4-(Pyridin-2-yl)-1,3-dithiol-2-one

Zhou, G.; Chen, X.

doi:10.1107/S1600536812001407

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o432

doi:10.1107/S1600536812001407

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4-(Pyridin-2-yl)-1,3-dithiol-2-one

Guoquan Zhou ^a,^b and Xinzhi Chen ^a ^*

^aDepartment of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, People's Republic of China, and ^bCollege of Chemical Engineering, Ningbo University of Technology, Ningbo 315016, People's Republic of China
^*Correspondence e-mail: xzchen@zju.edu.cn

(Received 28 December 2011; accepted 12 January 2012; online 18 January 2012)

In the title compound, C₈H₅NOS₂, the non-H atoms are approximately coplanar [maxium deviation = 0.060 (3) Å]. The dihedral angle between the least-squares planes of the pyridine and 1,3-dithiol-2-one rings is 5.96 (17)°. The crystal packing is stabilized by weak intermolecular C—H⋯O hydrogen bonds and by an S⋯S close contact [3.510 (5) Å].

Related literature

For background to the chemistry of pyridine-based tetrathiafulvalenes, see: Fabre (2004 ); Zhu et al. (2010 ). For the preparation and crystal structures of related compounds, see: Zhu et al. (2010); Han et al. (2007 ).

Experimental

Crystal data

C₈H₅NOS₂
M_r = 195.27
Orthorhombic, P n a 2₁
a = 11.157 (2) Å
b = 5.3216 (10) Å
c = 13.689 (3) Å
V = 812.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 223 K
0.60 × 0.25 × 0.20 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.564, T_max = 0.887
2825 measured reflections
1215 independent reflections
1144 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.081
S = 1.10
1215 reflections
110 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 430 Friedel pairs
Flack parameter: −0.09 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O1ⁱ	0.94	2.46	3.3486	158
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812001407/pk2379sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812001407/pk2379Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812001407/pk2379Isup3.cml

checkCIF report

Comment top

Bifunctional molecules featuring a TTF (tetrathiafulvalene) unit with a pyridine, TTF-py, have been explored and a series of new TTF compounds with transition metal centers have been synthesized. The title compound is an intermediate for synthesis of this type of TTF derivative and also a donor-acceptor ligand.

In the title compound (Fig. 1), all bonds lengths and angles are found to be within the range for 4-pyridine-4-yl-1,3-dithiol-2-one (Han et al., 2007). In addition, the non-H atoms are approximately planar [maxium deviation = 0.060 (3) Å] (Fig. 1). There are short S···S contacts [3.510 (5) Å] and weak C—H···O intermolecular hydrogen bonds in the crystal structure (Table 1, Fig.2).

Related literature top

For background to the chemistry of pyridine-based tetrathiafulvalenes, see: Fabre (2004); Zhu et al. (2010). For the preparation and crystal structures of related compounds, see: Zhu et al. (2010); Han et al. (2007).

Experimental top

The title compound was synthesized according to a literature procedure (Han et al., 2007). Slow evaporation of a solution in THF gave single crystals suitable for X-ray analysis.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalStructure (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipoids are drawn at the 30% probability level.
	Fig. 2. A crystal packing diagram viewed down the c axis. Dashed lines indicate the weak C—H···O interactions.

4-(Pyridin-2-yl)-1,3-dithiol-2-one top

Crystal data top

C₈H₅NOS₂	F(000) = 400
M_r = 195.27	D_x = 1.596 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: P 2c -2n	Cell parameters from 2396 reflections
a = 11.157 (2) Å	θ = 3.5–27.5°
b = 5.3216 (10) Å	µ = 0.60 mm⁻¹
c = 13.689 (3) Å	T = 223 K
V = 812.8 (3) Å³	Block, colorless
Z = 4	0.60 × 0.25 × 0.20 mm

