0.0706 (5)
S2	1.13825 (5)	0.27417 (4)	0.32673 (5)	0.04440 (15)
S1	0.87993 (6)	−0.06784 (4)	0.16546 (5)	0.05616 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0380 (9)	0.0282 (8)	0.0447 (9)	−0.0010 (6)	−0.0081 (7)	−0.0002 (7)
C2	0.0419 (9)	0.0322 (9)	0.0504 (11)	−0.0052 (7)	−0.0058 (8)	0.0033 (7)
C3	0.0401 (9)	0.0512 (11)	0.0483 (10)	−0.0018 (8)	0.0067 (8)	−0.0111 (9)
C4	0.0360 (9)	0.0328 (9)	0.0549 (11)	0.0003 (7)	0.0008 (8)	−0.0097 (8)
C5	0.0614 (11)	0.0279 (9)	0.0477 (10)	−0.0020 (8)	−0.0083 (9)	0.0071 (7)
C6	0.0671 (12)	0.0311 (9)	0.0463 (10)	−0.0027 (8)	0.0097 (9)	0.0012 (7)
C7	0.0380 (9)	0.0327 (8)	0.0415 (9)	−0.0037 (7)	0.0035 (7)	0.0037 (7)
C8	0.0782 (14)	0.0452 (11)	0.0527 (12)	−0.0052 (10)	−0.0172 (10)	−0.0010 (9)
C9	0.0630 (12)	0.0311 (10)	0.0815 (15)	0.0021 (8)	−0.0012 (11)	0.0003 (10)
C10	0.0481 (10)	0.0384 (10)	0.0610 (12)	0.0015 (8)	−0.0052 (9)	0.0091 (8)
N1	0.0382 (7)	0.0266 (7)	0.0445 (8)	0.0006 (5)	−0.0043 (6)	0.0001 (6)
N2	0.0426 (8)	0.0493 (9)	0.0473 (9)	−0.0054 (7)	0.0015 (7)	0.0029 (7)
N3	0.0496 (9)	0.0339 (8)	0.0464 (9)	−0.0016 (6)	−0.0042 (7)	0.0035 (6)
N4	0.0953 (14)	0.0412 (10)	0.0735 (13)	−0.0043 (9)	−0.0152 (11)	−0.0117 (9)
S2	0.0490 (3)	0.0346 (3)	0.0494 (3)	−0.00021 (18)	0.0004 (2)	0.01038 (18)
S1	0.0878 (4)	0.0359 (3)	0.0439 (3)	0.0014 (2)	−0.0074 (3)	−0.00664 (19)

Geometric parameters (Å, º) top

C1—N1	1.374 (2)	C6—S2	1.800 (2)
C1—C2	1.427 (3)	C6—H6A	0.9700
C1—S1	1.671 (2)	C6—H6B	0.9700
C2—N2	1.300 (2)	C7—N3	1.317 (2)
C2—H2	0.9300	C7—C8	1.388 (3)
C3—C4	1.344 (3)	C7—S2	1.761 (2)
C3—N2	1.356 (3)	C8—N4	1.315 (3)
C3—H3	0.9300	C8—H8	0.9300
C4—N1	1.363 (2)	C9—N4	1.328 (3)
C4—H4	0.9300	C9—C10	1.359 (3)
C5—N1	1.470 (2)	C9—H9	0.9300
C5—C6	1.515 (3)	C10—N3	1.339 (2)
C5—H5A	0.9700	C10—H10	0.9300
C5—H5B	0.9700

N1—C1—C2	113.79 (15)	S2—C6—H6B	108.7
N1—C1—S1	123.76 (13)	H6A—C6—H6B	107.6
C2—C1—S1	122.45 (14)	N3—C7—C8	121.60 (17)
N2—C2—C1	126.58 (17)	N3—C7—S2	120.77 (13)
N2—C2—H2	116.7	C8—C7—S2	117.60 (15)
C1—C2—H2	116.7	N4—C8—C7	122.3 (2)
C4—C3—N2	122.43 (17)	N4—C8—H8	118.9
C4—C3—H3	118.8	C7—C8—H8	118.9
N2—C3—H3	118.8	N4—C9—C10	122.09 (19)
C3—C4—N1	120.59 (16)	N4—C9—H9	119.0
C3—C4—H4	119.7	C10—C9—H9	119.0
N1—C4—H4	119.7	N3—C10—C9	122.29 (19)
N1—C5—C6	111.51 (15)	N3—C10—H10	118.9
N1—C5—H5A	109.3	C9—C10—H10	118.9
C6—C5—H5A	109.3	C4—N1—C1	120.57 (14)
N1—C5—H5B	109.3	C4—N1—C5	118.78 (15)
C6—C5—H5B	109.3	C1—N1—C5	120.53 (14)
H5A—C5—H5B	108.0	C2—N2—C3	116.02 (16)
C5—C6—S2	114.12 (13)	C7—N3—C10	115.77 (16)
C5—C6—H6A	108.7	C8—N4—C9	115.98 (18)
S2—C6—H6A	108.7	C7—S2—C6	101.42 (9)
C5—C6—H6B	108.7

N1—C1—C2—N2	−1.3 (3)	C6—C5—N1—C4	92.37 (18)
S1—C1—C2—N2	178.29 (14)	C6—C5—N1—C1	−83.77 (19)
N2—C3—C4—N1	−0.8 (3)	C1—C2—N2—C3	1.6 (3)
N1—C5—C6—S2	−65.89 (18)	C4—C3—N2—C2	−0.5 (3)
N3—C7—C8—N4	0.2 (3)	C8—C7—N3—C10	0.2 (3)
S2—C7—C8—N4	178.53 (18)	S2—C7—N3—C10	−178.07 (13)
N4—C9—C10—N3	1.5 (3)	C9—C10—N3—C7	−1.0 (3)
C3—C4—N1—C1	1.1 (2)	C7—C8—N4—C9	0.2 (3)
C3—C4—N1—C5	−175.01 (16)	C10—C9—N4—C8	−1.0 (3)
C2—C1—N1—C4	−0.2 (2)	N3—C7—S2—C6	−7.14 (16)
S1—C1—N1—C4	−179.72 (12)	C8—C7—S2—C6	174.49 (16)
C2—C1—N1—C5	175.90 (15)	C5—C6—S2—C7	−74.03 (14)
S1—C1—N1—C5	−3.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N4ⁱ	0.93	2.56	3.298 (3)	137
C2—H2···S2ⁱⁱ	0.93	2.99	3.544 (3)	119
C3—H3···S2ⁱⁱⁱ	0.93	2.92	3.741 (3)	148
C8—H8···S1^iv	0.93	2.97	3.738 (3)	140
C9—H9···S1^v	0.93	2.98	3.897 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄S₂
M_r	250.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.762 (7), 11.737 (9), 10.129 (8)
β (°)	92.628 (9)
V (Å³)	1159.2 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.32 × 0.20 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.873, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	6280, 2160, 1879
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.06
No. of reflections	2160
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.22

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N4ⁱ	0.93	2.56	3.298 (3)	137
C2—H2···S2ⁱⁱ	0.93	2.99	3.544 (3)	119
C3—H3···S2ⁱⁱⁱ	0.93	2.92	3.741 (3)	148
C8—H8···S1^iv	0.93	2.97	3.738 (3)	140
C9—H9···S1^v	0.93	2.98	3.897 (3)	169

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

Acknowledgements

This work was funded by the Guangxi Science Foundation of the Guangxi Zhuang Autonomous Region of the People's Republic of China (grant No. 2010GXNSFD 013017).

References

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