Data collection top

Rigaku Saturn CCD diffractometer	1215 independent reflections
Radiation source: fine-focus sealed tube	1144 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 14.63 pixels mm^-1	θ_max = 25.5°, θ_min = 3.9°
ω scans	h = −10→13
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −6→5
T_min = 0.564, T_max = 0.887	l = −15→16
2825 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.081	w = 1/[σ²(F_o²) + (0.0458P)² + 0.0545P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
1215 reflections	Δρ_max = 0.18 e Å⁻³
110 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 430 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.09 (11)

Crystal data top

C₈H₅NOS₂	V = 812.8 (3) Å³
M_r = 195.27	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 11.157 (2) Å	µ = 0.60 mm⁻¹
b = 5.3216 (10) Å	T = 223 K
c = 13.689 (3) Å	0.60 × 0.25 × 0.20 mm

Data collection top

Rigaku Saturn CCD diffractometer	1215 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	1144 reflections with I > 2σ(I)
T_min = 0.564, T_max = 0.887	R_int = 0.027
2825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.081	Δρ_max = 0.18 e Å⁻³
S = 1.10	Δρ_min = −0.23 e Å⁻³
1215 reflections	Absolute structure: Flack (1983), 430 Friedel pairs
110 parameters	Absolute structure parameter: −0.09 (11)
1 restraint

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	0.29937 (7)	1.06740 (15)	0.65200 (6)	0.0415 (2)
S2	0.53107 (7)	1.18329 (17)	0.55954 (7)	0.0439 (2)
O1	0.3307 (3)	1.4374 (5)	0.52711 (19)	0.0562 (7)
N1	0.2818 (2)	0.6783 (5)	0.7860 (2)	0.0407 (7)
C3	0.4232 (3)	0.8896 (6)	0.6876 (2)	0.0329 (7)
C4	0.3981 (3)	0.6970 (6)	0.7623 (2)	0.0328 (7)
C8	0.2525 (4)	0.5068 (7)	0.8529 (3)	0.0482 (9)
H8	0.1713	0.4931	0.8704	0.058*
C7	0.3323 (4)	0.3487 (7)	0.8980 (3)	0.0474 (9)
H7	0.3068	0.2274	0.9434	0.057*
C6	0.4513 (4)	0.3754 (7)	0.8740 (3)	0.0443 (8)
H6	0.5091	0.2738	0.9047	0.053*
C5	0.4867 (3)	0.5504 (6)	0.8052 (3)	0.0380 (8)
H5	0.5678	0.5695	0.7880	0.046*
C2	0.5273 (3)	0.9427 (6)	0.6451 (2)	0.0349 (7)
H2	0.5970	0.8523	0.6609	0.042*
C1	0.3772 (3)	1.2650 (6)	0.5707 (2)	0.0414 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0314 (4)	0.0446 (5)	0.0484 (5)	0.0045 (3)	−0.0023 (4)	0.0054 (5)
S2	0.0388 (5)	0.0469 (5)	0.0459 (4)	−0.0031 (4)	−0.0006 (4)	0.0105 (4)
O1	0.0569 (16)	0.0481 (15)	0.0636 (18)	0.0060 (12)	−0.0125 (14)	0.0169 (13)
N1	0.0335 (15)	0.0428 (17)	0.0456 (16)	−0.0022 (13)	0.0034 (13)	0.0024 (15)
C3	0.0306 (17)	0.0326 (16)	0.0354 (16)	−0.0010 (14)	−0.0022 (13)	−0.0021 (14)
C4	0.0295 (16)	0.0326 (17)	0.0362 (16)	0.0008 (14)	−0.0022 (14)	−0.0008 (14)
C8	0.0369 (18)	0.057 (2)	0.051 (2)	−0.0075 (19)	0.0089 (17)	−0.001 (2)
C7	0.057 (2)	0.0413 (19)	0.044 (2)	−0.0030 (19)	0.0045 (17)	0.0009 (17)
C6	0.051 (2)	0.0404 (18)	0.0418 (18)	0.0073 (17)	−0.0046 (16)	0.0032 (17)
C5	0.0345 (18)	0.041 (2)	0.0383 (18)	−0.0006 (17)	0.0015 (14)	−0.0001 (16)
C2	0.0292 (15)	0.0358 (16)	0.0397 (18)	0.0020 (13)	−0.0029 (17)	0.0013 (15)
C1	0.0367 (17)	0.0442 (18)	0.0433 (18)	−0.0036 (15)	−0.0062 (17)	−0.0061 (18)

Geometric parameters (Å, º) top

S1—C3	1.744 (3)	C4—C5	1.390 (5)
S1—C1	1.760 (4)	C8—C7	1.372 (5)
S2—C2	1.736 (3)	C8—H8	0.9400
S2—C1	1.778 (4)	C7—C6	1.375 (6)
O1—C1	1.211 (4)	C7—H7	0.9400
N1—C8	1.334 (5)	C6—C5	1.382 (5)
N1—C4	1.342 (4)	C6—H6	0.9400
C3—C2	1.329 (5)	C5—H5	0.9400
C3—C4	1.474 (4)	C2—H2	0.9400

C3—S1—C1	96.32 (17)	C6—C7—H7	121.4
C2—S2—C1	95.66 (16)	C7—C6—C5	120.5 (4)
C8—N1—C4	117.0 (3)	C7—C6—H6	119.7
C2—C3—C4	128.1 (3)	C5—C6—H6	119.7
C2—C3—S1	117.0 (2)	C6—C5—C4	117.6 (3)
C4—C3—S1	114.8 (2)	C6—C5—H5	121.2
N1—C4—C5	123.0 (3)	C4—C5—H5	121.2
N1—C4—C3	113.8 (3)	C3—C2—S2	118.3 (2)
C5—C4—C3	123.2 (3)	C3—C2—H2	120.9
N1—C8—C7	124.7 (4)	S2—C2—H2	120.9
N1—C8—H8	117.6	O1—C1—S1	123.6 (3)
C7—C8—H8	117.6	O1—C1—S2	123.8 (3)
C8—C7—C6	117.1 (4)	S1—C1—S2	112.63 (19)
C8—C7—H7	121.4

C1—S1—C3—C2	−2.3 (3)	C7—C6—C5—C4	0.3 (6)
C1—S1—C3—C4	177.7 (2)	N1—C4—C5—C6	1.2 (5)
C8—N1—C4—C5	−1.1 (5)	C3—C4—C5—C6	−179.7 (3)
C8—N1—C4—C3	179.7 (3)	C4—C3—C2—S2	−179.5 (2)
C2—C3—C4—N1	−175.8 (3)	S1—C3—C2—S2	0.5 (4)
S1—C3—C4—N1	4.3 (4)	C1—S2—C2—C3	1.5 (3)
C2—C3—C4—C5	5.1 (5)	C3—S1—C1—O1	−177.0 (3)
S1—C3—C4—C5	−174.9 (3)	C3—S1—C1—S2	3.1 (2)
C4—N1—C8—C7	−0.4 (5)	C2—S2—C1—O1	177.2 (3)
N1—C8—C7—C6	1.9 (6)	C2—S2—C1—S1	−2.9 (2)
C8—C7—C6—C5	−1.7 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.94	2.46	3.3486	158

Symmetry code: (i) −x+1/2, y−3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₅NOS₂
M_r	195.27
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	223
a, b, c (Å)	11.157 (2), 5.3216 (10), 13.689 (3)
V (Å³)	812.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.60 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.564, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	2825, 1215, 1144
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.081, 1.10
No. of reflections	1215
No. of parameters	110
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.23
Absolute structure	Flack (1983), 430 Friedel pairs
Absolute structure parameter	−0.09 (11)

Computer programs: CrystalClear (Rigaku, 2005), CrystalStructure (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1ⁱ	0.94	2.4585	3.3486	157.99

Symmetry code: (i) −x+1/2, y−3/2, z+1/2.

Acknowledgements

This work was supported bythe International Cooperation Fund of Ningbo City 2009D10014.

References

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